CHAPTER 4

BASIC CONCEPTS OF CRYSTAL STRUCTURE

A basic concept in crystal structure is the unit cell. It is the smallest unit of volume that permits
identical cells to be stacked together to fill all space… The first is the unit cell for a face-centered
cubic lattice, and the second is for a body-centered cubic lattice.

Types of Crystalline Solids

Crystals are formed by atoms, ions or molecules. We can classify crystals into four types
according to the kind of particles that make up the crystal and the forces that held them together.
1. Ionic crystals. Positive and negative ions are held in the crystal arrangement by electrostatic
attraction. Because these forces are strong, ionic substances have high melting points, ionic crystals
are hard and brittle. Figure 4.1 shows what happens if an attempt is made to deform an ionic crystal.
Because of the movement of one plain of ions over another, ions with the same charge are brought
next to one another. The crystal breaks into fragments. Ionic compounds are good conductors of
electricity when molten or in solution but not free to move

Figure 4.1 Effect of deformation on a) a metallic crystal and b) an ionic crystal

2. Molecular crystals. Molecules occupy positions in crystals of covalent compound. The

intermolecular forces that hold the molecules in the crystal structure are not nearly strong as the
electrostatic forces that hold ionic crystals together. Molecular crystals, therefore, are soft and have
low melting points, usually below 300oC.
London forces hold nonpolar molecules in the structure. In crystals of polar molecules, dipole-
dipole forces as well as London forces occur. Polar compounds, therefore generally melt at slightly
higher temperature than nonpolar compounds of comparable molecular size and shape.
In general, molecular substances do not conduct electricity in the solid or liquid states. A few
molecular compounds, such as water, dissociate to a very light extent and produce low
concentrations of ions; these liquids are poor electrical conductors.
3. Network crystals. In these crystals, atoms occupy positions and they are
joined by a network of covalent bonds. The entire crystal can be looked at as one giant molecule. In
diamond, an example of this type of crystal, carbon atoms are bonded by covalent bonds into a three-
dimensional structure (see fig. 4.2). Material of this type have high melting points and are extremely
hard because of the large number of covalent bond that would have to be broken to destroy the
crystal structure. Network crystals do no conduct electricity.
 Figure 4.2 Arrangement of atoms in a diamond crystal

4. Metallic crystals. The outer electrons of metal atoms are loosely held and move freely
throughout a metallic crystal. The remainder of the metal atoms, positive ions, occupy fixed position in
the crystal. The negative cloud of the freely moving electrons, sometimes called an electron gas or a
sea of electrons, binds the crystal together. This binding force is called a metallic bond. The metallic
bond is strong. Most metals have high melting points, high densities and structures in which the
positive ions are packed together closely (called closest packed arrangement). Unlike with ionic
crystals, the positions of the positive ions can be altered without destroying the crystal because
because of the uniform cloud of negative charge provided by the freely moving electron (see fig. 1).
Most metallic shape) and ductile (capable of being drawn into wire). The freely moving electrons are
also responsible for the fact that most metals are good conductors of electricity.

Table 4.1 Types of Crystalline Solid

Attractive
Crystal Particles Properties Examples
Forces
High m.p.
Ionic Positive and Electrostatic Hard, brittle NaCl, BaO, KNO3
negative ions attractions Good electrical
conductor in
molten state
Low m.p.
Molecular Polar molecules London and Soft H2O, NH3, SO2
dipole-dipole Non-conductor
or extremely
Nonpolar poor conductor
molecules London of electricity in H2, Cl2, CH4
liquid state
Very high m.p.
Network Atoms Covalent bonds Very hard C (diamond)
Non-conductor of SiC, AIN, SiO2
Electricity
Fairly high m.p.
Metallic Positive ions and Metallic bonds Hard or soft Ag, Cu, Na, Fe, K
mobile Malleable and
electrons ductile
Good electrical
Conductor

Crystals
A crystal structure is a symmetric array of atoms, ions or molecules arranged in a repeating
three dimensional pattern. The symmetry of a crystal can be described in terms of a crystal lattice. A
lattice is a three-dimensional arrangement of points that represent sites with identical surroundings in
the same orientation. If one starts with any lattice point and goes a definite distance in a set direction,
a second lattice point will be encountered. The points are identical and have identical surroundings. A
simple cubic lattice is shown in fig. 4.3.

