Basic Concepts of Crystal Structures ● Angle γ by edges a and b

CRYSTAL STRUCTURE Unit Cells

Categories of Solids
● Crystalline Solid
● Amorphous Solid

Crystalline Solid
● rigid, long-range order
● atoms occupy specific position
● arrangement: net attractive intermolecular
forces are at their maximum.
● molecular forces for the stability: covalent
bonds, van der Waals forces, hydrogen
bonds, or a combination.

Amorphous
● absence of well-defined and long-range
order

Atomic Hard-Sphere Model

● atoms or ions (crystalline structures) as
solid spheres having well-defined
diameters
● atomic hard-sphere model: spheres
representing nearest-neighbor atoms touch
one another.
● lattice: three-dimensional array of points
The Face-Centered Cubic Crystal
coinciding with atom positions or sphere
● unit cell of cubic geometry: found for many
centers
metals
● FCC - atoms located at each of the corners
Unit Cells
and the center of all the cube faces
● basic structural (repeating) unit of a
● ex: copper, aluminum, silver, and gold
crystalline solid
● for each sphere: it denotes an atom, ion, or
molecule and is called a lattice point.
● 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.
● each lattice point is occupied by an atom
● touch one another across a face diagonal
where cases are mostly metals

● APF: 74% (occupied); 26% (empty)

● cell Volume:
3
VC = 16𝑅 2
The Seven Types of Unit Cells ● volume of the atoms in a unit cell:
3
● Angle α is defined by edges b and c (4)
4
π𝑅
3
● Angle β by edges a and c
● coordination number: 12 atoms
Number of atoms per unit cell
● depends on an atom’s location, shared with ● cube length:
adjacent unit cells 𝑎 = 2𝑟
● some fraction of the atom is assigned to a 𝑁 = 0 +0+
8
= 1
8
specific cell
● APF: 52%;48%
● cell volume:
V = a3
Two Important Characteristics of Crystal Structure
● volume of the atoms in a unit cell:
● coordination number (for metals), each 3
4
atom has the same number of (1) 3
π𝑅
nearest-neighbor or touching atoms ● coordination number: 6 atoms
● atomic packing factor (APF), sum of the
sphere volumes of all atoms within a unit cell
(assuming the atomic hard-sphere model)
divided by the unit cell volume

The Body-Centered Cubic Crystal Structure

● has a cubic unit cell
● atoms located at all eight corners and a
single atom at the center of the cube The Hexagonal Close-Packed Crystal Structure
● the top and bottom faces of the unit cell
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
● corner and center atoms touch one another atoms to the unit cell
along with the diagonal of the cube ● the atoms in the midplane have as nearest
4𝑅
𝑎 = neighbors atoms in both of the adjacent two
3
planes

● AFP: 68%:32%
● cell volume:
(4𝑟 3)3
● volume of the atoms in a unit cell:
4 3
(2) 3
π𝑅
● coordination number: 8 atoms

Simple Cubic Crystal Structure

● atoms placed only at the corners of a cube
● ex: polonium (a metalloid or a semi-metal
that has a relatively low atomic packing Density Computations
factor) ● formula for theoretical density (ρ):
𝑛𝐴
ρ = 𝑉𝐶 𝑁𝐴

n = number of atoms associated with each unit cell

A = atomic weight
VC = volume of the unit cell
NA = Avogadro’s number (6.022 x 10^23 atoms/mol)
 ● most have high melting points: strong
X-Ray Diffraction by Crystals cohesive forces that holds the ions together
● refers to the scattering of X-rays by the units ● measure of the stability: lattice energy; the
of a crystalline solid. higher, the more stable
● used to deduce the particle arrangement ● ions are fixed in position, so solids do not
in the solid lattice conduct electricity
● X-rays are one form of electromagnetic ● ions are free to move in the molten state
radiation: waves exhibit such behavior under (melted) or dissolved in water, so the
relevant conditions resulting liquid can conduct electricity
● Max von Laue (1912) recommended that ● radii of the ions: helpful in understanding
since the wavelength of X-rays is the structure and stability; hard to measure
comparable in magnitude to the distances but sometimes possible with an estimation
between lattice points in a crystal, then the For example:
lattice should be able to diffract X-rays. NaCl (FCC) shows that the edge length of
● interference in the waves associated with the unit cell of NaCl is twice the sum of the ionic radii
X-rays produced an X-ray diffraction pattern of Na+ and Cl-.
● constructive interference (a) and = 2(95 + 181) pm, or 552pm
destructive interference (b) of two waves of
the same wavelength and amplitude The edge length shown was determined by
● A beam of X rays is directed at a mounted X-ray diffraction which has a value of 564pm.
crystal. Atoms in the crystal absorb some of
the incoming radiation and then re-emit it;
the process is called the scattering of X
rays.

