Solid State Chemistry

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Solid State Chemistry

Solid:
Matter which possess rigidity having definite shape & volume is called solid.
They are highly ordered three- dimensional structures are said to be crystalline.
Because the particles of a solid are not free to undergo long- range movement, solids are rigid.
Types of solid:
1. Crystalline Solid:
- Contain regular arrangement having short range & as well as long range order.
- Definite geometric shape, Sharpe melting point, they have definite heat fusion, they undergo clean cleavage, and they
are true solid.
Eg:- Metals And Non metals
2. Amorphous Solid:
Containing irregular arrangement having short range order only, irregular shape, melting over range of temp, they do
not have definite heat of fusion they undergo an irregular cut they are pseudo solid or super cooled solid.
Eg:- Rubber ,Glass ,Plastic
Classification of Crystalline Solid:
Crystal Lattice:
The main characteristic of crystalline solid is regular and repeating pattern of constituent particle.
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If the three dimensional arrangement of constituent particle in a crystal is present diagrammatically, in which each
particle is depicted as point, the arrangement is called crystal lattice.
Accordingly, a regular 3-D arrangement of constituent particles in space is known as crystal lattice or space lattice.
There are only 14 possible three dimensional arrangement of lattice corresponding to seven crystal system are known
as Bravais Lattice.
The following are the characteristics of crystal lattice
a. Each point in a lattice is called lattice point or lattice site.
b. Each point in crystal lattice represent one constituent particle which may be an atom or molecule.
c. Lattice point join straight line to bring out the geometry of lattice.
Unit Cell:
The smallest three dimensional portion of a complete space lattice which when repeated over and again in di erent
direction produces the complete space lattice is called unit cell.
Its dimensions along the three edges a, b and c, which may or may not me mutually perpendicular to each other.
The angle between the edges α (between b and c),β (between a and c)and γ(between a and b) therefore a unit cell is
characterized by six parameters a, b, c, α,β and γ.
Unit cell can be broadly divided into two types:
A) Primitive Unit Cell
B) Center Unit Cell
A) Primitive Unit Cell : The particles are present only on the corner positions of a unit cell.
B) Center Unit Cell : When a unit cell contain one or more particles present at position other than corner in addition to
those at corner is called center unit cell.
Generally this have three types.
a) Body center unit cell : Such unit cell contain one constituent particle at its body center besides the ones that are its
corner.
b) Face- center unit cell : Such unit cell contain one particle present at center of each face, beside the ones that are
corner.
c) End- center/Base-center unit cell: One constituent particle is present at the center of any two opposite faces along
with the ones present at its corner.
Basic Shapes of Unit Cell :
There are seven basic shapes of unit cell of crystal which give rise to seven crystal system.
Crystal system characterized on the basis of angle between edges of unit cell and length of edge which determine the
shape and size of the crystal.
Number of Atoms per Unit Cell:
a) Simple cubic unit cell: 1 (1/8th part at corner x 8) = 1

b) Body center unit cell: 1 (1/8th part at corner x 8) + 1 (center of the body) =2
c) Face center unit cell: 1 (1/8th part at corner x 8) + 3 (1/2 atom at each face x 6) = 4
d) Base center unit cell: 1 (1/8th part at corner x 8) + 1(1/2 atom at each face x 2) =2
Atomic Packing Factor:
Space occupied by atom in a unit cell is called atomic packing factor (APF) or atomic packing density or e iciency.
APF = (Volume of the atom in unit cell )/(volume of the unit cell)
Volume of the atom in unit cell = no. of atoms present in unit cell x volume of atoms i.e. ( 4/3 πr3) and simply volume of
the cubic unit cell is a3 i.e. (edge length)3
a) Simple Cubic Unit Cell:
No. of Atom in SC = 1
Volume of Atoms = 4/3 πr3
Volume of Unit Cell = a3
Relation between r and a is a = 2r
APF = (1 ×4/3 πr3)/a3
= (1 ×4/3 πr3)/(2r)3
= 0.52
APF of SC system is 0.52 or in percentag 52%.
b) Body Center Cubic Unit Cell (BCC) :
No. of atom in BCC = 2