Figure 4.3 Simple cubic space lattice (A unit cell is shown in color)

A crystal lattice can usually be derived from a crystal structure by replacing the centers of the
material units (atoms, for example) with lattice points. Notice, however, that the definition of a crystal
lattice requires that the lattice points and surroundings be identical. A lattice of an ionic crystal,
therefore, can be define with the points centering on the cations, or in the anions, or on some sites
between the two.
A crystal lattice can be divided into identical parts called unit cells (see fig. 4.3). In theory, a
lattice can be produce by stacking its unit cells in three dimensions. The idea of a unit cell can also be
applied to a crystal structure. These unit cells are considered to consist of all the material units of
which the crystal is composed (both cations and anions of an ionic crystal) rather than just lattice
points. Keep in mind that the unit cell of a crystal structure has all the components of the crystal in
correct ratios. Repeating the unit cell of a crystal structure in three dimensions generates the structure
itself.

Figure 4.4 Cubic Structures

 The simplest types of unit cells are the cubic unit cells (fig. 4.4). Notice that is possible to
have points of positions rather than the corners of the unit cells in the body-centered cubic unit cell, a
point

In crystal of metals, we may assume that atoms occupy lattice positions (even though the
outer electrons of the metal atoms move freely throughout the structure). In counting the number of
atoms per unit cells, one must keep in mind that atoms on corners or faces are shared by adjoining
cells. Eight unit cells share each corner atom, and two unit cells share each face centered atom (see
fig. 4.5). A body-centered atom is not shared between unit cells and belongs exclusively to the unit
cell which it is found.
1. The simple cubic unit cell contains the equivalent of only one atom(eight corners at 1/8 atom atom)
2. The body-centered cubic unit cell contains two atoms (eight corners at 1/8 atom each and one
unshared atom in the center)
3. The face-centered cubic unit cell contains the equivalent of four atoms (eight corners at 1/8 atom
each and six face-centered atoms at ½ atm each)

Figure 4.5 In crystals, (a) a face-centered atom is shared by two cells , and (b) a corner
atom is shared by eight unit cells

Problems:
1. Nickel crystallizes in a face-centered cubic crystal. The edge of a unit cell is 352 pm. The atomic
mass of nickel is 58.7, and its density is 8.94 g/cm3. Calculate the Avogadro’s number from these
data. Solution:
-10
Since 1 pm = 10 cm
352 pm = 3.52 x 10-8 cm
The volume of one unit cell is ( 3,52 x 10-8 cm)3 = 4.36 x 10-23 cm3
Since the unit cell is face-centered, it contains four atoms
4 atoms = 4.36 x 10-23 cm3
From the density 1 cm3 = 8.94 g
The Avogadro’s number is the number of atoms in 58.7 g Ni
= 58.7 g Ni x 1 cm3 x 4 atoms __
-23 3
8.94 g Ni 4.36 x 10 cm
= 6.02 x 1023 atoms

2. Sodium crystallizes in a cubic structure, and the edge of a unit cell is 430 pm. The density of
3
sodium is 0.963 g/cm , and the atomic mass of sodium is 23.0. How many atoms of sodium are
contained in one unit cell? What type of cubic unit cell does sodium form?
 Solution: edge of 1 unit cell = 430 pm = 4.30 x 10 -8 cm
volume of the unit cell = (4.30 x 10-8 cm)3 - 7.95 x 10-23 cm3
1 mole Na = 23 g of Na
6.02 x 1023 atoms Na = 23 g of Na
no. of atoms = 7.95 x 10-23 cm3 x 0.963 g x 6.02 x 1023 atoms
3
cm 23 g
= 2 atoms
Sodium crystallizes in a body-centered cell since the body-centered cubic unit cell is the
only cubic cell that contains two atoms.
3. The edge length of a unit cell of Ta, is 330.6 pm, the unit is a body-centered cubic. Tantalum has a
density of 16.69 g/cm3. a) Calculate the mass of tantalum atom, b) Calculate the atomic mass of
tantalum in g/mole.
Solution: edge length, a = 330.6 pm = 330.6 x 10-10 cm = 3.306 x 10-8 cm
volume of the unit cell
V = a3 = (3.306 x 10-8 cm)3 = 3.613 x 10-23 cm3
mass of the 2 tantalum atoms in the body-centered cubic unit cell
m = dV = (16,69 g/cm3)(3.613 x 10-23 cm3) = 6.031 x 10-22 g
mass of one atom of Ta
= 6.031 x 10-22 g = 3 .015 x 10-22 g
2
atomic mass of Ta in g/mole
= 3.015 x 1022 g x 6.022 x 1023 atoms = 181.6 g/mole
atom mole
4. Krypton crystallizes with a face-centered cubic unit cell of edge 559 pm. What is the density of
solid krypton?
Solution: edge of the unit cell, a = 559 pm = 5.59 x 10 -8 cm
volume of the unit cell
V = a3 = (5.59 x 10-8 cm) = 1.747 x 10—22 cm3
average mass of one atom of Kr
= 83.798 g x 1 mole = 1.392 x 10-22 g/atom
mole 6.022 x 1023 atoms
mass of 4 Kr atoms in the face-centered cubic unit cell
-22 -22
= 1.392 x 10 g/atom x 4 atoms = 5.566 x 10 g
-22 3
density = mass = 5.566 x 10 g = 3.19 g/cm
-22 3
volume 1.747 x 10 cm

