Kinds of Chemical bonds

Ionic bond Covalent bond

Complete transfer of one or more Sharing electrons, then the atoms
electrons from each atom of one link through a and discrete
element to those of another. molecules are formed.
Metals-no metals No metals-no metals

The Metallic bond, in which large numbers of cations

are held together by a sea of electrons.
 Theme 7. METALLIC BOND AND CONDUCTIVITY
Contents:

Metallic Bond. Theoretical Models:

- Electron Sea Model
- Bands Theory (Molecular orbital Theory of metals)

Properties of Metals. Conductivity:

- Justification according to the Band Theory Model
- Conductors, Insulators and Semiconductors

Alloys
Metallic Bond. Generalities. Theories of the Metallic Bond.

In metals, atoms are quite tightly bonded (as in ionic and covalent
compounds).
In a conventional covalent bond, electrons that are located between two
positively charged nuclei (bonding, shared electrons) exert electrostatic
attraction, thus holding both atoms together.

Those two atoms are linked to one

another due to the attraction of
both nuclei caused by the electrons
located between them

Shared electrons
Elements that form covalent bonds (non
metals) have plenty of valence electrons, this
being the basis of the structure (many bonds
of this type) of covalent compounds (e.g.
diamond).
Metallic Bond. Generalities. Theories of the Metallic Bond.

Lithium ([Li]: 1s22s1), as all metals, has more orbitals in the valence shell than
electrons in them.

Then, due to having so few valence electrons, only two lithium atoms could be
covalently bonded (which is the case in the gaseous state). But in the solid
state, each lithium atom is surrounded by eight (8) more.

How can such a strong bond be achieved with so few electrons?

 Theories of the Metallic Bond.

Electron Sea Model. Bands Theory

(Molecular Orbital Theory to metals)
 Theories of the Metallic Bond. Electron Sea Model.

The Electron Sea Model describes metallic compounds as a regular

structure (lattice) of positive ions (metal atom nuclei and inner electrons)
in fixed positions, with the valence electrons freely moving throughout the
entire crystal (electron delocalization).

Metal nucleous
and inner electrons
This electron delocalization
(electron cloud) is responsible
of the high thermal and
electric conductivity of metals,
Valence electrons and also for their mechanical
(electron cloud) strength.

Simple and qualitative explanation to electrical and thermal conductivity,

malleability and ductility
Theories of the Metallic Bond. Bands Theory (Molecular Orbital Theory)

For lithium ([Li]: 1s22s1), two Li atoms would give rise to two molecular
orbitals (s2s and s*2s). A third lithium atom would result in three molecular
orbitals, and with four lithium atoms four molecular orbitals would result,
and so forth.

MO diagram
for
solid lithium
Theories of the Metallic Bond. Bands Theory (Molecular Orbital Theory)

The difference in energy between these molecular orbitals decreases

inversely to the number of Li atoms in the crystal. For a very large number
of Li atoms, the difference of energy between molecular orbitals will be
negligible, and the allowed states become a Continuous Band.
Continuous
MO’s Band

MO diagram for solid lithium

Theories of the Metallic Bond. Bands Theory (Molecular Orbital Theory)

As the Valence Band is half full, and the difference in energy between all
the states (molecular orbitals) in the band is so small, electrons can move
very easily from occupied to non occupied molecular orbitals.
These mobile electrons justify the high electric conductivity of the metal.
Conductivity is explained by the facility with which electrons go from filled
MO (bonding) to unfilled (antibonding).

Electrons moving
from occupied fo
unoccupied MO’s

MO’s for solid lithium

Theories of the Metallic Bond. Bands Theory (Molecular Orbital Theory)

For Berilum ([Be]: 1s22s2), a similar reasoning is applied. The combination of n

2s atomic orbitals would give rise to n molecular orbitals, half of them bonding
(s2s) and the other half antibonding (s*2s), all together constituting the Valence
Band.
MO diagram for solid beryllium

There is some overlap

between those two
Bands, so that electrons
can freely move
Theories of the Metallic Bond. Bands Theory (Molecular Orbital Theory)

MO diagram for solid beryllium

There is some overlap

between those two
Bands, so that electrons
can freely move

Conductivity in Berilium (and other metals) is explained by that the empty 2p atomic
orbitals of Be also combine into another Band (Conductivity Band), which partially
overlaps with the Valence Band of 2s orbitals.
Therefore, electrons can jump (move) from Valence Band (2s) to Conductivity Band (2p).
Electrons can move very easily from occupied to non occupied molecular orbitals
(simply by applying an electric potential or a temperature difference) through the whole
lattice.
Properties of Metallic Compounds.

