1.

0 Crystal Structures

Crystalline and amorphous are the two categories of solids. For example, ice which is

a crystalline solid possesses the following characteristics: has rigid and long-range order

and its atoms, molecules, or ions occupy specific positions. In a crystalline solid, the

arrangement of particles is such that the net attractive intermolecular forces are at their

maximum. The molecular 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 forces. For

amorphous solids such as glass, absence of a well-defined arrangement and long-range

molecular order can be observed.

Atoms or ions (described as crystalline structures) are thought of as being solid

spheres having well-defined diameters. This is known as the atomic hard-sphere model in

which spheres representing nearest-neighbor atoms touch one another. Figure 2c showed

an example of the hard-sphere model for the atomic arrangement found in some of the

common element metals. In this specific case all the atoms are identical. Sometimes the word

lattice is used in the context of crystal structures; in this sense lattice means a three-

dimensional array of points coinciding with atom positions or sphere centers.

LEARNING OBJECTIVES

• Describe the basic structural unit or building block of the crystal

structure.

• Determine to compute the density of a solid given its unit cell.

• Classify the four types of crystals.

• Describe the characteristics of amorphous solids.

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A unit cell is the basic structural (repeating) unit of a crystalline solid. Figure 1 shows

a unit cell and its extension in three dimensions. For each sphere, it denotes an atom, ion, or

molecule and it is called a lattice point. In many crystals, the lattice point does not actually

contain such a particle. Rather, there may be several atoms, ions, or molecules identically

arranged about each lattice point. To be simple, we can assume that each lattice point is

occupied by an atom where cases are mostly metals. Table 1 shows the seven types of unit

cells where every crystalline solid can be expressed.

a) b)

Figure 1. (a) unit cell and (b) an extension of unit cell in three dimensions. The black spheres

denote either atoms or molecules (Chang & Goldsby, 2017).

Table 1. The seven types of unit cells. Angle α is defined by edges b and c, angle β by edges a

and c, and angle γ by edges a and b (Chang & Goldsby, 2017).

Unit cells Figure Dimensions and angle

Simple cubic � = � = �

� = � = � = 90°

Tetragonal � = � ≠ �

� = � = � = 90°

Orthorhombic � ≠ � ≠ �

� = � = � = 90°

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SCI 401 –GENERAL CHEMISTRY

� = � = � ≠ 90°

Monoclinic � ≠ � ≠ �

� ≠ � = � = 90°

Tricilinic � ≠ � ≠ �

� ≠ � ≠ � ≠ 90°

Hexagonal � = � ≠ �

� ≠ � = 90°, � = 120°

The Face-Centered Cubic Crystal Structure

A unit cell of cubic geometry is considered to be the crystal structure found for many

metals. The face-centered cubic (FCC) is a crystal structure with atoms located at each of

the corners and the center of all the cube faces. Some familiar metals having this crystal

structure are copper, aluminum, silver, and gold (See Table 2). Figure 2a shows a hard-

sphere model for the FCC unit cell, whereas in Figure 2b the atom centers are represented

by small circles to provide a better perspective on atom positions. The aggregate of atoms in

Figure 2c represents a section of crystal consisting of many FCC unit cells. These spheres or

ion cores touch one another across a face diagonal; the cube edge length a and the atomic

radius R are related through

� = 2�√2 Equation 1

Table 3 shows the relationship between the edge length (a) and radius (r) of atoms in the
SCC, BCC and FCC cell.

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Table 2. Atomic Radii and Crystal Structures for 16 Metals (Callister & Rethwisch, 2014).

Metal Crystal

Structure*

Atomic

Radius**

(nm)

Metal Crystal

Structure*

Atomic

Radius**

(nm)

Aluminum FCC 0.1431 Molybdenum BCC 0.1363

Cadmium HCP 0.1490 Nickel FCC 0.1246

Chromium BCC 0.1249 Platinum FCC 0.1387

Cobalt HCP 0.1253 Silver FCC 0.1445

Copper FCC 0.1278 Tantalum BCC 0.1430

Gold FCC 0.1442 Titanium (�) HCP 0.1445

Iron (�) BCC 0.1241 Tungsten BCC 0.1371

Lead FCC 0.1750 Zinc HCP 0.1332

*FCC = face-centered cubic; HCP = hexagonal close-packed; BCC=body-centered cubic.

nanometer value by 10.

