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The Solid State
General characteristics of solid state:
Definite mass, volume and shape
Short intermolecular distances
Strong intermolecular forces
Fixed lattice positions of the constituent particles
Incompressibility and rigidity
Classification of the solid state:
Crystalline
Amorphous (sometimes called pseudo solids or super-cooled liquids)
Differences between the crystalline and amorphous solids
Crystalline

Amorphous

Have definite characteristic
geometrical shape

Have irregular shape

Melt at a sharp and characteristic
temperature

Gradually soften over a range of
temperature

When cut with a sharp edged tool, the
newly generated pieces are plain and
smooth

When cut with a sharp edged tool, the
newly generated pieces are with
irregular surfaces

Have definite and characteristic heat
of fusion

Do not have definite heat of fusion

Are true solids

Are pseudo solids

Anisotropic in nature

Isotropic in nature

Have long-range order

Have only short-range order

Classification of crystalline solids (On the basis of the nature of intermolecular forces)
Molecular solids
Non-polar molecular solids →These consist either atoms or the molecules formed by non-polar
covalent bonds. Example: H2 , Cl2 , I 2
Polar molecular solids → The molecules ion these types of solids are held together by strong
dipole-dipole interactions. Example: Solid SO 2 , solid NH3
Hydrogen-bonded molecular solids → The molecules of such solids contain polar covalent bonds
between H and f, O or N atoms. Example: Ice (H2 O)
Ionic solids
Ions are the constituent particles; e.g., NaCl, KNO 3
Metallic solids
Each metal atom is surrounded by electrons; e.g., Fe, Cu
Covalent or network solids
Formed by covalent bonds; e.g., diamond, silicon carbide

Crystal lattice: A regular three-dimensional arrangement of points in space.
There are 14 Bravais lattices
Unit cells: There are two categories of unit cells –
Primitive unit cells: There are seven types of primitive unit cells –
Cubic (a = b = c, α =β = γ = 90°); e.g., NaCl
Tetragonal (a = b ≠ c, α =β = γ = 90°); e.g., CaSO 4
Orthorhombic (a ≠ b ≠ c, α =β = γ = 90°); e.g., KNO 3
Hexagonal (a = b ≠ c, α =β = 90°, γ = 120°); e.g., ZnO
Rhombohedral or Trigonal (a = b = c, α =β = γ ≠ 90°); e.g., CaCO 3
Monoclinic (a ≠ b ≠ c, α = γ = 90°, β ≠ 120°)
Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ ≠ 90°); e.g., Na2 SO 4.10H2 O
Centred unit cells: There are three types of centred unit cells –
Body-centred unit cells: Contain one constituent particle at its body centre along with the ones
present at corners
Face-centred unit cells: Contain one constituent particle at the centre of each face along with the
ones present at corners
End-centred unit cells: Contain one constituent particle at the centre of any two faces along with the
ones present at corners

Number of atoms in a unit cell:
Total number of atoms in one primitive cubic unit cell = 1
Total number of atoms in one body-centred cubic unit cell = 2
Total number of atoms in one face-centred cubic unit cell = 4

Close-packed structures:
Coordination number: The number of the nearest neighbours of a particle
Packing efficiency: The percentage of total space filled by the particles
Close-Packing in One dimension
Only one way of arrangement, i.e., the particles are arranged in a row, touching each other
Close-Packing in Two Dimensions
Square close-packing in two dimensions
Close-Packing in Three Dimensions
Three-dimensional close-packing is obtained by stacking two-dimensional layers (square closepacked or hexagonal close-packed) one above the other.
There are two highly efficient lattices of close-packing –
Hexagonal close-packed (hcp)
Cubic close-packed (ccp) [also called face-centred cubic (fcc) lattice]
In hcp and ccp, 74% space is filled, i.e., packing efficiency = 74%.
The remaining space is present in the form of voids.

