Solid State Chemistry

Types of Solids
Crystalline solid: well-ordered, definite arrangements of molecules, atoms or ions.
Crystals have an ordered, repeated structure. Polycrystalline material: comprised of many small crystals or grains

Amorphous solid: no definite arrangement of molecules, atoms, or ions (i.e., lack well-defined structures or shapes).
Amorphous solids vary in their melting points.

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RAG RAOLA

CE-100

June 2009

RAG RAOLA

CE-100

Structures of Solids
The smallest repeating unit in a crystal is a unit cell.
Unit cell is the smallest unit with all the symmetry of the entire crystal. Three-dimensional stacking of unit cells is the crystal lattice.

June 2009

RAG RAOLA

CE-100

Structures of Solids
Unit Cells

The smallest repeating unit that shows the symmetry of the pattern is called the unit cell.
June 2009 RAG RAOLA CE-100

Types of Unit Cells

Primitive Cubic Body-centered Cubic (BCC) Face-centered Cubic (BCC) Hexagonal Close Pack (HCP) Rhombohedral Cubic Diamond

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CE-100

Common Types of Unit Cells

Three common types of unit cell.
Primitive cubic, atoms at the corners of a simple cube
each atom shared by 8 unit cells;

Body-centered cubic (bcc), atoms at the corners of a cube plus one in the center of the body of the cube,
corner atoms shared by 8 unit cells, center atom completely enclosed in one unit cell;

Face-centered cubic (fcc), atoms at the corners of a cube plus one atom in the center of each face of the cube,
corner atoms shared by 8 unit cells, face atoms shared by 2 unit cells.
June 2009 RAG RAOLA CE-100

Unit Cells

June 2009

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CE-100

Unit Cells

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CE-100

Table showing Atom Fractions in Unit Cells

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Face-Centered Cubic Crystal Structure

The hard spheres or ion cores touch one another across a face diagonal the cube edge length, a= 2R2 The coordination number, CN = the number of closest neighbors to which an atom is bonded = number of touching atoms, CN = 12 Number of atoms per unit cell, n = 4. (For an atomthat is shared with m adjacent unit cells, we only count a fraction of the atom, 1/m). In FCC unit cell we have: 6 face atoms shared by two cells: 6 x 1/2 =3 8 corner atoms shared by eight cells: 8 x 1/8 = 1 Atomic packing factor, APF = fraction of volume occupied by hard spheres = (Sum of atomic volumes)/(Volume of cell) = 0.74 (maximum possible)

June 2009

RAG RAOLA

CE-100

Body-Centered Cubic Crystal Structure

The hard spheres touch one another along cube diagonal the cube edge length, a= 4R/3 The coordination number, CN = 8 Number of atoms per unit cell, n = 2 Center atom (1) shared by no other cells: 1 x 1 = 1 8 corner atoms shared by eight cells: 8 x 1/8 = 1 Atomic packing factor, APF = 0.68 Corner and center atoms are equivalent

June 2009

RAG RAOLA

CE-100

Hexagonal Close-Packed Crystal Structure

Unit cell has two lattice parameters a and c. Ideal ratio c/a = 1.633 The coordination number, CN = 12 (same as in FCC) Number of atoms per unit cell, n = 6. 3 mid-plane atoms shared by no other cells: 3 x 1 = 3 12 hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2 2 top/bottom plane center atoms shared by 2 cells: 2 x 1/2 = 1 Atomic packing factor, APF = 0.74 (same as in FCC) All atoms are equivalent

June 2009

RAG RAOLA

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Examples: 1. Face-Centered Cubic (FCC) Crystal Structure Cu, Al, Ag, Au 2. Body-Centered Cubic (BCC) Crystal Structure

Cr, -Fe, Mo
3. Hexagonal Close-Packed (HCP) Crystal Structure Cd, Mg, Zn, Ti
June 2009 RAG RAOLA CE-100

Polymorphism and Allotropy

Polymorphism - materials may exist in more than one crystal structure. Allotropy - when an elemental solid exhibits polymorphism. Example: - Carbon

June 2009

RAG RAOLA

CE-100