Example 1. Calculate the volume of an FCC unit cell in terms of the atomic

radius R.

Solution:

V = �+ ��� � =? �h�� ����� ��� �.

From the figure, solve for a: �! + �! = (4�)!

Therefore, � = 2�√2

The FCC unit cell volume �& may be computed from

�& = �+ = (2�√2)+ = ����√�

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SCI 401 –GENERAL CHEMISTRY

a) b) c)

Figure 2. For the face-centered cubic crystal structure, (a) a hard-sphere unit cell

representation, (b) a reduced- sphere unit cell, and (c) an aggregate of many atoms (Callister

& Rethwisch, 2014).

In determining the number of atoms associated with each unit cell that depends on

an atom’s location, shared with adjacent unit cells may be considered. That is, some fraction

of the atom is assigned to a specific cell. For example, for cubic unit cells, an atom completely

within the interior “belongs” to that unit cell, one at a cell face is shared with one other cell,

and an atom residing at a corner is shared among eight. The number of atoms per unit cell,

N, can be computed using the following formula:

<$

+ <&

8 Equation 2

Where Ni = the number of interior atoms; Nf = number of face atoms and Nc = number

of corner atoms

For the FCC crystal structure, there are eight corner atoms, six face atoms and no interior

atoms. Therefore, from Equation 2.

�=0+

2+

8=4

A total of four whole atoms may be assigned to a given unit cell.

There are two important characteristics of a crystal structure: (a) the coordination

number (for metals) wherein each atom has the same number of nearest-neighbor or

touching atoms; and (b) atomic packing factor (APF) which is the sum of the sphere

volumes of all atoms within a unit cell (assuming the atomic hard-sphere model) divided by

the unit cell volume. For FCCs, the coordination number is 12 as can be seen in Figure 2a.

Front face atoms has four nearest neighboring atoms around it, four face atoms that are link

from behind, and four other equivalent face atoms positioned in the next unit cell to the front

which is not shown.

From the definition of APF, the formula is:

��� = =.2>'? .@ AB? 1A.'C )* 1 >*)A &?22

D.A12 >*)A .@ &?22 =.2>'? Equation 3

MACALALAD – GAYETA - BASILAN | BATSTATEU

The Body-Centered Cubic Crystal Structure

A body-centered cubic (BCC) is another common metallic crystal structure that also

has a cubic unit cell with atoms located at all eight corners and a single atom at the center of

the cube. Figures 3a and 3b showed the diagrams of BCC unit cells with the atoms

represented by hard-sphere and reduced-sphere models while Figure 3c displayed a

collection of spheres depicting this crystal structure. Corner atoms and center touch one

another along with the diagonal of the cube, and unit cell length a and atomic radius R are

related by the way of

� = $E

√+

Equation 4

From Equation 2, the number of atoms per BCC is

� = �) +

<$

+ <&

8=1+0+8

8=2

Example 2. Show that the atomic packing factor for the FCC crystal structure

is 0.74.

Solution:
��� = =.2>'? .@ AB? 1A.'C )* 1 >*)A &?22

D.A12 >*)A .@ &?22 =.2>'? = ='

=&

Volume of a sphere (�C) in terms of the atomic radius R is equal to

��+, and the number of atoms per FCC unit cell if four. Therefore, the total

FCC atom or sphere volume is

�C = (4) $

��+ = (5

��+

From Example 1, the total unit cell volume is

�& = 16�+√2

Therefore, the atomic packing factor is

��� = ='

=&

!(

) GE)

(5E)√! = �. ��

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SCI 401 –GENERAL CHEMISTRY

The BCC crystal structure has 8 coordination number. The atomic packing factor for
BCC 0.68 which is lower than for FCC, since BCC has lesser coordination number.

a) b) c)

Figure 3. Body-centered cubic crystal structure, (a) a hard-sphere unit cell representation,

(b) a reduced-sphere unit cell, and (c) an aggregate of many atoms (Callister & Rethwisch,

2014).

