CHEMISTRY INVESTIGATORY PROJECT

CRYSTAL LATTICES
A Study of The Structures of Solids
Around Us
__

By Seshal Jain, XII E

Submitted to Mrs. Pratima Tiwari
Crystal Lattices

CERTIFICATE

This is to certify that the following is a bonafide record of the chemistry

project work done by Seshal Jain of The Shishukunj International
School, under the guidance of Mrs. Pratima Tiwari (Subject Teacher), in
partial fulfilment of curriculum of Central Board of Secondary Education
(CBSE) during the academic year 2018-2019.

_____________________ _____________________

Mrs. Pratima Tiwari External Examiner

_____________________ _____________________

Mrs. Lalita Singh School Stamp

Crystal Lattices

ACKNOWLEDGEMENT

This project would not have been possible without proper guidance and
support from the chemistry experts, Mr. Sundar and Mrs. Pratima Tiwari,
my chemistry teacher. I am highly indebted to the former for sharing her
indispensable time and knowledge to make this project a success. I am
grateful to Mr. Sundar for letting me use the chemistry lab. I would like
express my gratitude towards the school authorities and Mrs. Lalita Singh,
the principal, for providing me with best of the facilities and environment
and giving such wonderful opportunities to shine. Finally, I want to thank
my classmates who have willingly helped me in every possible manner.
Crystal Lattices

TABLE OF CONTENTS

Introduction ......................................................................................... 1

Types of Solids ..................................................................................... 1

Ionic Solids ....................................................................................... 1

Metallic Solids .................................................................................. 2

Covalent Solids................................................................................. 2

Molecular Solids ............................................................................... 3

Bravais Lattices .................................................................................... 4

Cubic ................................................................................................ 5

Tetragonal ........................................................................................ 5

Orthogonal ....................................................................................... 5

Monoclinic ....................................................................................... 6

Hexagonal ........................................................................................ 6

Rhombohedral .................................................................................. 6

Triclinic ............................................................................................ 6

Unit Cell ............................................................................................... 7

Simple Cubic Unit Cell...................................................................... 8

Body Centered Cubic Unit Cell ......................................................... 8

Face Centered Cubic Unit Cell .......................................................... 9

Crystal Lattices

Cubic Closed Packing and Hexagonal Closed Packing .................... 10

Octahedral and Tetrahedral Voids ...................................................... 11

Structures of Ionic Solids.................................................................... 12

Sodium Chloride (NaCl) Structure .................................................. 12

Zinc Blende (ZnS) Structure ........................................................... 12

CsCl (Caesium Chloride) Structure ................................................. 13

CaF2 (Fluorite) Structure ................................................................ 13

Defects in Ionic Solids ........................................................................ 14

Crystal Lattices [1]

INTRODUCTION
Over 90% of naturally occurring and man-made solids are crystalline. Most
solids form with a regular arrangement of their particles because the overall
attractive interactions between particles are maximized, and the total
intermolecular energy is minimized, when the particles pack in the most
efficient manner. The regular arrangement at an atomic level is often reflected
at a macroscopic level.

Types of Solids
Ionic Solids
The force of attraction between the ions is called an ionic bond. These crystals
are formed between constituents which have very large differences in electron
attracting power so as to allow complete transfer of electrons from one
constituent to another. The force of attraction between the ions is purely
electrostatic. Since these ions are held in fixed positions, they do not conduct
electricity in the solid state. They conduct electricity in the fused state. The
forces of attraction in ionic solids are very strong and therefore they exhibit
high melting points and cleave only if force is applied along certain directions.
All ionic solids are hard and brittle.
Crystal Lattices [2]

Metallic Solids
The constituent units of metallic solids are positive ions. This array of positive
ions is held together by the free moving electron charge cloud which arises due
to the grouping of all the valence electrons. It is because of free moving
electrons that these compounds show malleability, ductility and lustre Also,
since electrons can move freely throughout the lattice, the metals exhibit high
electrical and thermal conductivity. Examples of metallic solids include Cy, Ag,
Au, Na, K etc.

Covalent Solids
Atoms are the structural units of covalent solids. These atoms are bound to
other atoms by shared electron pair bonds. These solids are formed when a large
number of the atoms are held by strong covalent bonds. This bonding extends
throughout the crystal and as a covalent bond is directional, it results in a giant
interlocking structure.

