Chapter 3 the Structure of Simple Solids

1. Metallic bonding bonding that occurs in metals when each atom loses one
or more electrons to a common sea
a. The strength of the bonding results from the combined attractions
between all these freely moving electrons and the resulting cations
b. An alternative view is that metals are effectively enormous molecules
with a multitude of atomic orbitals that overlap to produce molecular
orbitals extending throughout the sample
2. Metals
a. Malleable and ductile
3. Ionic bonding ions of different elements are held together in rigid,
symmetrical arrays as a result of the attraction between their opposite
charges
a. Depends on electron loss and gain, so it is found typically in
compounds of metals with electronegative elements; however there
are many exceptions
4. Unit cells and the description of crystal structures
a. Lattice a three-dimensional, infinite array of points; collection of
points
b. Lattice points each of which is surrounded in an identical way by
neighboring points, and which defines the basic repeating structure of
the crystal
i. A lattice point in the body of, that is fully inside, a cell belongs
entirely to that cell and counts as 1
ii. A lattice point on a face is shared by two cells and contributes
to the cell
iii. A lattice point on an edge is shared by four cells and hence
contributes
iv. A lattice point at a corner is shared by eight cells that share the
corner, and so contribute 1/8
c. Unit cell an imaginary parallel-sided region which the entire crystal
can be built up by purely translational displacements; unit cells so
generated fit perfectly together with no space excluded; collection of
repetitive points which generate lattice
5. Types of packing
a. Simple cubic atoms are arranged at the corners of the cube
i. Relatively rare
b. Body-centered cubic atoms are arranged at the corners of the cube
with another atom at the cube center
c. Cubic close-packed (ccp) or face-centered cubic (fcc) - atoms are
arranged at the corners and center of each cube face of the cell
1. Each metal atom has 12 nearest neighbors; nearest
neighbors are called the coordination number
2. Six atoms surround an atom in the same plane, and the
central atom is then capped by 3 atoms on top, and 3
atoms below it

3. If the bottom and top caps are staggered, the unit cell
that results is a face-centered cube
4. ABC
d. Hexagonally close-packed (hcp)
1. If the bottom cap and the top cap are directly above
each other, the arrangement has a hexagonal unit cell
2. ABAB
6. Holes in Close Packed Crystals
a. Octahedral holes lie within two staggered triangular planes of atoms
i. The coordination number of an atom occupying an octahedral
hole is 6
ii. For n atoms in a close-packed structure, there are n octahedral
holes
b. Tetrahedral holes are formed by a planar triangle of atoms, with a 4 th
atom covering the indentation in the center.
i. The resulting hole has a coordination number of 4
ii. For a close-packed crystal of n atoms, there are 2n tetrahedral
holes
7. Ionic solids
a. High melting points
b. Soluble in polar solvents
c. Ionic model treats the solid as an assembly of oppositely charged
hard spheres that interact primarily by non-directional electrostatic
forces (Coulombic forces) and repulsions between complete shells in
contact
d. Rock-salt structure
i. Ccp or fcc
ii. Can be viewed as a face-centered cubic array of the anions, with
the cations in all of the octahedral holes
iii. A face centered cubic array of cations with anions in all of the
octahedral holes
iv. The coordination number is 6 for both ions
v. (6,6)
vi. CN = 6

vii.
e. Cesium Chloride structure

i. Alloys, less common

ii. Chloride ions occupy the corners of a cube, with a cesium ion in
the center (called a cubic hole)
iii. Both have coordination number of 8
iv. CN = 8
v. (8,8)

f.

vi.
Zinc Blend or Sphalerite structure
i. Ccp or fcc
ii. Anions (S2-) ions are in a face-centered cubic arrangement, with
cations (Zn2+) in half of the tetrahedral holes
iii. (4,4)

iv.
g. Fluorite (CaF2)
i. Ccp
ii. A face-centered cubic arrangement of Ca2+ ions with F- ions in
all of the tetrahedral holes.
iii. (8,4)

iv.
h. Anti-fluorite
i. Ccp
ii. (4,8)

iii. The anti-fluorite structure reverses the positions of the cation

anions
i.

Rutile
i. Hcp
ii. The structure can also be considered an example of hole filling
in a hcp anion arrangement, but now the cations occupy only
half the octahedral holes and there is considerable buckling of
the close-packed anion layers
iii. Each Ti4+ atom is surrounded by six O atom and each O atom is
surrounded by three Ti4+ ions; hence the rutile structure has
(6,3)-coordination
iv. (6,3)