There are two types of voids –
Octahedral voids
Tetrahedral voids
The packings other than hcp and ccp are not close packings as they have less packing efficiency.
Packing efficiency in bcc = 68%
Packing efficiency in simple cubic lattice = 52.4%
Number of octahedral voids = Number of close-packed particles
Number of tetrahedral voids = 2 × Number of close-packed particles
In ionic solids, the bigger ions (usually anions) form the close-packed structure and the smaller
ions (usually cations) occupy the voids.
The fraction of the octahedral or tetrahedral voids that are occupied depends on the chemical
formula of the compound.
Packing Efficiency
Percentage of total space filled by particles
packing efficiency
Calculations involving dimensions of unit cells:
Density of a unit cell =

Where,
d → Density
z → Number of atoms present in one unit cell
M → Molar mass
a → Edge length
N A→ Avogadro’s number

Imperfections in solids:
Line defects
-These arise due to irregularities in the arrangement of constituent particles in entire rows of a lattice point
Point defects
-These arise due to irregularities in the arrangement of constituent particles around a point or an atom
-There are three types of point defects: Stoichiometric, Impurity and Non-stoichiometric
Stoichiometric defects (intrinsic or thermodynamic defects)
Vacancy defect
-Developed when a substance is heated
-Decreases the density of the substance
Interstitial defect
-Increases the density of the substance
In ionic solids, the vacancy and interstitial defects exist as Frenkel and Schottky defects.
-Frenkel defect (also called dislocation defect): It occurs when there is a large difference in the size of
ions.
-Schottky defect: It is a vacancy defect and it decreases the density of the substance.
Impurity defects:
These defects arise when foreign atoms are present at the lattice site (in place of the host atoms).

Non-stoichiometric defects:
Metal excess defect
-Metal excess defect due to anionic vacancies
-Metal excess defect due to the presence of extra cations
Metal deficiency defect: Occurs when the metals show variable valency, i.e., the transition metals

Classification of solids on the bases of conductivities:
Conductors
Insulators
Semiconductors

Doping: Adding an appropriate amount of suitable impurity to increase conductivity
n-type semiconductor
-Doped with electron-rich impurities
p-type semiconductor
-Doped with electron-deficient impurities
Semiconductors are widely used in electronic industries.

Magnetic properties:
Magnetic properties of substances originate because each electron in an atom behaves like a tiny magnet.
-Classification of substances on the basis of magnetic properties:
Paramagnetic: e.g., O 2
Diamagnetic: e.g., H2 O
Ferromagnetic: e.g., CrO 2
Anti-ferromagnetic: e.g., MnO
Ferrimagnetic: e.g., Fe 3 O 4
Ferromagnetic substances can be made permanent magnets.
These magnetic properties are used in audio, video and other recording devices.

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Characteristics and Classification of Solids

