BONDING MODELS FOR METALS

1. ELECTRON SEA MODEL

2. MOLECULAR ORBITAL THEORY (BAND THEORY)
 references
• Brady & Senese, Chemistry (2004)
 METALLIC BONDING : ELECTRON SEA MODEL
The electrostatic attraction between the positive ions
and electron sea is called a metallic bond.
 all the metal atoms in a
metallic solid contribute • The electrons present in the
their valence electrons to outer energy levels of the
form a "sea" of electron. bonding metallic atoms are
not held by any specific and
can move easily from and
one atom to the next.
 Physical Properties of Metals

• Malleable and ductile

• Good conductors of electricity (electrical conductivity)

• Good conductors of heat (thermal conductivity)

• Higher melting point and boiling point

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 Malleable and ductile:

 Most of metals are malleable because they can be hammered into

different shapes (thin sheets).
 Metals are also ductile because they can be pulled out into wires.
 Malleability and ductility of metal can explained by the electron-sea
model:
 When a piece of metal is deformed by hammer, a layer metal ions
can slide over another without breaking the metallic bonding.

 This is because in metallic bonding, the valence electrons do not

belong to any particular metal atom.

metal is deformed

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Electrical conductivity and heat conductivity:

 Metals are good conductors of electricity because they have mobile

electrons.

 When a piece of metal is attached to a battery, electrons flow from

negative terminal into the metal and replace electrons flowing from
metal into the positive terminal.
 Copper wire used to carry an electric current.

 The heat conductivity of a metal is also accounted for by the mobility of

the electrons, which permits ready transfer of kinetic energy
throughout the solid.
 We feel a piece metal is colder than a piece of wood, even though they are
placed in same temperature.
 This is because delocalized electrons in the metal transfer the heat from our
hand quickly than the localized electron pairs in the covalent bonds of
wood.

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Melting point and boiling point:

 The values of melting point and boiling point are increasing when the
strength of the metallic bond increased.

 The strength of metallic bond depends mainly on the number of valence

electrons and the size of the metal cation.

number of valence electrons per atom

Strength of metallic bond α
size of metal cation

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 Moving along a period from left to right of the periodic table, there is an
increase in the strength of the metallic bond (melting and boiling point
increases).

Example:
Na atom and Mg atom lose 1 and 2
valence electrons, to form Na+ and
Mg2+ ions respectively. The more
electrons “swim” in the electron sea,
the stronger is the attractive force
between metal cation and valence
electrons, therefore the stronger is
the metallic bond produced.
Melting points of the Group 1A(1) and Group 2A(2) elements.
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 Melting and Boiling Points of Some Metals
Element mp(0C) bp(0C)

Lithium (Li) 180 1347

M
o
Tin (Sn) d 232 2623
e
r H
Aluminum (Al) a 660 i
2467
t g
e h
Barium (Ba) 727 e
1850
t r
o
Silver (Ag) 961 2155
hi
g
Copper (Cu) h
1083 2570

Uranium (U) 1130 3930

 Melting points are only moderately high because the attractions
between moveable cations and electrons need not be broken during
melting.

 Boiling a metal requires each cation and its electrons to break away
from the others, so the boiling points are quite high.

 The electron-sea model, however, does not adequately explain all

properties of metals.
 For example, the strength of bonding between metal atoms should
increase as the number of valence electrons increases, resulting
increase in melting points [ELECTRON SEA MODEL]
 However, for the transition metals, the strength of metallic bonding
first increases with increasing number of electrons and then
decreases.

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 For the transition metals, the strength of metallic bonding
first increases with increasing number of electrons and then
decreases.

Similar trends are seen in other physical properties of

the metals, such as the heat of fusion, hardness, and
boiling point.
• need a more refined model than the electron-
sea model to describe metallic bonding.
• a better model by applying the concepts of
molecular orbital theory to metals.
• FOR SOLIDS:
MOLECULAR ORBITAL THEORY KNOWN AS A
BAND THEORY
 If more atomic orbitals overlapped form more
molecular orbitals, the energies in MO (bonding and
Band Theory antibonding) so closely spaced that they form a
continuum or band of MO.

