CHM361

INORGANIC CHEMISTRY
BY CHM ADIBATUL HUSNA BINTI FADZIL
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012-5815605
Blok Pensyarah C, Aras 1
CHM361
INORGANIC CHEMISTRY
CHAPTER 3
CRYSTALLINE SOLID
 CONTENTS
Crystal Structures

• Metallic Crystal Structure (Simple Cubic, Body-

centered Cubic, Face- centered Cubic and
Hexagonal Close-packed)
• Ionic Lattice (NaCl and CsCl)
• Giant Molecule Crystal Structures (Graphite and
Diamond)

Crystal Defects: Point Defect

• Stoichiometric Defect: Schottky, Frenkel, Vacancy

and Interstitial Defect
• Non-stoichiometric Defect: Metal Excess and
Metal Deficiency
LEARNING OUTCOMES

Describe the crystal structures.

Explain the type of defect in crystal structure.

SOLID
Atoms, molecules or ions that are arranged closely together & regularly in
a complete order.
Solid molecules can only vibrate & rotate about fixed position rather
than move about.
Rigid arrangement.

The attractive forces between the atoms, ions, or molecules in solids are
very strong.
Cannot move freely without disrupting the whole structure.

The shape is independent of its container.

 SOLID
CRYSTALLINE AMORPHOUS
Regular and repeating arrangement of Irregular arrangement of atoms, ions or
components molecules
Ordered structure Disordered structure

Have a sharp melting point Melt over a range of a temperature

Definite heat fusion No definite heat fusion
Anisotropic Isotropic
Physical properties are different in Physical properties are same in all
different direction directions
Covalent bond, Ionic bond, VDW and Covalently bonded network
Metallic bond

salt, sugar, diamond plastic, glass, gels

 TYPE OF CRYSTALLINE SOLID

METALLIC IONIC

CRYSTALLINE

COVALENT NETWORK/
MOLECULAR
GIANT
 Crystal vs amorphous solid

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 TERM
UNIT CELL LATTICE POINTS COORDINATION NUMBER

The number of atoms

Smallest part of a Points or corner where or ions surrounding an
crystal which if atoms, ions or atom or ions in a
repeated in 3D space crystal lattice.
molecules are placed
would produce the
entire cell.
The value is a
measurement of how
tightly the spheres are
Basic building block of packed together.
the crystal.
The larger the value,
the closers the spheres
are to each other.
 CRYSTAL STRUCTURE
SIMPLE CUBIC BODY CENTERED FACE CENTERERED
CUBIC (BCC) CUBIC (FCC)

Also known as the Consist of 8 lattice Consist of 8 lattice

primitive cubic unit cell. point at the corners point at the corners
of the cube & of the cube &
Consist of 8 lattice which
are placed at each corner
of the cube 1 lattice point at the 1 lattice point at the
centre of the unit cell centre of each face
Coordination number
of 6

 Eg: Oxygen molecule  Eg: Na, Fe  Eg: Cu, Au

COUNTING THE NUMBER OF PARTICLES IN A UNIT CELL
Particles at the corner Particles at the face

✓ Shared by 8 unit ✓ Shared by 2 unit

cell. cell.

✓Contributes only ✓ Contributes only

1/8 towards its ½ towards its own
own unit cell. unit cell.

Particles at the edge Particles at the centre

✓Shared by 4 unit
✓ Belongs only to
cell.
one cell.
✓ Contributes only
¼ towards its
own unit cell.
COUNTING THE NUMBER OF
PARTICLES IN A UNIT CELL

▪ Particles in a unit cell can be seen at the lattice point but may
not contribute the whole entities to the unit.
▪ Particles located on edges, faces & corner are shared by
neighboring unit cell.

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 COUNTING THE NUMBER OF
PARTICLES IN A UNIT CELL
Particles at the corner Particles at the edge Particles at the face Particles at the centre

• Shared by 4 • Shared by 2
• Shared by 8 unit cell. unit cell. Belongs only to
unit cell. one cell.
• Contributes • Contributes
• Contributes only ¼ only ½
only 1/8 towards its towards its
towards its own unit cell. own unit cell.
own unit
cell.
 METALLIC SOLID
Simplest crystal structure.
Copper

Made up of metal atoms that are held together by metallic bonds.

Every lattice point in a crystal is occupied by an atom of the same metal.

The structure of metallic crystals is often described as a uniform distribution of

atomic nuclei within a “sea” of delocalized electrons.

Bonding-bonding electron are delocalized over the entire crystal. (moving around)

The mobility makes the metal good conductor of heat and electricity.
PROPERTIES OF METALLIC SOLID

High melting & boiling points

• Metallic bonds are strong and a lot of energy is needed to break them.

Conducting electricity

• Since the valence electron are free to move.

Metallic luster

• Delocalized valence electron can absorb & reemit electromagnetic radiation.