The possibility of a unit cell that consists of atoms placed only at the corners of a cube

do exist and it is called the simple cubic (SC) crystal structure. The illustration is shown in

Figure 4a and 4b. Polonium, a metalloid or a semi-metal is the only simple-cubic element that

has a relatively low atomic packing factor.

a) b)

Figure 4. Simple cubic crystal structure, (a) hard-sphere unit cell, and (b) a reduced-sphere

unit cell (Callister & Rethwisch, 2014).

Table 3. The Relationship Between the edge length (a) and radius (r) of atoms in the SCC,

BCC and FCC cell (Chang & Goldsby, 2017).

Unit cells Figure Relationship

Simple Cubic a= 2r

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Body-centered cubic

b2 = a2 + a2

c2 = a2 + b2 = 3a2

c = √3a = 4r
a = 4r

√3

Face-centered cubic

b = 4r

b2 = a2 + a2

16r2 = 2a2

a = √8r

The Hexagonal Close-Packed Crystal Structure

The final common metallic crystal structure to be discussed is the hexagonal close-

packed (HCP). The top and bottom faces of the unit cell is consist of six atoms that form

regular hexagons and surround a single atom in the center. Between the top and bottom

planes, there is another plane that provides three additional atoms to the unit cell. The atoms

in this midplane have as nearest neighbors atoms in both of the adjacent two planes. Figure

5a shows a reduced-sphere unit cell for HCP structure and Figure 5b presents an assemblage

of several HCP unit cells.

To compute the number of atoms per unit cell for HCP crystal structure, the formula

is shown below:

� = �) +

<$

+ <&

5 Equation 5
One-sixth of each corner atom is designated to a unit cell instead of 8 as with the cubic

structure. This is because, HCP has 6 corner atoms in each of the top and bottom faces for a

total of 12 corner atoms, 2 face center atoms (one from each of the top and bottom faces),

and 3 midplane interior atoms. Using Equation 5, the value of N for HCP can be found.

�=3+!

(!

+ (!

5 = 6 (there are 6 atoms assigned to each unit cell)

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SCI 401 –GENERAL CHEMISTRY

a) b)

Figure 5. The hexagonal close-packed crystal structure, (a) a reduced-sphere unit cell (a

and c represent the short and long edge lengths, respectively), and (b) an aggregate of

many atoms (Callister & Rethwisch, 2014).

3.0 DENSITY COMPUTATIONS

A theoretical density (�) can be computed with a knowledge of the crystal structure

of a metallic solid through the relationship

� = !"

#!$"

Equation 6

Where n = number of atoms associated with each unit cell

A = atomic weight

VC = volume of the unit cell

Example 3. Copper (A=63.5 g/mol) has an atomic radius of 0.128 nm, an FCC

crystal structure, and an atomic weigh of 63.5 g/mol. Compute its theoretical

density, and compare the answer with its measured density.

Solution:

� = !"#$

##$"

= !"#$

(&'(%)*)$"

= (, ./012/(4!5/ 6788))('9.; </108)

&')*(&.*= > &?&'61)%/4!5/ 6788] ('.?**>&?(%./012/10876487)

= �. �� �

���

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Example 4. Gold (Au) crystallizes in a cubic close-packed structure (the

face-centered cubic unit cell) and has a density of 19.3 g/cm3. Calculate the

atomic radius of gold in picometers.

