Physical Chemistry I (Solid State) : DR Fatah Eltaboni

Physical chemistry I(Solid state) Dr Fatah Eltaboni
 SOLIDS:
 Solid is one of the four states of matter (the others being

liquid, gas, and plasma). It is characterized by structural
rigidity and resistance to changes of shape or volume
 TYPES OF SOLIDS:
:
1. Crystalline solids
2. Amorphous solids
 A crystalline solid exists as small crystals, each crystal

having a characteristic geometrical shape.
 In a crystal, the atoms, molecules or ions are arranged in a

regular, repeating three dimensional pattern called the
crystal lattice.
 Sugar and salt are crystalline solids.
 An amorphous solid (Gr amorphous = no form) has atoms,

molecules or ions arranged at random and lacks the ordered
crystalline lattice.
 Examples are rubber and wax
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 ISOTROPY:
 In amorphous substances, as in liquids, the arrangement of
particles is random and disordered. They exhibit the same
value of any property in all directions.
 ANISOTROPY:
 Crystalline substances are anisotropic and the magnitude of
a physical property varies with directions.
 THE HABIT OF A CRYSTAL (external shape):
 The plane surfaces of the crystal are called faces.
 The angles between the faces are called interfacial angles.
 The interfacial angles for a given crystalline substance are

always the same.
 The habit of a crystal of a given compound depends on the

rate of development of the different faces.
 Slow growth from a slightly super-saturated solution or a

very slowly cooling solution gives large crystals.
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 Different crystals of the same substance may not look alike in

the presence of certain impurities, different faces grow at
different rates and give rise to many forms.
 For example, if sodium chloride is crystallised from its

supersaturated solution, it forms cubic crystals. But if urea is
added as impurity, it gives octahedral crystals.
 SYMMETRY OF CRYSTALS:
 Symmetry in crystals may be due to a plane, a line or a point.
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 Elements of Symmetry:
(1) Plane of Symmetry:
 A crystal is said to have a plane of symmetry if it can be

divided by an imaginary plane into two equal parts, each of
which is the exact mirror image of the other.
(2) Axis of Symmetry:
 An axis of symmetry is an imaginary line drawn through the

crystal such that during rotation of the crystal through 360º.
(3) Centre of Symmetry: (Point of symmetry)

 It is a point at the centre of the crystal.
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 CRYSTAL STRUCTURE:
 The particles in crystals are arranged in regular patterns

that extend in all directions.
 The overall arrangement of particles in a crystal is called the

CRYSTAL LATTICE or simply lattice.
 The simple basic unit or the building block of the crystal

lattice is called the UNIT CELL.
 How to Represent Crystal Lattice and Units Cells ?
 In 1850, August Bravais, a French mathematician observed

that the crystal lattice of substances may be categorised into
seven types. These are called Bravais lattices and the
corresponding unit cells are referred to as Bravais unit cells.
 The unit cells may be characterised by the following

parameters :
(1) relative lengths of the edges along the three axes (a, b, c).
(2) the three angles between the edges (α, β, γ).
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 CUBIC UNIT CELLS:
 Ionic solids and metals have crystal lattices containing cubic

unit cells.
SC BCC FCC
 Compute Atoms in a Unit Cell:
 Atoms on corners of faces are shared with adjoining cells.

Therefore the number of atoms in a cubic unit cell computed
as follows:
(1) Eight unit cells share each corner atom. Therefore the simple
cubic unit cell contains the equivalent of one atom.
(SC) At each corner we have = 1/8 atom

At 8 corners we have = 1/8 × 8 = 1 atom
(2) Each face-centred atom is shared by two unit cells. Therefore

the face-centred unit cell contains the equivalent of four atoms.
At 8 corners, 1/8 each = 1 atom