Malleable & ductile

• The layers of cations can easily slide past each other without breaking the
lattice structure.
METALLIC CRYSTAL STRUCTURE

STRUCTURE

Body Centered Face Centered Hexagonal

Cubic Cubic Closed Packed
(BCC) (FCC) (HCP)

Cu, Al, Ag, Cd, Mg, Zn,

Cr, Fe
Au Ti
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METALLIC CRYSTAL STRUCTURE

Body Centered Cubic Face Centered Cubic Hexagonal Closed

(BCC) (FCC) Packed (HCP)
No of particle in a unit cell : No of particle in a unit cell : No of particle in a unit cell :

Coordination No :
Coordination No : Coordination No :
 METALLIC CRYSTAL STRUCTURE
Body Centered Cubic(BCC)

Coordination number of 8.

The bcc unit cell consists of a net total of 2 atoms.

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8 at the corner : 8 = 1
8
1 at the centre : 1 1 = 1

Total of atom : 2 atoms

The bcc arrangement does not allow the atoms to pack together as
closely as the fcc or hcp arrangements.
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 METALLIC CRYSTAL STRUCTURE
Face Centered Cubic (FCC)

The fcc unit cell consists of a net total of four atoms;

Coordination number of 12. eight from corners atoms and six of the face atoms.

the atoms can pack closer together than they can in The atoms from one layer nest themselves in the
the bcc structure. empty space between the atoms of the adjacent layer.
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 METALLIC CRYSTAL STRUCTURE
Hexagonal Closed Packed (HCP)

there are 6 atoms in the HCP unit cell.

12 atoms in the corners of the top and bottom layers, the two atoms in
the center of the hexagon of both the top and bottom layers

and each of the three atom in the middle layer.

1
12 at the corner (top & bottom) : 12  = 2
6
1
2 at the center (top & bottom) : 2 = 1
2
3 at the middle : 3 1 = 3

Total of atom : 6 atoms

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 HCP
Six nearest neighbors in the same close packed layer, three in the
layer above and three in the layer below

The atoms from nest themselves in the empty between the atoms of just like in the fcc
one layer space the adjacent layer structure.

Has three In each the there are six atoms in the middle
in the shape and a seventh
layers of top and that arrange
of a hexagon atom that sits
of the
bottom layer, themselves hexagon.
atoms.
 IONIC SOLID
✓ Composed of positive and negative ions that are held together by
electrostatic attractions.
✓ The binding between the ions is rather strong
✓ There are no free electrons, ionic crystals are insulators.

• Strong electrostatic forces between ions of opposite

High melting charge.
point
• Requires more energy to overcome the attraction.
• Strong electrostatic force make it hard but, if a strong
force is applied, the ion layers shifts slightly.
Hard but brittle
• Ions of the same charge are brought side-by-side and so
the crystal repels itself.
Does not conduct • Ions are not free to move because are held strongly by
electricity in electrostatic force in fixed position.
solid but does so
in molten or • When the solid melt, ions are free to move thus
aqueous solution conducting electricity.
 IONIC SOLID (NaCl)

The unit cell can be drawn with either the Na+ ions
at the corners, or with the Cl- ions at the corners.

Na+ & Cl- are arranged alternately.

Face-centered Cubic (FCC)

• 6:6-co-ordinated.
• Only those ions joined by lines are actually touching each other.
The Cl- ion in the centre is being touched by 6 chloride ions.

Na+ Cl-
 IONIC SOLID (NaCl)
No of particle in a unit cell :

**4 sodium ions & 4 chlorides ion contained within the unit cell.
 IONIC SOLID (NaCl)
No of particle in a unit cell :
8 Na + ions at the corner = 1 Na + ions
1
: 8
8

6 Na + ions at the face = 3 Na + ions

1
: 6
2

Total of Na + ions : 4 Na + ions

12 Cl − ions at the edge = 3 Cl − ions

1
: 12 
4

1 Cl − ions at the centre : 1 1 = 1 Cl − ions

Total of Cl − ions : 4 Cl − ions

**4 sodium ions & 4 chlorides ion contained within the unit cell.
 IONIC SOLID (CsCl)
❖ Simple Cubic.

❖ 8:8-co-ordinated.

❖ Each caesium ion is touched by eight

chloride ions.

No of particle in a unit cell :

Cs+

Cl-

1 caesium ions & 1 chlorides ion contained within the unit cell.
 IONIC SOLID (CsCl)
❖ Simple Cubic.

❖ 8:8-co-ordinated.

❖ Each caesium ion is touched by eight

chloride ions.
No of particle in a unit cell :

1 Cs + ions at the centre : 1 1 = 1 Cs + ions

Total of Cs + ions : 1 Cs + ions

8 Cl − ions at the corner = 1 Cl − ions

1
: 8
8

Cs+
Total of Cl − ions : 1 Cl − ions

Cl-

1 caesium ions & 1 chlorides ion contained within the unit cell.
COVALENT NETWORK SOLID / GIANT
The atoms in these solids are held together by a
network of covalent bonds.
Non-metals.

