Recommended Reading:

1. Chapter 11. Chang R. Chemistry 12th Edition. McGraw-Hill, 2017.

2. Chapter 12. Brown et al. Chemistry: The Central Science 13th Edition. Pearson, 2015.
3. Chapter 12. Petrucci et al. General Chemistry: Principles and Modern Applications. Pearson Canada Inc., 2017

Solids
 Solids are a form of matter that has a definite shape, density, and volume.
 Solids are firm, rigid materials that generally resist changes in their shape.
 Examples of solids: Metals, gemstones, plastic, ice, human bones
There are different types of solids. The two main categories of solids are amorphous solids and crystalline
solids.
Crystalline Solids

💎 Crystalline solids have well-defined shapes because their particles occur in a rigid and orderly arrangement.
The forces responsible for the stability of a crystal can be ionic forces, covalent bonds, van der Waals forces,
hydrogen bonds, or a combination of these.

The basic repeating structural unit of a crystalline solid is a unit cell, represented by the cube below.

Each yellow sphere — called a lattice point — represents an atom, ion, or molecule. Any of the unit cells, when
repeated in space in all three dimensions, form the lattice structure characteristic of a crystalline solid.

As we'll see later in this chapter, lattice points are not restricted just to corners.

Each crystalline solid can be described in terms of one of the seven types of crystal systems shown below. For
this chapter, we will only discuss the simple cubic system and its related cubic cells: the simple cubic cell (scc),
the body-centered cubic cell (bcc), and the face-centered cubic cell (fcc).

7 Types of Crystal Systems. © Chang, R. Chemistry 12th Edition. McGraw-Hill, 2017

💡 The coordination number is the number of atoms (or ions) surrounding an atom in a crystal lattice. This tells
us how tightly the spheres are packed together — the larger coordination number, the closer packing, the greater
number of particles in a given volume.

© Chang, R. Chemistry 12th Edition. McGraw-Hill, 2017

An atom in the corner (left) in any cell is shared by eight (8) unit cells. An edge atom (middle) is shared by four
(4) unit cells. A face-centered atom (right) in a cubic cell is shared by two unit cells.

Simple Cubic Cell

When eight lattice points are on the corners of the cube, we get a simple cubic cell.

©
Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.

These lattice points touch along the edges but do not touch diagonally along the cube faces or through its center
(see middle figure)

Each sphere in this arrangement is said to have a coordination number of 6 because if we expand this portion of
the crystal, any particular atom (in this case indicated by →) has six immediate neighbors — 4 in its layer
(number 1 to 4), one above (a), and one below (b). We can see This cubic cell has one atom.
The total number of atoms in the actual simple cubic cell is 1.

Since each of its lattice points is shared by 8 cubes (4 above and 4 below), the remaining lattice point is 1/8 per
corner.

Multiply this by the number of lattice points, 8, then we get the actual number of atoms for this cubic cell.

© Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.

Body-centered Cubic Cell

A body-centered cubic cell's identical particles lie at each corner and at the center (pink) of the cube.

Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.

In each cell, the corners don't touch each other, but all touch the sphere in the center (middle figure). Each
particle is surrounded by eight nearest neighbors — four above and another four below — so the coordination
number is 8.

It has two atoms. (1/8 × 8) comes from the corners, calculated the same way as in a simple cubic cell and an
additional 1 for the whole atom in the middle.
© Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.

Face-centered Cubic Cell

Identical particles lie at each corner and in the center of each face (yellow) but not in the center of the cube.
Particles at the corners touch those in the faces but not each other.

The coordination number is 12 (indicated right, below)

This has four atoms: (1/8 × 8) from the corners and (1/2 × 6) from the face-centered atoms.

© Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.
© Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.

Closest Packing

Fruits in the Philippines © Certified Foodies

We often see fruits piled like this in large markets. This is similar to the ways atoms are packed together. Here,
we'll compare the packing efficiency of each unit cell.

The packing efficiency is the percentage of the total volume of the unit cell occupied by the spheres. The
higher the packing efficiency, the less empty space there is.

1. The simple cubic cell only has 52% unit-cell volume. 48% is empty space. This is because the second
layer is directly above the first, resulting in large diamond-shaped empty spaces. This is a very
inefficient way to pack spheres, so no atoms are typically packed this way.
2. The body-centered cubic cell has its second layer over the empty spaces of the first layer, instead of
directly above it. These produce a sort of zigzagging pattern with the vertical layers. Its packing
efficiency is 68%. Several metallic elements — like Cr, Fe, and all 1A elements — have a crystal
structure like this.
3. For a cubic unit cell, the face-centered structure is the most efficient. It has the same packing efficiency
as the hexagonal closest packing (the most efficient packing type) — 74%. A third layer (blue), is placed
in the white spaces left from the first two layers. Most metallic elements crystallize in either a face-
centered or hexagonal cubic packing structure.
 ©

Silberberg et al. Chemistry: The Molecular Nature of Matter and Change 9th Edition.
Hexagon closest packing (left) and face-centered cubic cell, the cubic closest packing (right). © Hexnet

For a 3D view of these cubic cells and packing structures, tap here.

Determining Atomic Radius

Using the metal's cubic structure, and the density of the metal or just the length of its edge, it is possible to
calculate an atom's radius. The edge length of the unit cell is obtained from x-ray crystallography. We then
apply the Pythagorean theorem to find atomic or ionic radii in any of the three cubic unit cells.
Example

Barium is the largest nonradioactive alkaline earth metal. It has a body-centered cubic cell and a density of 3.62
g/cm3. What is the atomic radius of barium?

Solution:

For BCC : 1 unit cell = 2 atoms

4r
Edge length , A = Volume, V = A 3
√3
m
D = V = 3.62 g/cm3

m = g

1 mol
g = 2 atoms Ba ( 23
¿ ¿ ) = 4.56 x 10−22 g Ba
6 .022 x 10 atoms Ba

In order to find the atomic radius we need to find the volume,

−22
m m 4.56 x 10 g
D = V = = = 1.26 x 10−22 cm3
V D 3.62 g /cm3

Edge length = A , V = A3

4r
A 3 = 1.26 x 10−22 cm3 A =
√3
A √3 5.013 x 10 cm √ 3
−8
A = ¿) 1/3
r = =
4 4

A = 5 . 013 x 10−8cm r = 2 .57 x 10−8 cm

Example

Cobalt has a face-centered unit cell and an atomic radius of 125 pm. Calculate the density of cobalt metal.

Solution:

For FCC: 1 unit cell = 4 atoms given : r = 125 pm

−12
1 x 10 100 cm
Edge length = A=√ 8 r = √ 8 (125 pm) = 353. 55 pm ( )( ) = 3.54 x 10−8 cm
1 pm 1m

m 1 mol
D = V , V = A3 m = g = 4 atoms ( 23
¿ ¿ ) = 3. 91 4 x 10−22 g
6 .022 x 10
 −22
m 3. 91 4 x 10 g
D = 3 = 3 = 8.85 g/ cm3
A (3.54 x 10¿¿−8 cm) ¿

Example

Copper adopts cubic closest packing — fcc, and the edge length of the unit cell is 361.5 pm. What is the atomic
radius of copper?

For FCC : Edge length , A = √8 r

A = √8 r
A 361.5 pm
r= = = 127. 80 pm
√8 √8