6 face-centred sites, 1/2 each = 3 atoms
(FCC) Total equivalent atoms = 1 + 3 = 4
(3) A body centred unit cell contains the equivalent of two atoms.
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At 8 corners at 1/8 each = 1 atom

central unshared = 1 atom
(BCC) Total equivalent atoms = 1 + 1 = 2
 Calculation of Mass of the Unit Cell:
 Unit Cell Mass = Mass of one atom x number of atoms in the

unit cell
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 Coordination Number (CN) of Crystal Lattice:
 The coordination number of a crystal structure is the number

of particles (ions, atoms or molecules) adjacent to each
particle in the lattice.
Example: CN of NaCl crystal:
Unit Cell n CN
SC 1 6
BCC 2 8
FCC 4 12
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 X–RAY CRYSTALLOGRAPHY:
 X-ray crystallography is a method used for determining the
atomic and molecular structure of a crystal, in which the
crystalline atoms cause a beam of X-rays to diffract into many
specific directions.
 BRAGG’S EQUATION:
 Bragg equation is a mathematical relation to determine

interatomic distances from X-ray diffraction patterns.
 DERIVATION OF BRAGG EQUATION:
Fig. 12.14 shows a beam of X-rays falling on the crystal

surface. Two successive atomic planes of the crystal are
shown separated by a distance (d). Let the X-rays of
wavelength (λ) strike the first plane at an angle (θ). Some of
the rays will be reflected at the same angle. Some of the rays
will penetrate and get reflected from the second plane. These
rays will reinforce those reflected from the first plane
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if the extra distance travelled by them (CB + BD) is equal to

integral number, n, of wavelengths.That is,
nλ = CB + BD ................................(i)
Geometry shows that: CB = BD = AB sin θ .......................(ii)
From (i) and (ii): nλ = 2AB sin θ or nλ = 2d sin θ
 This is known as the Bragg equation. The reflection

corresponding to n = 1 (for a given series of planes) is called
the first order reflection. The reflection corresponding to n =
2 is the second order reflection and so on.
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 CLASSIFICATION OF CRYSTALS ON THE BASIS OF BONDS:
 (a) Ionic crystals

 (b) Molecular crystals
 (c) Network covalent crystals
 (d) Metallic crystals
(1) IONIC CRYSTALS:
 In an ionic crystal the lattice is made of positive and negative

ions. These are held together by ionic bonds, example the
sodium chloride crystal:
 The increase of electrostatic repulsions along the displaced

plane causes the crystal to break.
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 Ionic solids are non-conducting because the ions are in fixed

positions. However, in the dissolved state the ions are
allowed freedom of movement so that it conducts electricity.
 Lattice Energy of an Ionic Crystal (Born-Haber Cycle):
 Lattice energy is defined as : the change in enthalpy (heat

change) that occurs when 1 mole of a solid crystalline
substance is formed from its gaseous ions.
 For example, the lattice energy of NaCl, is the change in

enthalpy, ΔHº, when Na+ and Cl– ions in the gas phase come
together to form 1 mole of NaCl crystal.
 Enthalpy change for direct formation:
 Enthalpy change by indirect steps:
 Step 1: Conversion of sodium metal to gaseous atoms

(sublimation).
 Step 2: Dissociation of chlorine molecules to chlorine atoms.

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 Step 3: Conversion of gaseous sodium to sodium ions by

losing electrons.
 Step 4: Chlorine atoms gain an electrons to form chloride

ions.
 Step 5: Sodium and chloride ions get together and form the
crystal lattice. The energy released in this process is the
negative of lattice energy.
 MOLECULAR CRYSTALS:
 Molecules are the structural units held together by van der
Waals’ forces.
Example: Crystal lattice of dry CO2 (dry ice)
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 NETWORK COVALENT CRYSTALS:

 In this type of crystals atoms occupy the lattice sites. These
atoms are bonded to one another by covalent bonds.
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 METALLIC CRYSTALS
 Metal crystal may be described as having positive ions at the

lattice positions surrounded by mobile electrons throughout
the crystal.
 STRUCTURE OF METAL CRYSTALS
 the close-packed metallic crystals are of two types :
(a) Hexagonal close-packed (hcp)
(b) Cubic close-packed (ccp)
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 CRYSTAL DEFECTS:
 A perfect crystal is one in which all the atoms or ions are

lined up in a precise geometric pattern.
 Crystal defects can affect the physical and chemical

properties of a solid.
 When foreign particles are trapped in vacant interstitial