Metals are lustrous in appearance (shiny).

Metals tend to have low ionization energies (tend to form cations relatively
easy). As a result, metals are oxidized (lose electrons) while undergoing
chemical reactions.
Properties of Metallic Compounds.

Solids at room temperature (with the exception of mercury).

The metallic bond is a strong one, so atoms are tightly bonded (by the
shared electrons).

The more shared electrons present, the higher the hardness and melting
points (alkali metals are soft, with comparatively low melting points, if
compared to other groups), but when antibonding MO’s get progressively
occupied then bonds become weaker (lower melting points).

Melting points to some period 4 atoms:

1 2 4 5 6 7 8 10 12
IA IIA IVB VB VIB VIIB VIIIB IIB
Element K Ca Ti V Cr Mn Fe Ni Zn
Mp (°C) 63.4 842 1668 1890 1907 1246 1538 1435 419
Properties of Metallic Compounds.

Example: Account, by using the Band Theory, for the difference of the
melting points of chromium (1907°C) and zinc (419°C).

[Cr]: [Ar]3d54s1
[Zn]: [Ar]3d104s2
Properties of Metallic Compounds.
Example: Account, by using the Band Theory, for the difference of the
melting points of chromium (1907°C) and zinc (419°C).

[Cr]: [Ar]3d54s1
[Zn]: [Ar]3d104s2

A valence band is formed by one 4s and five 3d orbitals per atom (resulting
in six bonding and antibonding molecular orbitals), which can accommodate
twelve electrons (per atom).
The Cr has strong bonds and a high Mp due to the fact that only the bonding
orbitals are occupied.
The lower melting point of zinc is due to that bonding and antibonding
orbitals are occupied, as this band is filled with more electrons.
In the case of Zn, the bands formed by 4p orbitals also overlap, thus
justifying its metallic character (as with beryllium).
Properties of Metallic Compounds.

Good heat and electricity conductors.

The ability of the electrons to easily move throughout the whole structure
(electron cloud) explains their electric conductivity.

Also, moving electrons readily help to transfer kinetic energy through the
whole metal upon response to temperature variations (heat transfer).

Malleable (can be pounded into thin sheets) and ductile (can be drawn into
wires).

Metal atoms are bonded to many other metal atoms, with the valence
electrons shared by all of them. When a metal is reshaped (atoms changing
positions), moving electrons can easily redistribute, reconstituting the
bond.
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

The possibility that the valence electrons freely move throughout the
conductivity band justifies the high electric conductivity of metals.

Conductivity of metals is explained by that there is no energy gap between

the valence and the conductivity bands.

Depending on the magnitude of this Energy (Band) Gap, elements can be

classified as conductors (metals), insulators and semiconductors.
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

Insulators have a large Energy Gap between the Valence Band and the
Conduction Band.

Large Energy gap between

Bands.
Electrons cannot jump to the
higher one

For diamond ([C]: 1s22s22p2), combination of 2s and three 2p atomic

orbitals per C atom gives rise to two bonding and two antibonding
molecular orbitals. As each C atom has four valence electrons, the bonding
MO’s (Valence Band) are completely filled, and the antibonding ones
(Conductivity Band) are empty.
The large gap between both bands (520 kJ/mol) implies that electrons
cannot promote to the conductivity band (no conductivity).
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

The molecular orbitals of semiconductors are quite similar to those of

insulators, but the energy gap between bands is far smaller.
Thus, some electrons in the valence band may have sufficient thermal
energy and jump to (populate) the conduction band.

Small energy gap between

bands.
Few electrons occupy the
antibonding MO’s

This implies that these (few) electrons in the conduction band can move
throughout this very band upon applying an electric potential, resulting in
some electric conductivity.
Semiconductors have some electric conductivity, but far less than ordinary
conductors (e.g. metals).
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

The size of the band gap (Eg) depends on the bond length (Eg increases as
length decreases) and on the difference of electronegativity between the
two elements for composed semiconductors (e.g. In-P, Eg increases with
the electronegativity difference).
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

The electric conductivity of semiconductors can be modulated by the

presence of impurity atoms.
Semiconductors whose conduction bands are populated with more
electrons will have higher electric conductivity.