5. Titanium metal has a body centered cubic unit cell. The density of titanium is 4.50 g/cm3. Calculate
the edge length of the unit cell and the atomic radius of titanium.
Solution: average mass of one atom of Ti
= 47.867 g__ x 1 mole_____ = 7.949 x 10-23 g/atom
mole 6.022 x 1023atoms
mass of Ti in the unit cell
= 7.949 x 1023 g/atom x 2 atoms = 1.590 x 10-22 g
volume of the unit cell
V = m = 1.590 x 10-22g = 3.533 x 10-23 cm3
d 4.50 g/cm3
edge length of the unit cell
V = a3, a = 3√ V = 3√ 3.533 x 10-23 cm3 = 3.28 x 10-8 cm
atomic radius of Ti, for body-centered cubic unit cell by Pythagorean Theorem:
(4r)2 = a2 + (√ 2 a)2
16r2 = a2 + 2 a2
16r2 = 3a2
4r = √ 3 a
 r = √ 3 a = √ 3 (3.28 x 10-8 cm) = 1.42 x 10-8 cm = 142 pm
4 4

Crystal data can be used to calculate atomic radii:

1. In the case of a simple cubic unit cell, the atomic radius, r, is one-half the length of the edge of the
cell, a (see fig. 4.4) r = a/2
2. In a face-centered cubic unit cell, the atoms that lie along an edge do not touch. We must
calculate the length of the face diagonal (see fig. 4.6a). From the Pythagorean Theorem of right
triangles Hypotenuse2 = side2 + side2
(face diagonal)2 = a2 + a2 = 2a2
face diagonal = a 2
This diagonal is equal to four radii
4r = a √ 2
r = a√2
4
3. We must determine the length of a cube diagonal to find the atomic radius of an atom that forms a
body-centered cubic unit cell (see fig. 4.6b)
(cube diagonal)2 = a2 + (a √ 2 )2 = 3a2
cube diagonal = a √ 3
This diagonal is equal to four atomic radii
4r = a √ 3
r = a√3
4

Example:
1. Sodium crystallizes in a body-centered cubic unit cell with the length of the edge equal to 430 pm.
What is the atomic radius of Na?
The cube diagonal of the unit cell
= a √ 3 = (430 pm) √ 3 = 745 pm
The length is equal to four atomic radii
4r = 475 pm
r = 186 pm = 1.86 x 10-8 cm
2. Aluminum crystallizes in the face-centered cubic system and the edge of a unit cell is 430 pm.
Calculate the atomic radius of Al.
Solution: edge of unit cell = 430 pm = 4.30 x 10 -8 cm
face diagonal = a √ 2
= (4.30 x 10-8 cm) √ 2
= 6.08 x 10-8 cm
the diagonal is equal to four radii (see fig. 4.6a)
4r = 6.08 x 10-8 cm
r = 1.52 x 10-8 cm

3. Chromium crystallizes in a body-centered cubic structure, the unit cell volume is 2.583 x 10-23 cm3.
Determine the atomic radius of Cr in pm.
Solution:
3
Vol. of the unit cell = (edge length)
V = a3
a = 3√ 2.583 x 10-23 cm3
a = 2.956 x 10-8 cm
By Pythagorean theorem, find the atomic radius
(4r)2 = a2 + ( a √ 2 )2 1 m = 100 cm
16r2 = a2 + 2 a2 1 m = 1012 pm
2 2
16r = 3 a
 4r = √ 3 a
r = √3 a
4
r = √ 3 (2.956 x 10-8 cm) = 1.28 x 10-8 cm
4
-8 12
r = 1.28 x 10 cm X 10 pm = 128 pm
100 cm
4. Palladium crystallizes in a face-centered cubic cell. Its density is 12.023 g/cm3. Calculate the
atomic radius of palladium.
Solution: average mass of 1 atom of Pd
= 106.42 g x 1 mole_______ = 1.767 x 10-22 g/atom
mole 6.022 x 1023 atoms
mass of 4 Pd atoms in a face-centered cubic unit cell
= 1.767 x 10-22 g/atom x 4 atoms = 7.069 g/ unit cell
volume of the unit cell
-23 3
V= mass___ = 7.069 g___ = 5.879 x 10 cm
3
density 12.023 g/cm
edge length of the unit cell
V = a3
a = 3√ V = 3√ 5.879 x 10-23 cm3 = 3.888 x 10-8 cm
By Pythagorean Theorem in fig. 4.6a
(4r)2 = a2 + a2
16r2 = 2a2
4r = √ 2 a
r = √ 2_ a = √ 2 (3.888 x 10-8 cm)
4 4
-8
r = 1.375 x 10 cm
5. Barium has a radius of 224 pm and crystallizes in a body-centered cubic structure. What is the
edge length of the unit cell?
Solution: atomic radius, r = 224 pm = 2.24 x 10 -8 cm
for body-centered cubic unit cell, the edge length by Pythagorean Theorem:
2 2 2
(4r) = a + (√ 2 a)
2 2 2
16r = a + 2 a
2 2
16r = 3 a
4r = √3 a a = 4r_ = 4 _ (2.24 x 10-8 cm) =5.17 x 10 -8 cm = 517 pm
√3 √3