The difference between these two values

tells us that the radius of an ion actually varies slightly
from one compound to another.
● X-ray diffraction technique: most accurate
method for determining bond lengths and
bond angles in molecules in the solid state
● an electron-density contour map can be
constructed from the diffraction patterns
because X-rays are scattered by electrons ● CsCl has the simple cubic lattice because
● electron-density contour map tells us the Cs+ is considerably larger than Na+.
relative electron densities at various
locations in a molecule
● the densities reach a maximum near the
center of each atom, then we can determine
the positions of the nuclei and the
molecular geometric parameters ● ZnS has the zincblende structure, which is
based on the face-centered cubic lattice. If
Types of Crystals the S2- ions occupy the lattice points, the
● kinds of forces is important to determine Zn2+ ions are located one-fourth of the
structures and properties of crystals distance along each body diagonal.
● has four types: ionic, covalent, molecular, or ● other ex: CuCl, BeS, CdS and HgS
metallic

Ionic Crystals
● two important characteristics:
○ composed of charged species and
○ anions and cations are generally quite ● CaF2 has the fluorite structure. The Ca2+
different in size ions occupy the lattice points, and each F-
 ion is tetrahedrally surrounded by four ○ there is a presence of oxygen atom
Ca2+ions. between each pair of Si atoms
● other ex: SrF2, BaF2, BaCl2, and PbF2 ○ polarity exist in Si - O bond because Si
and O have different electronegativities
Covalent Crystals ○ SiO2 is still similar to diamond in many
● exist when atoms are held in an extensive aspects because of its hardness and high
three-dimensional network altogether by melting point of 1610 °C
covalent bonds
● ex: two allotropes of carbon - diamond & Molecular Crystals
graphite ● lattice points in a molecular crystal are
● each carbon atom of diamond is sp3 occupied by molecules which has a van der
hybridized: bonded to four other atoms Waals forces and/or hydrogen bonding.
● “sp3 hybridization” - mixing of one ● ex: solid sulfur dioxide (SO2)
2s-orbital and three 2p-orbitals to create four ○ predominant attractive force:
hybrid orbitals with same characteristics dipole-dipole interaction
● for an atom to be sp3 hybridized, it must ● intermolecular hydrogen bonding:
have an s orbital and three p orbitals. responsible for maintaining the
● unusual hardness and very high melting three-dimensional lattice of ice
point (3550°C) of diamond are attributed with ● other ex: I2, P4, and S8
the strong covalent bonds that exist in three ● molecules (except for ice) packed together
dimensions as closely as their size and shape allow
● for graphite, carbon atoms are arranged in ● van der Waals and hydrogen bonding are
six-membered rings quite weak, this crystals are more easily
● atoms are all sp2-hybridized, each atom is broken apart
covalently bonded to three other atoms ● most melt at temperature below 100 °C
● there is a remaining unhybridized 2p orbital
that is used in pi bonding Metallic Crystals
● simplest structure: as every lattice points
are occupied by an atom of the same metal
● most are usually BCC, FCC, AND HCP,
therefore they are usually very dense
● bonding electrons in a metal are delocalized
over the entire crystals (diff from others)
Diamond: each carbon is tetrahedrally bonded to four ● atoms can be imagined as an array of
other carbon atoms positive ions immersed in a sea of
Graphite: the distance between successive layers is delocalized valence electrons
335 pm ● these makes metals a good conductor of
● Graphite: good conductor of electricity in heat and electricity
direction along the planes of carbon atoms ● metal’s strength is caused by the great
○ electrons are free to move around in this cohesive forces resulting from delocalization
extensively delocalized molecular orbital
○ hardness of graphite: caused by the
covalent bonds that exist in its layers
which are held together by weak van der
Waals forces
○ the layers of graphite can slide one
another: slippery to the touch and is
effective as lubricant
○ also used in pencils and ribbons for
printers and typewriters
● Quartz (SiO2)
○ silicon atoms has a similar arrangement
to that of carbon in diamond
Types of Crystals and General Properties ○ color: because of the presence of metal
ion (as oxides)
○ ex:
■ Green glass - Iron (III) Oxide (Fe2O3)
or Copper (II) Oxide (CuO)
■ Yellow glass - Uranium (IV) Oxide
(UO2)
■ Blue glass - Cobalt (II) (CoO) and
Copper (II) Oxides (CuO)
■ Red glass - small particles of Gold and
Copper
*derived from the transition metals

Amorphous Solids
● when crystalline solidify rapidly then its
atoms do not have time to align
themselves and may be locked in positions
● lack a regular three-dimensional
arrangement of atoms
● ex: Glass - optically transparent fusion
product of inorganic materials that has
cooled to a rigid state without crystallizing
○ fusion: glass is formed by mixing molten
silicon dioxide (SiO2), with sodium oxide
(Na2O), boron oxide (B2O3), and certain
transition metal oxides
○ chief component of glass: Silicon Oxide
○ sometimes acts more like a liquid than a
solid
○ lacks a long-range periodic order as
shown in X-ray diffraction studies

(a) crystalline quartz (b) non crystalline quartz glass

○ small spheres represent silicon

○ structure of quartz: three-dimensional

Composition and Properties of Three Types of Glass

○ there are about 800 different types of

glass