Allotropes of carbon.

Pure forms of the same element that differ in structure

Diamond Graphite
 DIAMOND
Composed of single element (C) arranged in 3D network.

Each C atom covalently bonded to 4 other C in tetrahedral arrangement by strong

covalent bonding.

Used in cutting tools & grinding.

So no free moving electron to conduct electricity.

• Diamond does not conduct electricity.

Very strong covalent bond.

• So have high melting point 3550°C.
• Very hard.
 GRAPHITE

Each C is connected with 3 other C by covalent bond forming 6-member rings that form flat layer
which are held loosely by weak VDW forces.

C use only 3 of its 4 valence electron, so it has one unused electron .

• The electron are able to move freely thus conduct electricity.

• Graphite is an electric conductor.

Used as lead in pencil & lubricant.

Has a high melting point, similar to that of diamond.

• - In order to melt graphite, it isn't enough to loosen one sheet from another.
• - must break the covalent bonding throughout the whole structure.

6-member rings form flat layer which are held loosely by weak VDW forces.

• - The layers can slide past each other, resulting in softness of graphite.
 CRYSTAL DEFECT
CRSYTAL DEFECT
- Irregularity in the arrangement
of constituent particles in solids.
- Ideal crystal does not exist.
- all contain large no. of defects
or -imperfections .

STOICHIOMETRIC DEFECT NON-STOICHIOMETRIC DEFECT

Irregularities or deviation from Presence of constituent particles In
ideal arrangement of constituent non-stoichiometric ratio in the
particles around the point or crystal structure
atom in a crystalline solid

INTERSTITIAL METAL METAL

VACANCY SCHOTTKY FRENKEL
EXCESS DEFICIENCY
 VACANCY DEFECT

An atom is missing from its regular atomic site.

When some lattice sites left vacant while the formation of crystal.

Because of missing the atom, the density of substance decreases.

The vacancy defect develops on heating of substance.

When the temperature is sufficiently high, the atoms vibrate around their regular positions, some acquire
enough energy to leave the site completely.
 SCHOTTKY DEFECT

A pair of one cation and one anion missing from regular sites in ionic crystal.

Because of missing ions, the density of substance decreases

Almost similar in size, such as NaCl, KCl, CsCl

the number of missing cations is equal to the number of missing anions in order to maintain the electrical
neutrality of the ionic compound.
 INTERSTITIAL DEFECT

When an atom occupies a definite position in the lattice that is not normally
occupied in the perfect crystal.
some atoms occupy sites at which; generally there is no atom in the crystal
structure.
Because of the interstitial defects, the number of atoms becomes larger than the
number of lattice sites.
Increase in number of atoms increases the density of substance
 FRENKEL DEFECT

An ion displaced from a regular site to an interstitial site in ionic crystal.

As cations are generally the smaller ones, it is possible for them to get displaced into the void
space.

Anions do not get displaced as the void space is too small compared to the size of the anions.

As there are a number of cations and anions (which remain equal even because of defect); the
density of the substance & the overall electrical neutrality of the crystal does not change.

such as ZnS, AgCl, AgBr, AgI

Schottky defects Frenkel defects
Occurs if the difference in size Occurs if size of anion is quite
between cation and anion is small. large as compared to that of the
cation

Both cation and anion Only the smaller ion (cation)

leaves the solid crystal. leaves its original lattice site;

STOICHIOMETRIC
whereas, the anion remains in
corresponding lattice site

DEFECT
Two atoms leave the solid crystal One atom shifts from original
lattice site to the interstitial
position

Two vacancies occur in One vacancy and one self-

Schottky defec interstitial occur in Frenkel defect

One Schottky defect leads The number of atoms present in

to the reduction of two the crystal before and after
atoms from the crystal. Frenkel defect remains same.

Schottky defect reduces Density of the solid crystal

density of the solid. before and after Frenkel
defect remains same as no
atom leaves the solid.
 MED : ANIONIC VACANCIES

• Missing of anions from regular site leaving a hole which is

occupied by electron to maintain the neutrality of the
compound.

o The trapped electrons are called F-centers or color centers because

they are responsible for imparting color to the crystal.

o This defect is common in NaCl, KCl, LiCl,.

 MED : EXTRA CATIONS

o Extra cations occupying interstitial sites while electrons occupy

another interstitial site to maintain electrical neutrality

o Similar to Frenkel defect.

METAL DEFIENCY
DEFECT
Arise due to cationic vacancies. It occurs
when positive ions are missing from its crystal
lattice.

To maintain electrical neutrality, one of the

nearest metal ion acquires two positive charge.

This type of defect occurs in compounds where

the same metal can exhibit variable valency.

Transition metal compounds like NiO, FeO,

FeS.
 REVISION

TYPE OF CRYSTAL FORCES / BONDING GENERAL PROPERTIES

IONIC

GIANT

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