The Solid State • Topic 1 of 3

Crystalline Solids & Unit Cells

A solid is the state of matter in which constituent particles are held in fixed positions by strong intermolecular or interionic forces, giving it a definite shape, volume and high density. Solids are broadly classified into two types based on how their particles are arranged.

Crystalline solids have a long-range, regular and repeating arrangement of particles. They are anisotropic (physical properties such as refractive index and electrical conductivity differ with direction), have sharp melting points, definite geometry, and are true solids. Examples: NaCl, diamond, quartz, ice, metals. Amorphous solids (Greek amorphos = no form) have only short-range order, are isotropic, soften over a range of temperature, lack a sharp melting point, and are regarded as supercooled liquids or pseudo-solids. Examples: glass, rubber, plastics.

Crystalline solids are further classified by the nature of the binding force and the particles occupying the lattice points:

  • Ionic solids — ions held by electrostatic force; hard, brittle, high melting, conduct only when molten/aqueous (NaCl, ZnS).
  • Covalent (network) solids — atoms in a continuous covalent network; very hard, very high melting, insulators except graphite (diamond, $\text{SiO}_2$).
  • Molecular solids — molecules held by van der Waals, dipole or hydrogen bonds; soft, low melting, non-conducting ($\text{I}_2$, dry ice $\text{CO}_2$, ice).
  • Metallic solids — kernels in a sea of delocalised electrons; malleable, ductile, lustrous, good conductors (Cu, Fe, Mg).

The orderly three-dimensional arrangement of points representing particle positions is the crystal lattice (space lattice); each point is a lattice point. The smallest repeating portion that, on translation in three dimensions, generates the whole lattice is the unit cell. A unit cell is described by three edge lengths $a,b,c$ and three angles $\alpha,\beta,\gamma$ between them. There are 7 crystal systems and 14 Bravais lattices.

Unit cells are either primitive (simple) — particles only at the eight corners — or centred — having additional particles. Centred cells include body-centred (bcc) (one extra particle at the centre of the body), face-centred (fcc/ccp) (one extra at the centre of each of the six faces) and end-centred (one extra at the centre of two opposite faces).

Each particle is shared between adjoining cells, so we count fractional contributions: a corner contributes $\tfrac{1}{8}$ (shared by 8 cells), a face $\tfrac{1}{2}$ (2 cells), an edge $\tfrac{1}{4}$ (4 cells), and a body-centre $1$ (one cell). Hence $z$ per unit cell is: simple cubic $z=8\times\tfrac{1}{8}=1$; bcc $z=8\times\tfrac{1}{8}+1=2$; fcc $z=8\times\tfrac{1}{8}+6\times\tfrac{1}{2}=4$.

bcc and fcc unit cells with labelled atomsbcc (z = 2)bodyfcc / ccp (z = 4)face
1
Worked Example
How many atoms belong to a simple (primitive) cubic unit cell? Show the counting.
Solution
  1. In a simple cubic cell, atoms sit only at the 8 corners.
  2. Each corner atom is shared by 8 unit cells, contributing $\tfrac{1}{8}$.
  3. $z=8\times\tfrac{1}{8}=1$.

Answer: $z=1$ atom per unit cell.

2
Worked Example
Calculate the number of atoms in a body-centred cubic (bcc) unit cell.
Solution
  1. Corners: 8 atoms each contributing $\tfrac{1}{8}$ give $8\times\tfrac{1}{8}=1$.
  2. Body centre: 1 atom belonging entirely to the cell gives $1$.
  3. $z=1+1=2$.

Answer: $z=2$ atoms per unit cell.

3
Worked Example
Calculate the number of atoms in a face-centred cubic (fcc) unit cell.
Solution
  1. Corners: $8\times\tfrac{1}{8}=1$.
  2. Face centres: 6 faces, each face atom shared by 2 cells, $6\times\tfrac{1}{2}=3$.
  3. $z=1+3=4$.

Answer: $z=4$ atoms per unit cell.

4
Worked Example
An ionic compound has anions A forming the fcc lattice and cations B occupying all the body-centre + edge-centre positions. How many of each ion are present per unit cell?
Solution
  1. Anions A (fcc): corners $8\times\tfrac{1}{8}=1$ plus faces $6\times\tfrac{1}{2}=3$, total $A=4$.
  2. Cations B at the body centre: $1\times1=1$.
  3. Cations B at the 12 edge centres: $12\times\tfrac{1}{4}=3$, so $B=1+3=4$.
  4. Formula ratio $A:B=4:4=1:1$, i.e. AB.

Answer: 4 A and 4 B per cell; formula AB.

5
Worked Example
Why are crystalline solids anisotropic while amorphous solids are isotropic?
Solution
  1. In a crystal the arrangement of particles differs along different directions.
  2. So a property measured (e.g. refractive index, conductivity) depends on the direction of measurement — this is anisotropy.
  3. Amorphous solids have a random, irregular arrangement that is statistically the same in all directions, so properties are identical in every direction — isotropy.

Answer: Anisotropy arises from directional regularity in crystals; isotropy from the random arrangement in amorphous solids.

6
Worked Example
Classify each as ionic, covalent, molecular or metallic: (a) diamond, (b) NaCl, (c) dry ice ($\text{CO}_2$), (d) copper.
Solution
  1. Diamond — a continuous network of C–C covalent bonds, so covalent (network) solid.
  2. NaCl — $\text{Na}^+$ and $\text{Cl}^-$ held by electrostatic force, so ionic solid.
  3. Dry ice — discrete $\text{CO}_2$ molecules held by weak van der Waals forces, so molecular solid.
  4. Copper — metal kernels in a sea of delocalised electrons, so metallic solid.

Answer: (a) covalent, (b) ionic, (c) molecular, (d) metallic.

Key Points

  • Crystalline solids have long-range order, are anisotropic and melt sharply; amorphous solids have short-range order, are isotropic and soften over a range (pseudo-solids).
  • Crystalline solids are ionic, covalent (network), molecular or metallic, differing in binding force, hardness, melting point and conductivity.
  • A crystal lattice is a 3-D array of points; the smallest repeating part is the unit cell, defined by $a,b,c$ and $\alpha,\beta,\gamma$ (7 systems, 14 Bravais lattices).
  • Unit cells are primitive (corners only) or centred (bcc, fcc, end-centred).
  • Contributions: corner $\tfrac{1}{8}$, face $\tfrac{1}{2}$, edge $\tfrac{1}{4}$, body $1$ — giving $z=1$ (simple), $z=2$ (bcc), $z=4$ (fcc).
Tap an option to check your answer0 / 4
Q1.Which of the following is an amorphous solid?
Explanation: Glass has only short-range order, no sharp melting point, and is isotropic — it is an amorphous (pseudo-) solid.
Q2.The number of atoms in a face-centred cubic unit cell is:
Explanation: $z=8\times\tfrac{1}{8}+6\times\tfrac{1}{2}=1+3=4$.
Q3.A particle present at the centre of an edge is shared by how many unit cells?
Explanation: An edge is shared by 4 unit cells, so an edge particle contributes $\tfrac{1}{4}$ to each.
Q4.Diamond is an example of a:
Explanation: In diamond each carbon is covalently bonded to four others forming a giant 3-D network — a covalent (network) solid.