a
 b
Figure 4.6 Determination of (a) a face diagonal and (b) a cube diagonal

CRYSTAL STRUCTURE OF METALS

In the large majority of cases, metal crystal belong to one of three classification: body-
centered cubic (fig.4.4), face-centered cubic (fig.4.4), and hexagonal closest packed (fig.4.7). The
geometric arrangement of atoms in the face-centered cubic and the hexagonal closest-packed crystal
is such that each atom has a coordination number of 12 (each is surrounded by 12 other atoms at
equal distances). If the atoms are viewed as spheres, there is a minimum of empty in these two types
of crystals(about 26%), and both of the crystal lattices are called closest-packed structure. The
body-centered cubic arrangement is slightly more open than either of the closest-packed arrangement
(about 32% empty space); each atom of a body-centered cubic crystal has a coordination of 8.

Figure 4.7 Hexagonal closest-packed structure

The difference between the two closest-packed structures may be derived from a
consideration of fig.4.8. The shaded circles of the diagram represent the first lyer of spheres, which
are placed as close together as possible. The second layer of spheres (open circles) are placed in the
hollows formed by adjacent spheres of the first layer. The first two layers (a and b) of both the face-
centered cubic and the hexagonal closest-packed arrangement are the same. The difference arises in
the placement of the third and subsequent layers.
In the hexagonal closest-packed arrangement, the spheres of the third layer are placed so
that they are directly over those of the first layer. The sequence of layers may be represented as
ababab…. In the face-centered cubic structure, however, the spheres in the third layer are placed
over the holes (pink squares in fig. 4.8) formed by the arrangements of the first two layers. The
spheres of the fourth layer of the face-centered cubic structure are placed so that they are directly
over of the first layer, and the sequence of layers is abcabc….
 Figure 4.8 Schematic representation of the two layers
closest-packed arrangements

Table 4.2 Crystal Structure of Metals

The crystal structure of metals are summarized in Table 4.2. Equal numbers of metal crystallize in
each of the three structure (hexagonal closest packed, face-centered cubic, and body-centerd cubic).
The closest packing of most metallic cystals helps to explain the relative densities of metals. The
structure of a few metals (for ex. Manganese and mercury) do not fall in any of the three categories,
and the symbols for these metals do not appear in the table. Some metals exhibit crystal allotropy;
that is, different crystal forms of the same metal are stable under different conditions. For example, a
modification of calcium exists in each of the three structures. The crystal structure of each metal that
is indicated in the table is the one that is stable under ordinary conditions. In addition to many metals,
the noble gases (except for He) also crystallize in the face-centered cubic lattice.

IONIC CRYSTALS
The structures of ionic crystals are more complicated than those of metallic crystals. An ionic
crystal must accommodate ions of opposite charge and different size in the proper stoichiometric ratio
and in such a way that electrostatic attraction outweigh electrostatic repulsions.
The potential energy of interaction (PE) between two ions is directly proportional to the
product of the charges between the two ions (q1 and q2) and inversely proportional to the distance
between the centers of the two ions (d):
PE = kq1q2_
d
where k is equal to 8.988 x 109 J.m/C2 if q1 and q2 are expressed in coulombs (C) and d expressed in
meters. If the charges have the same sign, they will repel each othe and the potential energy will be a
positive value (energy is required to push the ions together). On the other hand, if the charges have
unlike signs, they will attract each other and the potential energy will be negative value (energy is
released when the ions come together). The most stable structure for a given compound, therefore, is
one in which the largest possible number of cation-anion attractions exist and one in which the
positive and negative ions are as close together as possible (small value of d).
The three most common crystal types for ionic compounds of formula MX shown in fig. 4.9. In
each diagram, there are as many cations per unit cell as there are anions (one each in CsCl and four
each in NaCl and ZnS, taking into account sharing of adjacent cells). A 1:1 stoichiometric ratio is
represented in each case.