  • 1. The Solid State General characteristics of solid state: Definite mass, volume and shape Short intermolecular distances Strong intermolecular forces Fixed lattice positions of the constituent particles Incompressibility and rigidity Classification of the solid state: Crystalline Amorphous (sometimes called pseudo solids or super-cooled liquids) Differences between the crystalline and amorphous solids Crystalline Amorphous Have definite characteristic geometrical shape Have irregular shape Melt at a sharp and characteristic temperature Gradually soften over a range of temperature When cut with a sharp edged tool, the newly generated pieces are plain and smooth When cut with a sharp edged tool, the newly generated pieces are with irregular surfaces Have definite and characteristic heat of fusion Do not have definite heat of fusion Are true solids Are pseudo solids Anisotropic in nature Isotropic in nature Have long-range order Have only short-range order Classification of crystalline solids (On the basis of the nature of intermolecular forces) Molecular solids Non-polar molecular solids →These consist either atoms or the molecules formed by non-polar covalent bonds. Example: H2 , Cl2 , I 2 Polar molecular solids → The molecules ion these types of solids are held together by strong dipole-dipole interactions. Example: Solid SO 2 , solid NH3
  • 2. Hydrogen-bonded molecular solids → The molecules of such solids contain polar covalent bonds between H and f, O or N atoms. Example: Ice (H2 O) Ionic solids Ions are the constituent particles; e.g., NaCl, KNO 3 Metallic solids Each metal atom is surrounded by electrons; e.g., Fe, Cu Covalent or network solids Formed by covalent bonds; e.g., diamond, silicon carbide Crystal lattice: A regular three-dimensional arrangement of points in space. There are 14 Bravais lattices Unit cells: There are two categories of unit cells – Primitive unit cells: There are seven types of primitive unit cells – Cubic (a = b = c, α =β = γ = 90°); e.g., NaCl Tetragonal (a = b ≠ c, α =β = γ = 90°); e.g., CaSO 4 Orthorhombic (a ≠ b ≠ c, α =β = γ = 90°); e.g., KNO 3 Hexagonal (a = b ≠ c, α =β = 90°, γ = 120°); e.g., ZnO Rhombohedral or Trigonal (a = b = c, α =β = γ ≠ 90°); e.g., CaCO 3 Monoclinic (a ≠ b ≠ c, α = γ = 90°, β ≠ 120°) Triclinic (a ≠ b ≠ c, α ≠ β ≠ γ ≠ 90°); e.g., Na2 SO 4.10H2 O Centred unit cells: There are three types of centred unit cells – Body-centred unit cells: Contain one constituent particle at its body centre along with the ones present at corners Face-centred unit cells: Contain one constituent particle at the centre of each face along with the ones present at corners End-centred unit cells: Contain one constituent particle at the centre of any two faces along with the ones present at corners Number of atoms in a unit cell: Total number of atoms in one primitive cubic unit cell = 1
  • 3. Total number of atoms in one body-centred cubic unit cell = 2 Total number of atoms in one face-centred cubic unit cell = 4 Close-packed structures: Coordination number: The number of the nearest neighbours of a particle Packing efficiency: The percentage of total space filled by the particles Close-Packing in One dimension Only one way of arrangement, i.e., the particles are arranged in a row, touching each other Close-Packing in Two Dimensions Square close-packing in two dimensions Close-Packing in Three Dimensions Three-dimensional close-packing is obtained by stacking two-dimensional layers (square closepacked or hexagonal close-packed) one above the other. There are two highly efficient lattices of close-packing – Hexagonal close-packed (hcp) Cubic close-packed (ccp) [also called face-centred cubic (fcc) lattice] In hcp and ccp, 74% space is filled, i.e., packing efficiency = 74%. The remaining space is present in the form of voids. There are two types of voids – Octahedral voids Tetrahedral voids The packings other than hcp and ccp are not close packings as they have less packing efficiency. Packing efficiency in bcc = 68% Packing efficiency in simple cubic lattice = 52.4% Number of octahedral voids = Number of close-packed particles Number of tetrahedral voids = 2 × Number of close-packed particles In ionic solids, the bigger ions (usually anions) form the close-packed structure and the smaller ions (usually cations) occupy the voids. The fraction of the octahedral or tetrahedral voids that are occupied depends on the chemical formula of the compound.
  • 4. Packing Efficiency Percentage of total space filled by particles packing efficiency Calculations involving dimensions of unit cells: Density of a unit cell = Where, d → Density z → Number of atoms present in one unit cell M → Molar mass a → Edge length N A→ Avogadro’s number Imperfections in solids: Line defects -These arise due to irregularities in the arrangement of constituent particles in entire rows of a lattice point Point defects -These arise due to irregularities in the arrangement of constituent particles around a point or an atom -There are three types of point defects: Stoichiometric, Impurity and Non-stoichiometric Stoichiometric defects (intrinsic or thermodynamic defects) Vacancy defect -Developed when a substance is heated -Decreases the density of the substance Interstitial defect -Increases the density of the substance In ionic solids, the vacancy and interstitial defects exist as Frenkel and Schottky defects. -Frenkel defect (also called dislocation defect): It occurs when there is a large difference in the size of ions.
  • 5. -Schottky defect: It is a vacancy defect and it decreases the density of the substance. Impurity defects: These defects arise when foreign atoms are present at the lattice site (in place of the host atoms). Non-stoichiometric defects: Metal excess defect -Metal excess defect due to anionic vacancies -Metal excess defect due to the presence of extra cations Metal deficiency defect: Occurs when the metals show variable valency, i.e., the transition metals Classification of solids on the bases of conductivities: Conductors Insulators Semiconductors Doping: Adding an appropriate amount of suitable impurity to increase conductivity n-type semiconductor -Doped with electron-rich impurities p-type semiconductor -Doped with electron-deficient impurities Semiconductors are widely used in electronic industries. Magnetic properties:
  • 6. Magnetic properties of substances originate because each electron in an atom behaves like a tiny magnet. -Classification of substances on the basis of magnetic properties: Paramagnetic: e.g., O 2 Diamagnetic: e.g., H2 O Ferromagnetic: e.g., CrO 2 Anti-ferromagnetic: e.g., MnO Ferrimagnetic: e.g., Fe 3 O 4 Ferromagnetic substances can be made permanent magnets. These magnetic properties are used in audio, video and other recording devices.