Solution:

The sequence of steps is summarized as follows:

Density of unit cellàvolume of unit cellàedge length of unit cellàradius

of Au atom

� = ����
������ ; ����� ��� ���� �� � ���� ����

� = $ 1A.'C

( >*)A &?22

( '.2

5.0!!H(0*)1A.'C

(I4.0 - J>

( '.2 J> =

1.31 � 103!( -K1'

>*)A &?22

Solve for volume

�='

L = (.+(H(0+*!-

(I.+ ,

&-)

= 6.79�103!+��+

Solve for the edge a

� = �+; �h�������, � = √�) =

√6.79�1�3!+��+ = 4.08�1038�� )

From Table 2 we see the radius of an Au sphere (r) is related to the edge

length by
� = √8 �

Therefore,

�=1

√8 = $.08H(0+#&'

√8 = 1.44�1038 �� �

(H(0+*'

( &' �

(M'

(H(0+!*'

� = ��� ��

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SCI 401 –GENERAL CHEMISTRY

4.0 X-Ray Diffraction by Crystals

X-ray diffraction refers to the scattering of X-rays by the units of a crystalline solid. The

patterns produced by scattering, or diffraction are used to deduce the particle arrangement

in the solid lattice.

Figure 5 shows the interference phenomenon associated with waves. Since X-rays are

one form of electromagnetic radiation, therefore, we would expect that waves exhibit such

behavior under relevant conditions. In 1912, Max von Laue, a German physicist

recommended that since the wavelength of X-rays is comparable in magnitude to the

distances between lattice points in a crystal, then the lattice should be able to diffract X-rays.

Interference in the waves associated with X-rays produced an X-ray diffraction pattern.
Figure 6. Constructive interference (a) and destructive interference

(b) of two waves of the same wavelength and amplitude (Chang &

Goldsby, 2017).

a) b)

Figure 7 shows a typical X-ray diffraction setup. A beam of X rays is directed at a

mounted crystal. Atoms in the crystal absorb some of the incoming radiation and then reemit

it; the process is called the scattering of X rays

Figure 7. (a) An arrangement for obtaining the X-ray diffraction pattern of a crystal. The

shield prevents the strong undiffracted X rays from damaging the photographic plate. (b) X-

ray diffraction pattern of crystalline lysozyme, a protein. The white "L" is a shadow of the

sample holder and shield (Chang & Goldsby, 2017).

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The X-ray diffraction technique gives the most accurate method for determining bond

lengths and bond angles in molecules in the solid state. Chemists can construct an electron-

density contour map from the diffraction patterns because X-rays are scattered by electrons

but it is with the use of a complex mathematical procedure. An electron-density contour map

basically tells us the relative electron densities at various locations in a molecule. The
densities reach a maximum near the center of each atom and in this manner we can

determine the positions of the nuclei and thus the molecular geometric parameters.

5.0 TYPES OF CRYSTALS

In determining the structures and properties of crystals, such as melting point,

density, and hardness it is important to consider the kinds of forces that hold the particles

together. The classification of any crystal has four types: ionic, covalent, molecular, or

metallic.

Ionic Crystals

There are two important characteristics of ionic crystals and they are as follows: (1)

They are composed of charged species and (2) anions and cations are generally quite

different in size. The radii of the ions must be known because it is helpful in understanding

the structure and stability of these compounds. It is hard to measure the radius of an

individual ion but sometimes it is possible to come up with an estimation. For example, if we

know the radius of �3 �� �� is about 216 pm, we can determine the radius of �N��� ��
��,

and from that, the radius of ��3 �� ���, and so on. For example, the ���� crystal which has

a face-centered cubic lattice (see Figure 8) shows that the edge length of the unit cell of ����

is twice the sum of the ionic radii of ��N ��� ��3. Getting the values of ionic radius given in

some references the we calculate the length of the edge to 2(95 + 181) ��, �� 552 ��. In

Figure 8, the edge length shown was determined by X-ray diffraction which has a value of

564 ��. The difference between these two values tells us that the radius of an ion actually

varies slightly from one compound to another. Figure 9 shows the portions of the Na+ and

Cl- ions within a unit cell.

Figure 8. Relation between the radii of Na+ and Cl- ions and the unit cell dimensions. Here

the cell edge length is equal to twice the sum of the two ionic radii (Chang & Goldsby, 2017).