Adding just few impurity atoms, or

doping, to the semiconductor will
change its electric conductivity by
orders of magnitude.

Depending on the kind of the atom

impurity, two main types of doped
semiconductors will result:
- n-type semiconductors
- p-type semiconductors
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

Adding just few impurity atoms, or doping, changes its electric

conductivity by orders of magnitude:

- n-type semiconductors have, after doping, an excess of electrons on the

conduction band (e.g. few phosphorus or antimmonium atoms in a pure
silicon semiconductor).

The extra electrons from

phosphorus or antimmonium
are forced to occupy the
conduction band (the valence
band is full with electrons from
silicon atoms).
This results in a conductivity
increase.
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

Adding just few impurity atoms, or doping changes the electric

conductivity by orders of magnitude:

- p-type semiconductors are doped with atoms that have less electrons
than the semiconductor element (e.g. boron or aluminium atoms in a
pure silicon semiconductor).

The missing electrons due to

the boron atoms create a hole
(a virtual positive charge, due
to that electron vacancy), that
is occupied by another electron
from silicon, so that this hole
moves throughout the valence
band.

This also results in a

conductivity increase, but
conductivity is in the valence
band in this case.
Metallic Bond. Band Theory Model. Conductors, Semiconductors and
Insulators.

Kind of semiconductors (Summary)

Diodes, transistors, solar cells and other devices are based on the junction
of n- and p-semiconductors.
Metallic Bond. Metallic Compounds. Alloys.

An alloy is a material (homogeneous or heterogeneous mixture) composed

of two or more elements and that has the properties of a metal.

Alloys are made to modify (improve) the properties of a pure metal.

Examples are bronze, brass, steel and 14 carat gold.

There are four types of Alloys: Increase its hardness and strength.
Prevent the corrosion or rusting.
- substitutional alloys
Improve the appearance of the metal
- interstitial alloys surface.
- heterogeneous alloys
- intermetallic compounds
Metallic Bond. Metallic Compounds. Alloys. Substitutional Alloys.

Substitutional and interstitial alloys are solid solutions (Homogeneous

Mixtures)

In substitutional alloys, a different atom is placed at the position of an

original one.

Elements must have similar atomic radii and bonding features (e.g. gold
and silver).
Metallic Bond. Metallic Compounds. Alloys. Interstitional Alloys.

Substitutional and interstitial alloys are solid solutions (homogeneous

mixtures).

In interstitial alloys, a different atom is placed in an interstice in the lattice.

The additional atom must be far smaller. Normally it is a non metal that
covalently binds to several surrounding metallic atoms, rendering the
lattice harder and stronger (e.g. steel).
Metallic Bond. Metallic Compounds. Alloys. Heterogeneous Alloys.

In heterogeneous alloys components are not evenly distributed, and

different phases are formed.

Pearlite is an heterogeneous alloy made of iron (cubic centered) and

cementite (Fe3C).

Their properties depend on the proportion of each phase, and on how these
phases are distributed (how the alloy has been prepared).
Metallic Bond. Metallic Compounds. Alloys. Intermetallic Alloys.

Intermetallic compounds are compounds (with definite composition), rather

than mixtures.

Their atoms are ordered, in fixed positions, instead of being randomly

distributed, in a way that leads to more stable structures (for special
applications, …).
 Theme 6. METALLIC BOND AND CONDUCTIVITYc
Contents:

Metallic Bond. Theoretical Models:

- Electron Sea Model
- Band Theory Model (Molecular orbital Theory to metals)

Properties of the Metals. Conductivity:

- Justification according to the Band Theory Model
- Conductors, Insulators and Semiconductors

Alloys


EJERCICIOS
1. Diga cuales de las siguientes frases son ciertas y cuáles son falsas:
 
____Metales tienen conductividades eléctricas elevadas porque sus
electrones de valencia están deslocalizados.

____Metales tienen conductividades eléctricas elevadas porque son

más densos que otros sólidos.

____Metales tienen conductividades térmicas elevadas porque se

expanden al ser calentados.

____Metales tienen conductividades eléctricas bajas porque sus

electrones deslocalizados no pueden transmitir fácilmente la energía
cinética impartida al metal en el proceso de calentamiento.
1. Diga cuales de las siguientes frases son ciertas y cuáles son falsas:
 
V
____Metales tienen conductividades eléctricas elevadas porque sus
electrones de valencia están deslocalizados.