Volume of atoms = 4/3 πr3
Volume of unit cell = a3
Relation between r and a is 4r =√(3 )a ( apply Pythagoras theorem)
APF = (2 ×4/3) πr3)/(a)3
= (2 ×4/3 πr3)/(4/√3 a)3
= 0.68
APF of BCC system is 0.68 or in percentag 68%.
c) Face Center Cubic Unit Cell (FCC) :
No. of atom in BCC = 4

Volume of atoms = 4/3 πr3
Volume of unit cell = a3
Relation between r and a is 4r =√(2 )a (apply Pythagoras theorem)
APF = (4 ×4/3 πr3)/(a)3
= (2 ×4/3 πr3)/(4/√2 a)3
= 0.74 %
d) Hexagonal Closed Packed (HCP):
e) Cubic Unit Cell Summary:
Summary:
Atom Positions in Cubic Unit Cells :

Cartesian coordinate system is use to locate atoms.
In a cubic unit cell :
- y axis is the direction to the right.
- x axis is the direction coming out of the paper.
- z axis is the direction towards top.
- Negative directions are to the opposite of positive directions.
Atom positions are located using unit distances along the axes.
Direction in Cubic Unit Cell :

In cubic crystals, direction indices are vector components of directions resolved along each axes, resolved to smallest
integers.
Direction indices are position coordinates of unit cell where the direction vector emerges from cell surface, a er
converted to integers.
Procedure for finding direction Indices:
Lattice Plane
Miller Indices are used to refer to specific lattice planes of atoms.

(The method of making the plane symbolically was made by English crystallographer Miller and hence the indices of
planer called Miller indices).
They are reciprocals of the fractional intercepts (with fractions cleared) that the plane makes with the crystallographic
x, y and z axes of three nonparallel edges of the cubic unit cell. It write in a bracket (h k l)and read as e.g. (1 1 1) one one
one.
Important features of miller indices of crystal plane
1. All the parallel equidistance plane have the same Miller indices. Thus Miller indices define set of parallel planes.
2. If the Miller indices of two planes have same ratio (i.e.) (8 4 4) and (2 1 1 ) then plane are parallel to each other.
3. Any two plane with indices (h1 k1 l1) and (h2 k2 l2) will be perpendicular to each other if : h1h2 + k1k2 + l1l2 =0
4. Angle between any two planes is given by formulae:
Procedure for finding Miller indices
Examples:
Miller Bravais Indices for Hexagonal System:

Directions and planes in hexagonal lattices and crystals are designated by the 4-index (h k i l) Miller-Bravais notation.
The first three indices are a symmetrically related set on the basal plane, the third index is a redundant one (which can
be derived from the first two as in the formula i = - (h+k)) and is introduced to make sure that members of a family of
directions or planes have a set of numbers which are identical this is because in 2D two indices su ice to describe a
lattice (or crystal) the fourth index represents the 'c' axis (I to the basal plane).
Hence the first three indices in a hexagonal lattice can be permuted to get the di erent members of a family; while, the
fourth index is kept separate.
Basal Plane a1 = h , a2= k, a3=i and l=c Hexagonal system with (h k i l)

Examples:
Interplaner Distance :
To find the interplanar spacing for the set of planes with Miller indices (hkl), take the origin on any one plane of this set
and erect axes in the directions of crystal axes a, b and c.
The interplanar spacing d for the planes of indices (hkl) is equal to the distance from origin to the nearest plane of the
set under question.
The distance d is measured along the normal drawn from origin to the plane (hkl). Let the normal to the plane make
angles 1, 2 and 3 with a-axis, b-axis and c-axis respectively.
The plane (hkl) intersects a-axis at a/h, b-axis at b/k and c-axis at c/l.
Most probably used for cubic system a er rearranging equation
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Solid State Chemistry