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SCI 401 –GENERAL CHEMISTRY

Figure 9. Portions of ��N ��� ��3 Na+ ions within a face-centered cubic unit cell (Chang &

Goldsby, 2017).

Figure 10 shows the crystal structures of three ionic compounds:

����, ���, ��� ���!. ���� has the simple cubic lattice because ��N is considerably
larger

than ��N. ��� has the zincblende structure, which is based on the face-centered cubic lattice.

If the �!3 ions occupy the lattice points, the ��!N ions are located one-fourth of the distance

along each body diagonal. Other ionic compounds that have the zincblende structure include

����, ���, ���, ��� ���. ���! has the fluorite structure. The ��!N ions occupy
the lattice

points, and each �3 ion is tetrahedrally surrounded by four ��!N ions. The compounds

���!, ���!, ����!, ��� ���! also have the fluorite structure.

a) b) c)

Figure 10. Crystal structures of (a) ����, (b) ���, and (c) ���!. In each case, the cation is the

smaller sphere (Chang & Goldsby, 2017).

Most ionic crystals have high melting points which is an indication of the strong

cohesive forces holding the ions together. A measure of the stability of ionic crystals is the

lattice energy; the higher the lattice energy, the more stable the compound. Since the ions

are fixed in position, therefore these solids do not conduct electricity. The ions are free to

move when in the molten state (melted) or dissolved in water, thereby the resulting liquid

is conducting electricity.

Covalent Crystals

Covalent crystals exists when atoms are held together in an extensive three-

dimensional network altogether by covalent bonds. Examples are the two allotropes of
carbon: diamond and graphite. Each carbon atom of diamond is ��+ h��������� where it is

bonded to four other atoms (Figure 11). The unusual hardness and very high melting point

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(3550°�) of diamond are attributed with the strong covalent bonds that exist in three

dimensions while for graphite, carbon atoms are arranged in six-membered rings. The atoms

are all sp2-hybridized and each atom is covalently bonded to three other atoms. There is a

remaining unhybridized 2� orbital that is used in �� bonding.

a) b)

Figure 11. (a) The structure of diamond. Each carbon is tetrahedrally bonded to four other

carbon atoms. (b) The structure of graphite. The distance between successive layers is 335

pm (Chang & Goldsby, 2017).

Graphite is considered as a good conductor of electricity in directions along the planes

of carbon atoms, this is because electrons are free to move around in this extensively

delocalized molecular orbital. The hardness of graphite is caused by the covalent bonds that

exist in its layers which are held together by weak van der Waals forces. Furthermore, the

layers of graphite can slide one another, that’s why it is slippery to the touch and is effective

as lubricant. It is also used in pencils and ribbons made for computer printers and

typewriters.

Another example of covalent crystal is quartz (���!). The silicon atoms in quartz has

a similar arrangement to that of carbon in diamond, but in quartz there is a presence of

oxygen atom between each pair of �� atoms. A polarity exist in �� − � bond because �� and

� have different electronegativities. Still, ���! is similar to diamond in many aspects because

of its hardness and high melting point of 1610 °�.

The lattice points in a molecular crystal are occupied by molecules which has a van

der Waals forces and/or hydrogen bonding. Solid sulfur dioxide (��!) is an example in which

the predominant attractive force is a dipole-dipole interaction. The intermolecular hydrogen

bonding is mainly responsible for maintaining the three-dimensional lattice of ice.

�!, �$ ��� �8 are other examples of molecular crystals.

The molecules in a molecular crystals (except for ice) are packed together as closely

as their size and shape allow. Since van der Waals and hydrogen bonding are generally quite

weak as compared with ionic and covalent bonds, molecular crystals are more easily broken

apart than ionic and covalent crystals. Additionally, most molecular crystals melt at

temperature below 100 °�.