Since every atom is held rigidly in its position by four strong covalent bonds, it
results in a very hard solid. Covalent solid usually have high melting points, are
quite hard and are bad conductors of electricity. They have high latent heat of
fusion and low coefficient of expansion.
Crystal Lattices [3]

Molecular Solids
The constituent units of molecular solids are the molecules, rather than atoms
or ions. Thus, these solids have relatively high coefficients of expansion. They
melt at low temperatures and have low heat of fusion. The bonding within the
molecules is covalent and strong whereas the forces which operate between
different molecules of the crystal lattice are the weak van der Waals forces. As
a result of these weak forces, the molecular solids are soft and vaporize very
readily. These solids do not conduct electricity. The electrons are localized in
the bonds of each molecule. They are, therefore, unable to move from one
molecule to another on the application of electric field. Examples of these solids
are iodine, sulphur, phosphorus, sugar etc.

Dry ice, a molecular solid

Diamond, a covalent solid
Crystal Lattices [4]

BRAVAIS LATTICES
Crystalline structures have long range order and are anisotropic in nature.
However, every such structure can be represented by a crystal lattice, which is
a regular, three-dimensional arrangement known as a crystal lattice.

Alexander Bravais, a French mathematician described all 14 possible

arrangements of crystal lattices, which are named after him.
Crystal Lattices [5]

Cubic

Tetragonal

Orthogonal
Crystal Lattices [6]

Monoclinic

Hexagonal Rhombohedral

Triclinic
Crystal Lattices [7]

Unit Cell
The structure of a crystalline solid, whether a metal or not, is best described by
considering its simplest repeating unit, which is referred to as its unit cell. The
unit cell consists of lattice points that represent the locations of atoms or ions.
The entire structure then consists of this unit cell repeating in three
dimensions.

Each unit cell is characterized by its

i. dimensions along the three edges, a, b

and c,
ii. angles between the edges, α, β and γ.
Crystal Lattices [8]

There are several types of unit cells:

Simple Cubic Unit Cell

In a simple cubic arrangement, only the lattice
points or the “vertices” of the cube are
occupied.

As is seen in the image above, only a part of

1
each atom, th of it is inside the cell. Thus, a
8
1
total of × 8 = 1 atom is received by each cell.
8

Since each atom is surrounded by 6 other atoms, the simple cubic arrangement
has a coordination number of 6.

The simple cubic arrangement is a relatively inefficient arrangement because

only about 52% of the unit cell is occupied by the atoms.

Body Centered Cubic Unit Cell

Some metals crystallize in an arrangement that has a cubic unit cell with atoms
at all of the corners and an atom in the center, as shown in Figure 6. This is
called a body-centered cubic (BCC) solid. Atoms in the corners of a BCC unit
cell do not contact each other but contact the atom in the center. A BCC unit
cell contains two atoms: one-eighth of an atom at each of the eight corners
1
( × 8 = 1 atom from the corners) plus one atom from the center. Any atom in
8

this structure touches four atoms in the layer above it and four atoms in the
layer below it. Thus, an atom in a BCC structure has a coordination number of
8.
Crystal Lattices [9]

Face Centered Cubic Unit Cell

An FCC unit cell contains four atoms: one-eighth of an atom at each of the eight
1
corners ( × 8 = 1 atom from the corners) and ½ of an atom on each of the six
8
1
faces ( × 6 = 3 atoms from the faces). The atoms at the corners touch the
2

atoms in the centers of the adjacent faces along the face diagonals of the cube.
Because the atoms are on identical lattice points, they have identical
environments.

Atoms in an FCC arrangement are packed as closely together as possible, with

atoms occupying 74% of the volume. Hence, his structure is also called cubic
closest packing (CCP).

Face Centered Cubic Unit Cell Body Centered Cubic Unit Cell
Crystal Lattices [10]

Cubic Closed Packing and Hexagonal Closed Packing

In CCP, there are three repeating layers of hexagonally arranged atoms. Each
atom contacts six atoms in its own layer, three in the layer above, and three in
the layer below. In this arrangement, each atom touches 12 near neighbors, and
therefore has a coordination number of 12.