X-ray di raction and Bragg’s equations
The history of X-Ray
In November 1895, Wilhelm Röntgen discovered X-rays while working at the University of Wurzburg, Germany.
Röntgen was investigating cathode rays in di erent types of evacuated glass tubes and trying to determine their range
in air.
He noticed that while the rays were being produced, a screen coated in fluorescent barium platinocyanide would glow.
He was intrigued because the screen was too far from the tube to be a ected by the cathode rays.
He assumed unkown rays, X-rays, were being emitted from the walls of the tube while the cathode ray tube was
running.
To his amazement, Röntgen found that the rays could pass straight through his hand and cast shadows of his bones on
the fluorescent screen.
He spent several weeks privately investigating the rays before publishing his results at the end of the year.
Bragg’s law:
Bragg's law is the result of experiments derived by physicist Sir William Lawrence Bragg in 1912 and first presented on
the same year to the Cambridge Philosophical Society.
William Lawrence Bragg and his father, Sir William Henry Bragg, were awarded the Nobel Prize in physics in 1915 for
their work in determining crystal structures beginning with NaCl, ZnS, and diamond.
A er Wilhelm Roentgen discovered X rays in 1895, William Henry Bragg pioneered the determination of crystal structure
by X-RAY di raction methods, began a lifelong investigation of the nature of radiation, principally X rays but also alpha
and beta particles and gamma rays.
A er the discovery of the di raction of X rays by crystals in 1912, Bragg and his son, William L., derived Bragg's law,
which relates the wavelength of X rays to the glancing angle of reflection.
In 1913 the elder Bragg built the first X-ray spectrometer, which he initially used to study X-ray spectral distributions.
Within several years they were able to use this instrument and Bragg's law to derive the structure of crystals and show
the exact positions of atoms.
Subsequently, they demonstrated that the properties and behavior of a large variety of substances can be related to the
position of their constituent atoms.
William Lawrence Bragg went on to become director of the Cavendish Laboratory in Cambridge England.
It was at this lab, while he as director, in the early 1950's that J.D. Watson and F.H. C. Crick, using the X-ray di raction
techniques that Bragg pioneered, deduced the double helical structure of Deoxyribonucleic acid.
(DNA) Biotechnology has many forms today: Crime detection, forensic science, recombinant DNA to strengthen plants
and animals as well as fetal analysis to detect birth defects just to name a few.
None of these would be possible if Watson and Crick had not deduced the structure of DNA using X-ray di raction.
Just as the engineer who is building a tall building must understand steel and cement, a scientist must understand the
double helix before she can build a molecule.
In 1915, William Henry Bragg and William Lawrence Bragg were awarded the Nobel Prize for their contributions to
crystal structure analysis.
They were the first and (so far) the only father-son team to have jointly won the prize.
Other father/son laureates include Niels and Aage Bohr, Manne and Kai Siegbahn, J. J. Thomson and George Thomson,
Hans von Euler-Chelpin and Ulf von Euler, and Arthur and Roger Kornberg, who were all awarded the prize for separate
contributions.
W. L. Bragg was 25 years old at the time, making him the youngest Nobel laureate to date.
The Mathmetical Form of Bragg's Law
n λ = 2d⋅sinθ (1)
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n is an integer (n=1,2,3,4,….) determined by the order given. In expt. n is set as equal to 1.