F
____Metales tienen conductividades eléctricas elevadas porque son
más densos que otros sólidos.

F
____Metales tienen conductividades térmicas elevadas porque se
expanden al ser calentados.

F
____Metales tienen conductividades eléctricas bajas porque sus
electrones deslocalizados no pueden transmitir fácilmente la energía
cinética impartida al metal en el proceso de calentamiento.
2. ¿En qué tipo de material la separación de energía entre la banda de
valencia y la de conducción es mayor: metal, semiconductor o aislante?
Justificarlo brevemente.

3. ¿Cuántos niveles de energía están presentes en la banda de

conducción 3s de un monocristal de sodio que pesa 26.6 mg? ¿Cuántos
electrones están presentes en esta banda?

4. El magnesio es un excelente conductor eléctrico, aunque en su

estado fundamental tiene la subcapa 3s totalmente llena ([Mg]:[Ne]3s 2).
Emplear la Teoría de Bandas para justificar la conductividad del
magnesio.

5. Diga si el silicio formará semiconductores de tipo n o de tipo p con

los siguientes elementos: Ga, Sb, Al, As. Justificarlo brevemente.
2. ¿En qué tipo de material la separación de energía entre la banda de
valencia y la de conducción es mayor: metal, semiconductor o aislante?
Justificarlo brevemente.
La conductividad depende del nivel de ocupación y del
espaciamiento entre las bandas de valencia y conductividad.
Los aislantes tienen la banda de conductividad vacía y muy
separada de la de valencia, como se indica en la siguiente
figura.
 3. ¿Cuántos niveles de energía están presentes en la banda de conducción 3s
de un monocristal de sodio que pesa 26.6 mg? ¿Cuántos electrones están
presentes en esta banda?

Es un caso similar al litio: la banda de valencia y la banda de conducción están en la

misma banda 3s. La mitad está llena y la otra mitad vacía.

0.0266 g Na x (6.02 x 1023 átomos/22.9898 g) = 1.922 x 1019 átomos Na

 
Eso implica que la banda 3s tiene 1.922 x 1019 niveles, de los que la mitad constituirán
la banda de conducción, en la que no hay electrones (los 1.922 x 1019 electrones
están en la banda de valencia, que es la mitad inferior de la banda 3s).
4. El magnesio es un excelente conductor eléctrico, aunque en su
estado fundamental tiene la subcapa 3s totalmente llena ([Mg]:[Ne]3s 2).
Emplear la Teoría de Bandas para justificar la conductividad del
magnesio.

La banda 3s (llena) se solapa con la banda 3p (vacía).

5. Diga si el silicio formará semiconductores de tipo n o de tipo p con

los siguientes elementos: Ga, Sb, Al, As. Justificarlo brevemente.

Con Ga y Al formará semiconductores de tipo p (positivo), ya que Ga y

Al solo tienen tres electrones de valencia y originarán un hueco en el
superconductor. Con Sb y As, con cinco electrones de valencia, hay un
exceso de electrones, que pasarán a la capa de conductividad con la
aplicación de un pequeño voltaje.
6. La estructura electrónica de un semiconductor dopado es la
indicada en la figura.

¿Cuál de las bandas, A o B, es la banda

de valencia?
¿Y la de conductividad?
¿Qué banda está constituida por orbitales
moleculares enlazantes?
¿Se trata de un semiconductor de tipo n o
de tipo p?
Si el semiconductor es germanio, ¿cuál
de los siguientes elementos podría ser el
dopante: Ga, Si o P?
6. La estructura electrónica de un semiconductor dopado es la
indicada en la figura.

¿Cuál de las bandas, A o B, es la banda

de valencia?
¿Y la de conducción?
¿Qué banda está constituida por orbitales
moleculares enlazantes?
¿Se trata de un semiconductor de tipo n o
de tipo p?
Si el semiconductor es germanio, ¿cuál
de los siguientes elementos podría ser el
dopante: Ga, Si o P?

A es la banda de valencia, y B la de conducción. Ambas bandas están

constituidas por orbitales moleculares enlazantes y antienlazantes,
respectivamente. En un semiconductor de tipo p. El dopante en este
caso sólo puede ser Ga.