There is another type of arrangement in metals: Hexagonal Closed Packing, or

HCP. It differs from CCP in the sense that the third layer is positioned in a
different way. In HCP, atoms in the third layer are directly above atoms in the
first layer (i.e., the third layer is also type A), and the stacking consists of
alternating type A and type B close-packed layers (i.e., ABABAB…). In CCP,
atoms in the third layer are not above atoms in either of the first two layers (i.e.,
the third layer is type C), and the stacking consists of alternating type A, type
B, and type C close-packed layers (i.e., ABCABCABC…).
Crystal Lattices [11]

Octahedral and Tetrahedral Voids

In simple ionic structures, we usually find the anions, which are normally larger
than the cations, arranged in a closest-packed array. The smaller cations
commonly occupy one of two types of holes (or interstices) remaining between
the anions. The smaller of the holes is found between three anions in one plane
and one anion in an adjacent plane. The four anions surrounding this hole are
arranged at the corners of a tetrahedron, so the hole is called a tetrahedral hole.
The larger type of hole is found at the center of six anions (three in one layer
and three in an adjacent layer) located at the corners of an octahedron; this is
called an octahedral hole.
Crystal Lattices [12]

Structures of Ionic Solids

Sodium Chloride (NaCl) Structure
Sodium Chloride has a distinctive structure,
which is also seen in NH4Cl, NH4Br, NH4I,
AgF, AgCl and AgBr.

In this arrangement, Chloride ions are in a

CCP type of arrangement and Sodium ions
occupy all the octahedral sites.

Since each Sodium ion is surrounded by 6 Chlorine ions, this structure has a 6:6
coordination.

Zinc Blende (ZnS) Structure

This structure is found in binary
compounds in which the cation is smaller
than the anion, like CuCl, CuBr, CuI AgI
and BeS.

The Zinc atoms are in a CCP type of

arrangement and Sulphur atoms occupy
alternating tetrahedral sites. Since each
Zinc atom is surrounded by 4 Sulphur atoms and in turn each Zinc atom is also
surrounded by 4 Zinc atoms, the coordination of Zinc Blende structure is
described as 4:4.
Crystal Lattices [13]

CsCl (Caesium Chloride) Structure

In this structure, the Cesium ions from the
simple cubic arrangement and Chloride ions
occupy the cubic interstitial sites, i.e., each
Chloride ion has 8 Cesium ions as its nearest
neighbors.

Other examples of this type of structure are CsBr

and CsI. This structure is observed only when the
cations are comparable in size to the anions.

CaF2 (Fluorite) Structure

In this structure, the Ca ions form the ccp
arrangement. Fluoride ions occupy the tetrahedral
sites and the coordination number of F ion is 4.

As there are two tetrahedral sites available for

every Ca ion, the fluoride ions occupy all the
tetrahedral sites. The stoichiometry of the
compound is 1:2.

Each fluoride ion is surrounded by 4 Ca ions whereas each Ca ions is surrounded

by 8 fluoride ions giving the compound a coordination of is 8:4

Other examples of compounds which show this type of structure are SrF2, BaF2,
SrCl2, CdF2, HgF2, and PbF2.
Crystal Lattices [14]

DEFECTS IN IONIC SOLIDS

All crystalline solids contain some defects in the arrangement of their units.

These defects are broadly divided in two types: point defects, which arise from
deviations around a point, and line defects, which arise from deviations in
entire rows of lattice points.

Stoichiometric Defects
These do not affect the stoichiometry of the solid. They are also called intrinsic,
or thermodynamic defects.

In ionic solids, because of electrical neutrality, stoichiometric defects exist as

Frenkel and Schottky defects.

Frenkel defects are also called

dislocation defects. In crystals with
such defects, the smaller ion is
dislocated from its normal site to an
interstitial site, creating a vacancy
defect at its original site, and an
interstitial defect at the new site.

Such crystals must have a large

Frenkel Defect in Zinc Blende
difference in the size of their
constituent cations and anions.

Frenkel defect does not change the density of the solid.

Crystal Lattices [15]

Schottky defects, on the other hand, are

vacancy defects.

Crystals with Schottky defect have equal

number of anionic and cationic
deficiencies to maintain electrical
neutrality. Such crystals usually have
high coordination numbers and ions of
similar sizes.

They reduce the density of the solid.

Crystal Lattices

BIBLIOGRAPHY

“Lattice Structures in Crystalline Solids”, Rice University, http://opentextbc.ca

“Table of Interactive 3D Structures”, University of Liverpool,

http://chemtube3d.com

“Structure of Solid”, Minerva University,

http://minerva.mlib.cnr.it/

NCERT Chemistry Textbook