λ is the wavelength of x-rays, and moving electrons, protons and neutrons.
d is the spacing between the planes in the atomic lattice,
θ is the angle between the incident ray and the scattering planes.
The Derivation of Bragg's Law
Bragg di raction occurs when electromagnetic radiation or subatomic particle waves with wavelength comparable to
atomic spacings, are incident upon a crystalline sample, scattered by the atoms in the system and undergo constructive
interference in accordance to Bragg's law.
Consider conditions necessary to make the phases of the beams coincide when the incident angle equals and reflecting
angle.
The rays of the incident beam are always in phase and parallel up to the point at which the top beam strikes the top
layer at atom z.
The second beam continues to the next layer where it is scattered by atom B.
The second beam must travel the extra distance AB + BC if the two beams are to continue traveling adjacent and
parallel.
This extra distance must be an integral (n) multiple of the wavelength (λ) for the phases of the two beams to be the
same:
nλ = AB + BC (2)
Recognizing d as the hypotenuse of the right triangle Abz, we can use trigonometry to relate d and θ to the distance (AB
+ BC).
The distance AB is opposite θ so,
AB = d sinθ (3)
Because AB = BC eq. (2) becomes:
nλ = 2 AB (4)
Substituting eq. (3) in eq. (4) we have :
nλ = 2d.sinθ (5)
Bragg's Law has been derived.
Note that if only two rows of atoms are involved, the transition from constructive to destructive interference as θ
changes is gradual.
However, if interference from many rows occurs, then the constructive interference peaks become very sharp with
mostly destructive interference in between.
This sharpening of the peaks as the number of rows increases is very similar to the sharpening of the di raction peaks
from a di raction grating as the number of slits increases.
Crystal structure determination from X-ray data
-> As di raction occurs only at specific Bragg angles, the chance that a reflection is observed when a crystal is
irradiated with monochromatic X-rays at a particular angle is small (added to this the di racted intensity is a small
fraction of the beam used for irradiation).
-> The probability to get a di racted beam (with su icient intensity) is increased by either varying the wavelength (λ) or
having many orientations (rotating the crystal or having multiple crystallites in many orientations).
The three methods used to achieve high probability of di raction are shown below.
Among all this method powder method is more popular.

THE POWDER METHOD
-> In the powder method the specimen has crystallites (or grains) in many orientations (usually random).
-> Monochromatic X-rays are irradiated on the specimen and the intensity of the di racted beams is measured as a
function of the di racted angle.
-> In this elementary text we shall consider cubic crystals.
λ = 2d.sinθ (1)
For cubic system:
As we shall see soon the ratios of (h2 + k2 + l2) is proportional to sin2θ which can be used in the determination of the
lattice type.
Allowed reflections in SC, FCC, BCC & DC Crystals:
Determination of Crystal Structure from 2θ versus Intensity Data in Powder Method :

In the power di raction method a 2θ versus intensity (I) plot is obtained from the di ractometer (and associated
instrumentation).
Powder di raction pattern from Al
Radiation: Cu Kα, λ = 1.54 Å
To know the lattice type we need only the position of the peaks (as tabulated below)
From the ratios in column 6 we conclude that, given crystal structure has FCC arrangement.
Close Packed Structure
Matters exist in solid state because of close packing of their constituent particles.
There are two types of close packing found in solids.
These are Cubic Close Packed (ccp) and Hexagonal Close Packed (hcp) lattice.
Cubic Closed Packed (CCP)
In this type of packing, the spheres of molecules are adjacent to each other that each row of spheres in a particular
dimension is a repetition of the pervious row.
The spheres of a particular row don’t fit in the depressions between two adjacent spheres of the previous row.
This types of arrangement is called AAAA type arrangement.
This is also known as face centered cubic (fcc).
This type of close packing of constituent particles is found in metals like copper, silver, etc.
Lattice of this cubic close packed is simple cubic and its unit cell is primitive cubic unit cell.
Hexagonal Close Packed (HCP)
In this type of packing, the spheres of molecules of a particular row in a particular dimension are in a position that they
fit into depressions between adjacent spheres of the previous row.
This type of arrangement is called ABAB type arrangement.
This type of packed lattice is found in many metals such as magnesium, zinc, etc.
Coordination Number:
The number of adjacent particles of atoms is called coordination number.
In both ccp and hcp, each sphere is surrounded by 12 adjacent atoms, thus coordination number is equal to 12 in each
case.
Formation of void in closed packing
Empty space le a er the packing is called void.
Two types of voids are formed in ccp and hcp structures.
These are tetrahedral voids and octahedral voids.
Tetrahedral voids are formed because of formation of tetrahedron between the layers of atoms.
Thus, voids in the shape of tetrahedron are called tetrahedral voids.
Octahedral voids are formed because of formation of octahedron between the layers of atoms.
Thus, voids in the shape of octahedron are called octahedral voids.
Number of Voids:
The number of formation of voids depends upon the number of close packed spheres.
The number of tetrahedral voids is formed twice as the number of octahedral voids while close packing of atoms in ccp
and hcp structures.
Thus, if number of close packed spheres is equal to ‘N’.
Therefore, number of octahedral voids formed = N
And, the number of tetrahedral voids formed = 2N
Formula of a compound and number of voids filled:
Bigger ions, usually anions, form close packed structure and smaller ions, usually cations occupy the voids in ionic
solids.
If cations are bigger in size, they occupy octahedral voids and if are smaller enough then they occupy tetrahedral voids.
The occupation of number of voids depends upon the chemical formula of compound.
It may be possible to occupy all the voids or fraction of voids.
Examples:
(a) If cation of an ionic solid occupies all the octahedral voids, then the formula of the compound can be obtained as
follows:
Let ‘A’ are cations and ‘B’ are anions in the compound.
Since the number of close packed sphere is equal to the number of octahedral voids formed, thus the cations and
anions must be in the ratio of 1:1.
Therefore, A and B will be combined in the ratio of A:B. Thus the formula of the compound will be AB.
(b) If there are two ions A and B in an ionic compound and cations occupy all the tetrahedral voids formed because of
close packing, then the formula of the compound can be obtained as follows:
Let A is the cation and B is the anion in given compound.
Since, number of tetrahedral voids formed = 2 X number of close packed spheres.
This means A and B will combined in the ratio of 1:2 .
Therefore, formula of the compound will be AB2
Defects in Solids
Point Defects and Line Defects
Imperfections or Defects:
Any deviation from the perfect atomic arrangement in a crystal is said to contain imperfections or defects.
In fact, using the term “defect” is sort of a misnomer since these features are commonly intentionally used to
manipulate the mechanical properties of a material.
Adding alloying elements to a metal is one way of introducing a crystal defect.
Crystal imperfections have strong influence upon many properties of crystals, such as strength, electrical conductivity
and hysteresis loss of ferromagnets.
Thus some important properties of crystals are controlled by as much as by imperfections and by the nature of the host
crystals.
-> The conductivity of some semiconductors is due entirely to trace amount of chemical impurities.
-> Color, luminescence of many crystals arise from impurities and imperfections
-> Atomic di usion may be accelerated enormously by impurities or imperfections
-> Mechanical and plastic properties are usually controlled by imperfections.
Imperfections in crystalline solids are normally classified according to their dimension as follows:
1. Point imperfections (Zero dimensional defects)
2. Line imperfections (one dimensional defects)
3. Plane or surface imperfections (Two dimensional defects)
4. Volume imperfections (three dimensional defects)
Point Defect
-> The simplest of the point defect is a vacancy, or vacant lattice site.
-> All crystalline solids contain vacancies.
-> Principles of thermodynamics is used explain the necessity of the existence of vacancies in crystalline solids.
-> The presence of vacancies increases the entropy (randomness) of the crystal.
-> The equilibrium number of vacancies for a given quantity of material depends on and increases with temperature as
follows: (an Arrhenius model)
Schottky defect
-> Vacancy defect
-> Number of cation and anion missing are same
-> decrease density of crystal
-> The compound having small di erence in cation and anion size shows schottky defect
e.g. Nacl, Kcl. Cscl and AgBr
- Number of schottky defect is:
n= Nexp(-Es/2kT) where n is number of schottky defect
N= no of atomic sites
Es= energy required to produce defect
k= Boltzmann constant
T is temperature
Frenkel defect
-> Vacancy defect
-> cation are missing normal sites and goes in interstitial sites
-> It does not change density but dielectrical constant value increase
-> All halides shows frenkel defect.
-> The compound having larger di erence in cation and anion size shows Frenkel defect
Number of schottky defect is :
n= (NNi)1/2 exp(-Ev/2kT)
n is number of schottky defect
N= no of atomic sites
Ni= no. of interstitial sites
Ev= energy required to produce defect
k= Boltzmann constant
T is temperature
Metal excess defect due to anionic vacancies:

In this case, negative ions may be missing from their lattice sites leaving holes in which the electrons remain entrapped
to maintain the electrical neutrality.
This type of defect is observed in those crystals which are likely to form Schottky Defects.
For example, Alkali metal halides like NaCl and KCl show this type of defect.
When crystals of NaCl are heated in an atmosphere of sodium vapour, the sodium atoms are deposited on the surface
of the crystal.
The Cl– ions di use to the surface of the crystal and combine with Na atoms to give NaCl.
This happens by loss of electron by sodium atoms to form Na+ ions.
The released electrons di use into the crystal and occupy anionic sites.
As a result the crystal now has an excess of sodium.
The anionic sites occupied by unpaired electrons are called F-centres (from the German word Farbenzenter for colour
centre).
They impart yellow colour to the crystals of NaCl.
The colour results by excitation of these electrons when they absorb energy from the visible light falling on the crystals.
Similarly, excess of lithium makes LiCl crystals pink and excess of potassium makes KCl crystals violet (or lilac).
Metal excess defect due to the presence of extra cations at interstitial sites:
In this case, there are extra positive ions occupying interstitial sites and the electrons in another interstitial sites to
maintain electrical neutrality.
The defect may be visualised as the loss of non-metal atoms which leave their electrons behind.
The excess metal ions occupy interstitial positions.
The common example is Zinc Oxide.
Zinc oxide is white in colour at room temperature.
On heating it loses oxygen and turns yellow.
ZnO —-> Zn2+ + 1/2 O2 +2e-
Now there is excess of zinc in the crystal and its formula becomes Zn1+xO.
The excess Zn2+ ions move to interstitial sites and the electrons to neighbouring interstitial sites.
Metal Deficiency Defects

These contain less number of positive ions than negative ions.
These arise due to two ways:
(i) Cation Vacancies:
In some cases, the positive ions may be missing from their lattice sites.
The extra negative charge may be balanced by some nearby metal ion acquiring two positive charges instead of one.
This type of defect is possible in metals which show variable oxidation states.
The common examples of compounds having this defect are ferrous oxide, ferrous sulphide, nickel oxide etc.
(ii) Extra anions occupying interstitial sites:
In the case, the extra anions may be occupying interstitial positions.
The extra negative charge is balanced by the extra charges on the adjacent metal ions.
Such type of defect is not common because the negative ions usually very large and they cannot easily fit into the
interstitial sites.
Example: Defect due to cationic Fe2+ vacancy.
-> FeO heated in oxygen atmosphere → FexO (x < 1)
-> Vacant cation sites are present
-> Charge is compensated by conversion of ferrous to ferric ion:
Fe2+ → Fe3+ + e-
-> For every vacancy (of Fe cation) two ferrous ions are converted to ferric ions → provides the 2 electrons required by
excess oxygen.
Line or Lattice imperfection