 Bandtheory is a another model of metallic bonding which an extension of

molecular orbital theory.
 In MO theory, recall that when two atoms form a diatomic molecule, their
atomic orbitals combine to form an equal number of molecular orbitals.

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Band model proposes that
 lower energy MO are occupied by the valence electrons and make up the
valence band.
 higher energy MO are empty orbitals that make up the conduction band.

 The key to understanding metallic properties is that in metal,

the valence and conduction bands are contiguous, which means that
electrons can jump from the filled valence band to the unfilled conduction band
if they receive an energy.

 In other words, the electrons are completely delocalized; they are free to
move throughout the piece of metal.

 Thus, metals conduct electricity so well because an applied electric field easily
excites the highest electrons into empty orbitals, and they more through the
sample.

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 Metallic luster (shininess) is another effect of the continuous band of
MO energy level. With so many closely spaced levels available, electrons
can absorb and release photons of many frequencies as they move
between the valence band and conduction band.

 Malleability and ductility also result from the completely delocalized

electrons. Under an externally applied force, layers of positive metal
ions simply move past each other, always protected from mutual
repulsions by the presence of the delocalized electrons.

 For thermal conductivity, when a metal wire is heated, the highest

electrons are excited and their extra energy is transferred as kinetic
energy along the wire’s length.

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 categories of solids
• based on their conducting properties:
– conductors
– semiconductors
– Insulators
Three categories of materials may be easily
understood by differences in terms of the size of
the energy gaps between the valence and
conduction bands.

Energy gap =forbidden gap =Band gaps : can be

measured by absorption spectroscopy. The lowest
energy light to be absorbed corresponds to the
band gap.
  Three categories of materials may be easily understood by differences
in terms of the size of the energy gaps between the valence and
conduction bands.

conductor semiconductor insulator

•Electrons flow when even a
tiny electrical potential
difference is applied.
• When temperature is raised,
greater random motion of the
atoms hinders electron
movement, which decreases
the conductivity of a metal
• Thermally excited • The gap between the
electrons can across the bands is too large for
gap, allowing small electrons to jump even
current to flow. when the substance is
• The conductivity of a heated, so no current
semiconductor increases is observed.
when it is heated.
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• Na: 3s1 : Valence band and Conduction band
are the same
• Mg: 3s2 (fully filed): 3s valence band can not
transport electrons. BUT the vacant 3p
conduction band overlaps the valence band
and can be populated by electrons when
voltage is applied : this permits Mg to be a
conductor. The electrons are delocalised
Why for the transition metals, the strength of metallic bonding
first increases with increasing number of electrons and then
decreases?

Transition metals

Row 4 of elements

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 The energy states that lead to the band for transition metals can likewise be
divided into two types:
 lower energy states that result from metal-metal bonding interaction.
 higher energy states that result from metal-metal antibonding interactions.

 The metal chromium possess the correct number of electrons to fill the valence
band and leave the conduction band empty.

 Transition metals with a smaller number of electrons than Cr have fewer metal-
metal bonding orbitals occupied.

 Transition metals with a greater number of electrons than Cr have more metal-
metal antibonding orbitals occupied.

 In each case the metal-metal bonding should be weaker than that in Cr,
consistent with the trends in melting points.

OTHER Factors that play a role in determining the properties of metals:

the number of electrons, atomic radius, nuclear charge,
packing structure of the metal

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REVIEW QUESTION

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Valence band: Band occupied by the outermost electrons
Conduction: Lowest band with unoccupied states

Conductor: Valence band partially filled (half full) Cu.

or Conduction band overlaps the valence band
Splitting of Atomic Levels in Sodium
Occupation of Bands Sodium