spaces, it is called interstitial impurity.
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 ALLOYS:
 SEMICONDUCTORS:
 SOLAR CELLS:
 It is a device to convert light energy into electrical energy.
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 LIQUID CRYSTALS:
 The liquid crystals have a structure between that of a liquid

and that of a crystalline solid. Thus the liquid crystals have
the fluidity of a liquid and optical properties of solid crystals.
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 APPLICATIONS OF LIQUID CRYSTALS:
 Number Displays:
 When a thin layer of nematic liquid crystal is placed between

two electrodes and an electric field is applied, the polar
molecules are pulled out of alignment. This causes the
crystal to be opaque. Transparency returns when electrical
signal is removed. This property is used in the number
displays of digital watches, electronic calculators, and other
instruments.
 Monitoring Body Temperature:
 Like the solid crystals, liquid crystals can diffract light. Only
one of the wavelengths of white light is reflected by the
crystal which appears coloured. As the temperature
changes, the distance between the layers of molecules also
changes. Therefore the colour of the reflected light changes
correspondingly. This cholesteric liquid crystal undergoes a
series of colour changes with temperature. These crystals
are used in indicator tapes to monitor body temperature or to
spot areas of overheating in mechanical systems.
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Physical chemistry I(Solid state) Dr Fatah Eltaboni

 Solid is one of the four states of matter (the others being

 A crystalline solid exists as small crystals, each crystal

 In a crystal, the atoms, molecules or ions are arranged in a

 Sugar and salt are crystalline solids.

 An amorphous solid (Gr amorphous = no form) has atoms,

 Examples are rubber and wax

 THE HABIT OF A CRYSTAL (external shape):

 The plane surfaces of the crystal are called faces.

 The angles between the faces are called interfacial angles.

 The interfacial angles for a given crystalline substance are

 The habit of a crystal of a given compound depends on the

 Slow growth from a slightly super-saturated solution or a

 Different crystals of the same substance may not look alike in

 For example, if sodium chloride is crystallised from its

 Symmetry in crystals may be due to a plane, a line or a point.

(1) Plane of Symmetry:

 A crystal is said to have a plane of symmetry if it can be

(2) Axis of Symmetry:

 An axis of symmetry is an imaginary line drawn through the

(3) Centre of Symmetry: (Point of symmetry)

 The particles in crystals are arranged in regular patterns

 The overall arrangement of particles in a crystal is called the

 The simple basic unit or the building block of the crystal

 How to Represent Crystal Lattice and Units Cells ?

 In 1850, August Bravais, a French mathematician observed

 The unit cells may be characterised by the following

(2) the three angles between the edges (α, β, γ).

 CUBIC UNIT CELLS:

 Ionic solids and metals have crystal lattices containing cubic

 Compute Atoms in a Unit Cell:

 Atoms on corners of faces are shared with adjoining cells.

(SC) At each corner we have = 1/8 atom

(2) Each face-centred atom is shared by two unit cells. Therefore

At 8 corners, 1/8 each = 1 atom

At 8 corners at 1/8 each = 1 atom

 Calculation of Mass of the Unit Cell:

 Unit Cell Mass = Mass of one atom x number of atoms in the

 Coordination Number (CN) of Crystal Lattice:

 The coordination number of a crystal structure is the number

Example: CN of NaCl crystal:

 Bragg equation is a mathematical relation to determine

 DERIVATION OF BRAGG EQUATION:

Fig. 12.14 shows a beam of X-rays falling on the crystal

if the extra distance travelled by them (CB + BD) is equal to

Geometry shows that: CB = BD = AB sin θ .......................(ii)

From (i) and (ii): nλ = 2AB sin θ or nλ = 2d sin θ

 This is known as the Bragg equation. The reflection

 CLASSIFICATION OF CRYSTALS ON THE BASIS OF BONDS:

 (a) Ionic crystals

(1) IONIC CRYSTALS:

 In an ionic crystal the lattice is made of positive and negative

 The increase of electrostatic repulsions along the displaced

 Ionic solids are non-conducting because the ions are in fixed

 Lattice Energy of an Ionic Crystal (Born-Haber Cycle):

 Lattice energy is defined as : the change in enthalpy (heat

 For example, the lattice energy of NaCl, is the change in

 Enthalpy change for direct formation: