DEPARTMENT OF CHEMISTRY

FACULTY OF SCIENCES

CHEMISTRY 221: Inorganic Chemistry (I)

Chapter 4
The Structures of Simple Solids

Dr. Adnan S. Abu-Surrah

Professor of Inorganic Chemistry

(Office: 204, Tel. 4315), E-mail: asurrah@hu.edu.jo

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 The Structures of Simple Solids
• Metals have:
– High thermal and electrical conductivity
– Are malleable
– Are Ductile
• The reason for this is they are like small
spheres packed together and bonded equally
with other metal atoms in all directions.

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 Crystal Lattices
• Unit cells: smallest repeating unit (imaginary parallel-sided
region) that through translation can recreate a lattice. (also
called the asymmetric unit)
• Lattice: a two or three dimensional array of objects with a well
defined order.
• The ‘crystal lattice’ is the pattern formed by the points and used
to represent the positions of these repeating structural
elements.

Amorphous means a disordered array 3

 Unit cells
A two-dimensional solid and two choices of a unit cell. The
entire crystal is reproduced by translational displacements
of either unit cell,

a b
Two possible choices of repeating unit are shown but (b) would
be preferred to (a) because it is smaller.
 Lattice and Units Cells
The relationship between the lattice parameters in three
dimensions as a result of the symmetry of the structure
gives rise to the seven crystal systems
Most common types: cubic
orthorhombic
monoclinic
triclinic
Less common types: hexagonal
tetragonal
trigonal
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 The angles (a, b , g) and lengths (a,
b, c) used to define the size and
shape of a unit cell are the unit cell
parameters (the ‘lattice
parameters’);

Angle between b and c is a

Angle between a and c is b
Angle between a and b is g
(or rhombohedral)
 Rules to determine number of lattice points in a
three-dimensional unit cell
1) A lattice point in the body of, that is fully
inside, a cell belongs entirely to that cell and
counts as 1.
2) A lattice point on a face is shared by two cells
and contributes 1/2 to the cell.
3) A lattice point on an edge is shared by four
cells and contributes 1/4.
4) A lattice point at a corner is shared by eight
cells that share the corner, and so contributes
1/8.
The same process can be used to count the
number of atoms, ions, or molecules that the
unit cell contains.

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Simple Cubic denoted by the symbol P

The number of lattice

points is:
(8 x1/8 ) = 1.

Lattice points describing the translational symmetry

of a primitive cubic unit cell.
Body Centered Cubic (BCC) denoted by the symbol I

The number of lattice

points is:
(1x1) + (8 x1/8 ) = 2.

Lattice points describing the translational

symmetry of a cubic unit cell.
Face Centered Cubic (FCC)
denoted by the symbol F

The number of lattice

points is:
(6x1/2) + (8 x 1/8) = 4

Lattice points describing the translational symmetry of a

face-centred cubic unit cell.
cubic: a=b=c
a = b = g = 90°

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 The close packing of spheres
The close packing of identical spheres can result in a variety of
polytypes, of which hexagonal and cubic close-packed
structures are the most common”
1. hexagonal close-packed (hcp)

2. cubic close packed (ccp).

Some aspects to remember for ionic bonding:

• Electronegative atoms will generally gain enough electrons to fill their
valence shell and more electropositive atoms will lose enough electrons
to empty their valence shell.
• Example:
• Na: [Ne]3s1  Na+: [Ne] Ca: [Ar]4s2  Ca+2: [Ar]
• Cl: [Ne]3s2 3p5  Cl-: [Ar] O: [He]2s2 2p4  O-2: [Ne] 12
 Ionic Compounds

The cations and anions are held together by electrostatic

attraction.
• Coordination numbers are generally low, giving low densities.
• Their structures are generally close-packed arrays of spherical
cations and anions.
• The array usually consists of anions packed in a hcp or ccp lattice
with the cations occupying the octahedral and/or tetrahedral
holes.
• In both cases (hcp and ccp), the spheres occupy 75% of the
available space.
• Because anions are usually bigger than cations, it is generally the
anions that dominate the packing arrangement.
• The ionic bonds are strong, multidirectional and electrostatic.
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• Usually, the smaller cations will be found in the holes in the
anionic lattice, which are named after the local symmetry of
the hole
•i.e. six equivalent anions around the hole makes it
octahedral, four equivalent anions makes the hole
tetrahedral).

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 Crystal Lattices
Two main types of arrays:

• Open: occupies 68% of the space

• Close-packed: occupies 75% of the space

– Two types of close-packed arrays: hexagonal and cubic. (ABAB...

versus ABCABC... ) next slide

– Close-packed structures have layers of octahedral
and tetrahedral holes --

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 Cubic Close-Packed (ccp)
• ABCABC
• first layer in a hexagonal arrangement of atoms or ions
• second layer over depressions in the first layer, over tetrahedral
holes
• third layer over depressions in the second which are not over the
depressions in the first that the atoms in the second occupy, over
octahedral holes
• fourth layer is identical to the first
• fifth layer is identical to the second
• sixth layer is identical to the third
• face-centered-cubic, standing on its body diagonal, is camouflaged
by ccp
• C. N. = 12

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 Hexagonal Close-Packed (hcp)
- ABABAB
- first layer in a hexagonal arrangement of atoms or ions
- second layer over depressions in the first layer, over tetrahedral
holes
- odd numbered layers identical to the first
- even numbered layers identical to the second
- 12 nearest neighbors,

C. N. = 12

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Examples in nature of Hexagonal Close Packing
 Coordination Numbers:
Coordination Number: the number of nearest neighbors.

Hexagonal close-packing of sphere gives a

coordination number (CN) of 12 and leaves
interstitial sites capable of coordination numbers
6 or 4.
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 Structures of Metals……….omitted
• In addition to ccp and hcp, metals also have simple cubic and
body-centered cubic structures.
• The CN of ccp or hcp = 12, simple or primitive cubic = 6, body-
centered cubic (bcc) = 8.
• Note that bcc is favored for Group 1 and 2 metals. This is due to
the weaker “electron sea” which prevents close-packing.

a regular array of organized cations 20

surrounded by delocalized sea of electrons.
Structures of Metals
Polytypism
Polytypes involving complex stacking arrangements of
close-packed layers occur for some metals.

a close-packed structure need not be either of the

common ABAB...or ABCABC...polytypes.
cobalt is an example of a metal that displays more
complex polytypism above 500C. The structure that
results is a nearly randomly stacked set (
ABACBABABC….

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Nonclose-packed structures

A common nonclose-packed metal structure is body-

centred cubic; a primitive cubic structure is occasionally
encountered. Metals that have structures more complex
than those described so far can sometimes be regarded as
slightly distorted versions of simple structures.
One commonly adopted arrangement has
the translational symmetry of the body-
centred cubic lattice and is known as the
body-centred cubic structure (cubic-I or
bcc) in which a sphere is at the centre of a
cube with spheres at each corner (See
Fig).

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Polymorphism of metals

Polymorphism is a common consequence of the low

directionality of metallic bonding. At high temperatures
a bcc structure is common for metals that are close-
packed at low temperatures on account of the
increased amplitude of atomic vibrations.
Iron, for example, shows several solid–solid phase
transitions; a-Fe, which is bcc, occurs up to 906°C, g-Fe,
which is ccp, occurs up to 1401°C, and then a-Fe occurs
again up to the melting point at 1530°C. The hcp
polymorph, b-Fe, is formed at high pressures and was to
believed to be the form that exists at the Earth’s core.

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Atomic radii of metals

The Goldschmidt correction converts atomic radii of metals to the value

they would have in a close-packed structure with 12-fold coordination.

A brief illustration. The empirical atomic radius of Na is 185 pm, but

that is for the bcc structure in which the coordination number is 8. To
adjust to 12-coordination we multiply this radius by 1/0.97 = 1.03 and
obtain 191 pm as the radius that a Na atom would have if it were in a
close-packed structure.