Figure 4.9 Crystal Structure of ionic compounds of the MX type

Table 4.3 Crystal Structures of Some Ionic Compounds

Structure Examples
cesium chloride CsCl, CsBr, CsI, TlCl, TlI, NH4Cl, NH4Br
+ + + +
sodium chloride halides of Li , Na . K , Rb
2+ 2+ 2+ 2+ , 2+ 2+
oxides and sulphides of Mg , Ca , Sr , Ba , Mn , Ni
AgF, AgCl, AgBr, NH4I
zinc blende sulfides of Be2+, Zn2+, Cd2+, Hg2+
CuCl, CuBr, CuI, AgI
 fluorite fluorides of Ca2+, Sr2+, Ba2+, Cd2+, Pb2+
BaCl2, SrCl2, ZrO2, ThO2, UO2
antifluorite oxides and sulfides of Li +, Na+, K+, Rb+
rutile fluorides of Mg2+, Ni2+, Mn2+, Zn2+, Fe2+
oxides of Ti4+, Mn4+, Sn4+, Te4+

In the cesium chloride (CsCl) structure, the Cs+ ion (the central ion in the CsCl structure
shown fig 4.9) has eight Cl - ions as nearest neighbors (the Cs+ is said to have a combination number
of 8). In the sodium chloride (NaCl) crystal, a Na+ ion has six Cl- ions as nearest neighbors (a
coordination number of 6). In the zinc blende (ZnS) structure, each Zn 2+ ion has four S2- ions at
nearest neighbors (a coordination of 4). In terms of crystal stability brought about by plus-minus
+
attractions, the CsCl crystal in which each Cs ion has a coordination of 8, would appear to be best.
There is, however, another factor to take into consideration: the distance between cation and the
anion, d, which becomes a matter of comparison of the size of the cation to the size of the anion. In
the CsCl structure, the Cs+ ion in the center is assumed to touch each of the Cl - ions at the corners
Consider a compound in which the cation is much smaller than the anion. A small cation could not
touch the anions that surround it since electrostatic repulsions between the anions would prevent the
anions from being squeezed together. As a result, the size of the plus-minus attraction would be
comparatively low (d would be larger than necessary). In such an event, the compound would
crystallize in a pattern with a lower coordination but one that would permit close cation-anion contact.

EXERCISES

Solve the following problems:

1. Iridium has a face-centered cubic unit cell with an edge length of 383.3 pm. The density of iridium
3
is 22.61 g/cm . Use these data to calculate a value for Avogadro’s number.

2. Vanadium crystallizes with a body-centered unit cell. The radius of a vanadium atom is 131 pm.
Calculate the density of vanadium in g/cm3.

3. A metal crystallizes in a face-centered cubic structure and has a density of 11.9 g/cm3. If the radius
of the metal atom is 138 pm, what is the most probable identity of the metal?

4. At a certain temperature and pressure an element has a simple body-centered cubic unit cell. The
corresponding density is 4.53 g/cm3 and the atomic radius is 1.78 Ao. Calculate the atomic mass fo
this element.

5. Metallic iron crystallizes in a type of cubic unit cell. The unit cell edge length is 287 pm. The density
of iron is 7.87 g/cm3. How many iron atoms are there within one unit cell?

CHEMISTRY LABORATORY

ACTIVITY 5
CRYSTALLINE STRUCTURE

1. Mo crystallizes in a body-centered cubic arrangement. Calculate the radius of one atom, given the
3
density of Mo is 10.28 g/cm .
2. Iridium crystallizes in a face-centered cubic unit cell that has an edge length of 3.833 A o.
a) Calculate the radius of an iridium atom.
b) Calculate the density of iridium metal.

3. An element crystallizes in a body-centered cubic lattice. The edge of a unit cell is 2.86 A o and the
density of the crystal is 7.92 g/cm3. Calculate the atomic mass of the element.

4. A metal crystallizes in a face-centered cubic unit cell. The radius of the atom is 0.197 nm. The
density of the element is 1.54 g/cm3. What is this metal?

5. Silver crystallizes in a cubic system and the edge of the unit cell is 408 pm. The density of silver is
10.6 g/cm3. How many atoms of Ag are contained in the unit cell? What type of unit cell does Ag
form?