1. Edge Dislocation:
In perfect crystal, atoms are arranged in both vertical and horizontal planes parallel to the side faces.
If one of these vertical planes does not extend to the full length, but ends in between within the crystal it is called ‘edge
dislocation’.
In the perfect crystal, just above the edge of the incomplete plane the atoms are squeezed and are in a state of
compression.
Just below the edge of the incomplete plane, the atoms are pulled apart and are in a state of tension.
The distorted configuration extends all along the edge into the crystal.
Thus as the region of maximum distortion is centered on the edge of the incomplete plane, this distortion represents a
line imperfection and is called an edge dislocation.
Edge dislocations are represented by '⊥' or 'T' depending on whether the incomplete plane starts from the top or from
the bottom of the crystal.
These two configurations are referred to as positive and negative edge dislocations respectively.
2. Screw Dislocation
In this dislocation, the atoms are displaced in two separate planes perpendicular to each other.
It forms a spiral ramp around the dislocation.
The Burgers Vector is parallel to the screw dislocation line.
Speed of movement of a screw dislocation is lesser compared to edge dislocation. Normally, the real dislocations in the
crystals are the mixtures of edge and screw dislocation.
Mixed dislocation.
This dislocation has both edge and screw character with a single Burgers vector consistent with the pure edge and pure
screw regions.
Plane defect:
1. Grain boundary
They are the imperfections which separate crystals or grains of di erent orientation in a poly crystalline solid during
nucleation or crystallization.
It is a two dimensional imperfection. During crystallization, new crystals form in di erent parts and they are randomly
oriented with respect to one another.
They grow and impinge on each other.
The atoms held in between are attracted by crystals on either side and depending on the forces, the atoms occupy
equilibrium positions.
These positions at the boundary region between two crystals are distorted.
As a result, a region of transition exists in which the atomic packing is imperfect.
The thickness of this region is 2 to 10 or more atomic diameters.
The boundary region is called a crystal boundary or a grain boundary.
The boundary between two crystals which have di erent crystalline arrangements or di erent compositions, is called
as interphase boundary or commonly an interface.
2. Tilt Boundary
This is called low-angle boundary as the orientation di erence between two neighbouring crystals is less than 10°.
The disruption in the boundary is not so severe as in the high-angle boundary.
In general low-angle boundaries can be described by suitable arrays of dislocation.
Actually a low-angle tilt boundary is composed of edge dislocation lying one above the other. The angle or tilt will be
θ=b/D where b = Burgers vector and D = the average vertical distance between dislocations.
3. Twin Boundary
If the atomic arrangement on one side of a boundary is a mirror reflection of the arrangement on the other side, then it
is called as twin boundary.
As they occur in pair, they are called twin boundaries.
At one boundary, orientation of atomic arrangement changes. At another boundary, it is restored back.
The region between the pair of boundaries is called the twinned region.
These boundaries are easily identified under an optical microscope.
Volume Imperfection
Volume defects such as cracks may arise in crystals when there is only small electrostatic dissimilarity between the
stacking sequences of close packed planes in metals. Presence of a large vacancy or void space, when cluster of atoms
are missed is also considered as a volume imperfection.
Foreign particle inclusions and non-crystalline regions which have the dimensions of the order of 0.20 nm are also
called as volume imperfections.
Theoretical Density of the Crystal
If the length of edge of the unit cell is known we can calculate the density of the crystal as follows:
Let length of edge of the unit cell be a.
Volume of the unit cell (V) = (side)3 =(a)3
Density of the unit cell = (Mass of unit cell)/(Volume of unit cell)
Mass number of the unit cell = number of atoms in a unit cell × Mass of one atom = n × mg
But mass of one atom (m) = (Atomic wt.(M))/(Avagadro number (NA))
Density of unit cell = (n ×M)/(V ×NA)
Example 1.
An element (atomic mass = 60) having face-centred cubic crystal has a density of 6.23 g cm-3 What is the edge length of
the unit cell.
Solution: since element has fcc structure hence there are 4 atoms in a unit cell (or n = 4).
Atomic mass is 60 (or M = 60) .
Density of unit cell = (n ×M)/(V ×NA)
Therefore, 6.23 g cm-3 =(4 ×60)/(V ×6.023×(10)23 )
A er simplify, V= 6.4 x 10-24 cm3
∴ a = 4 x 10-8 cm.
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10/18/2017 IfAS : India's No - 1 Life Science & Chemical Science (NET , GATE , M.Sc.

Solid State Chemistry

Classification of Crystalline Solid:

Number of Atoms per Unit Cell:

a) Simple cubic unit cell: 1 (1/8th part at corner x 8) = 1

No. of atom in BCC = 2

No. of atom in BCC = 4

e) Cubic Unit Cell Summary:

Atom Positions in Cubic Unit Cells :

Direction in Cubic Unit Cell :

Procedure for finding direction Indices:

Miller Indices are used to refer to specific lattice planes of atoms.

Procedure for finding Miller indices

Miller Bravais Indices for Hexagonal System:

Basal Plane a1 = h , a2= k, a3=i and l=c Hexagonal system with (h k i l)

Most probably used for cubic system a er rearranging equation

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Solid State Chemistry

n is an integer (n=1,2,3,4,….) determined by the order given. In expt. n is set as equal to 1.

Among all this method powder method is more popular.

Allowed reflections in SC, FCC, BCC & DC Crystals:

Determination of Crystal Structure from 2θ versus Intensity Data in Powder Method :

Metal excess defect due to anionic vacancies:

Metal Deficiency Defects

Line or Lattice imperfection

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