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 Alloys
• Substitutional solid solution
• Interstitial solid solution

substitutional Interstitial Another lattice

Examples:
Brass – up to 40% Zn in Cu
Bronze – a metal other than Zn or Ni in Cu
Stainless steel – over 12% Cr in Fe
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 Substitutional Solid Solutions -- conditions

• The atomic radii of the elements are within

15% of each other
• The crystal structures of the two pure metals
are the same
• The electropositive characteristics of the two
metals are similar
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Interstitial Solid Solutions

• True compounds – simple whole number

ratios of atoms

• Solid solutions – small atoms distributed

randomly in the available holes in the lattice

Compounds with Particular Crystal Structures

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30
 The Structure of NaCl
 It is a fcc array of chloride ions as the packing layers.

 The sodium ions are in all the octahedral holes.

 The coordination number of both ions is 6.

 The unit cell has four net sodium ions and four chloride
ions.

 Other salts with this structure are: LiX, NaX, KX, RbX
where X = F, Cl, Br, I; also MgO, MgS, CaO, etc.

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 Rock Salt (NaCl) Structure

Rock Salt structure (6,6) coordination

Face-centered cubic (fcc)
e.g. NaCl, LiCl, MgO, AgCl
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CsCl Unit Cell--Contd--

(8,8)-coordination
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Extrinsic defects are defects introduced into
a solid as a result of doping with an impurity
atom. Example is the introduction of As into
Si to modify the latter’s semi-conducting
properties. 34
 lattice energy (Uo,
Ionic Bonding: lattice energy, Uo,
•The energy that holds the arrangement of ions together is called the
lattice energy, Uo, and this may be determined experimentally or
calculated.
•A lattice energy must always be exothermic.
•E.g.: Na+(g) + Cl-(g)  NaCl(s) Uo = -788 kJ/mol

Lattice energies are determined experimentally using a

Born-Haber cycle such as this one for NaCl. This approach
is based on Hess’s law and can be used to determine the
unknown lattice energy from known thermodynamic values.

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 Lattice Energy, Uo
DHfo = DHoie + DHosub + DHod + DHoea - Uo
where DHosub => heat of sublimation
- endothermic process
- always positive number
DHod=> bond dissociation energy
- endothermic process
- always positive number

where DHfo => standard state enthalpy of formation

- can be either endothermic or exothermic
- therefore, value may be positive or negative
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 Ionic Bonding -- Born-Haber cycle
DH°sub DH°ie
Na(s)  Na(g)  Na+(g)

½ Cl2(g)  Cl(g)  Cl-(g)

Lattice Energy, Uo
DH°d DH°ea

NaCl(s)
DH°f

DH°f = DH°sub + DH°ie + 1/2 DH°d + DH°ea - Uo

-411 = 109 + 496 + 1/2 (242) + (-349) - Uo

Uo = -788 kJ/mol
You must use the correct stoichiometry and signs to obtain the correct lattice energy.

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Practice Born-Haber cycle analyses at: http://chemistry2.csudh.edu/lecture_help/bornhaber.html
 Ionic Bonding
If we can predict the lattice energy, a Born-Haber cycle analysis can tell us
why certain compounds do not form. E.g. NaCl2
(DH°ie1 + DH°ie2)
Na(s)  Na(g)  Na+2(g)
DH°sub

Cl2(g)  2 Cl(g)  2Cl-(g)

Lattice Energy, Uo
DH°d DH°ea

NaCl2(s)
DH°f
DH°f = DH°sub + DH°ie1 + DH°ie2 + DH°d + DH°ea - Uo

DH°f = 109 + 496 + 4562 + 242 + 2*(-349) + -2180

DH°f = +2531 kJ/mol

This shows us that the formation of NaCl2 would be highly endothermic and very
unfavourable. Being able to predict lattice energies can help us to solve many
problems so we must learn some simple ways to do this. 38
K(g) + ½ Cl2(g)  KCl(s)

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