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SCI 401 –GENERAL CHEMISTRY

Metallic Crystals

Metallic crystals has the simplest structure because every lattice points in the crystal

are occupied by an atom of the same metal. Metallic crystals are usually body-centered cubic,

face-centered cubic or hexagonal close-packed, therefore metallic elements are usually very

dense.

The bonding electrons in a metal are delocalized over the entire crystals which is

actually different from other types of crystals. The metal atoms in a crystal can be imagined

as an array of positive ions immersed in a sea of delocalized valence electrons and these

delocalized electron makes metals a good conductor of heat and electricity. And also, metal’s

strength is caused by the great cohesive forces resulting from delocalization.

Table 4 summarizes the properties of the four different types of crystals.

Table 4. Types of Crystals and General Properties (Chang & Goldsby, 2017).

Type of Crystal Force(s) Holding

General Properties Examples

Ionic Electrostatic

attraction

Hard, brittle, high

melting point, poor

conductor of heat

and electricity

NaCl, LiF, MgO,

CaCO3

Covalent Covalent bond Hard, high melting

point, poor

conductor of heat

and electricity

C (diamond)**, SiO2

(quartz)

Molecular* Dispersion forces,

dipole-dipole forces,

hydrogen bonds

Soft, low melting

point, poor
conductor of heat

and electricity

Ar, CO2, I2, H2O,

C12H22O11 (sucrose)

Metallic Metallic bond Soft to hard, low to

high melting point,

good conductor of

heat and electricity

All metallic

elements; for

example, Na, Mg, Fe,

Cu

*Included in this category are crystals made up of individual atoms.

**Diamond is a good thermal conductor.

6.0 AMORPHOUS SOLIDS

We all know that crystalline form of solids are most stable, but if it solidify rapidly

then its atoms or molecules do not have time to align themselves and may become locked in

positions other than those of regular crystals. This resulting solid is said to be amorphous.

Amorphous solids lack a regular three-dimensional arrangement of atoms.

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Glass is an example of an amorphous solid. Glass commonly refers to an optically

crystallizing. By product of a fusion, we mean that the glass is formed by mixing molten

silicon dioxide (���!), with compounds such as sodium oxide (��!�), boron oxide (�!�+),

and certain transition metal oxides for color and other properties. Silicon dioxide is the chief

component of glass. In some aspect glass acts more like a liquid than a solid. Glass lacks a

long-range periodic order as results shown in X-ray diffraction studies.

X-ray diffraction studies show that

Figure 12 shows two-dimensional schematic representations of crystalline quartz

and amorphous quartz glass.

a) b)

Figure 12. Two-dimensional representation of (a) crystalline quartz and (b) noncrystalline

quartz glass. The small spheres represent silicon. In reality, the structure of quartz is three-

dimensional. Each Si atom is tetrahedrally bonded to four O atoms (Chang & Goldsby, 2017).

There are about 800 different types of glass in common use today. Figure 12 shows

two-dimensional schematic representations of crystalline quartz and amorphous quartz

glass.

Table 5. Composition and Properties of Three Types of Glass (Chang & Goldsby, 2017)

Name Composition Properties and Uses

Pure quartz glass 100% SiO2 Low thermal expansion, transparent to

wide range of wavelengths. Used in

optical research.

Pyrex glass SiO2, 60-80%

B2O3, 10-25%

Al2O3, small amount

visible and infrared, but not to UV

radiation. Used mainly in laboratory

and household cooking glassware.

Soda-lime glass SiO2, 75%

Na2O, 15%

CaO, 10%

Easily attacked by chemicals and

sensitive to thermal shocks. Transmits

visible light, but absorbs UV radiation.

Used mainly in windows and bottles.

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SCI 401 –GENERAL CHEMISTRY

The color of the glass is because of the presence of metal ion (as oxides). For example,

green glass contains iron(III) oxide, ��!�+, or copper(II) oxide, ���; yellow glass contains

uranium(IV) oxide, ��!; blue glass contains cobalt(II) and copper(II) oxides, ��� ��� ���;

and red glass which contains small particles of gold and copper. Most of the ions mentioned

are derived from the transition metals.