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\
The height of unit cell (h) =
2
4r
3
The area of the base is equal to the area of six equilateral triangles, =
2
3
6 (2r)
4
. The volume of the unit cell =
2
3 2
6 (2r) 4r
4 3
.
Therefore,
PF =
3
2
4
6
r
3
3 2
6 (2r) 4r
4 3
~
0.74; VF ~ 0.26 BY MUKESH SHARMA ,DPS JODHPUR
Type of Lattice point Contribution to one unit cell
Corner of cube 1/8
Edge centre of cube 1/4
Facecenter of cube 1/2
Body Center of cube 1
Type of Lattice point Contribution to one unit cell
Corner of Hexagonal unit cell 1/6
Facecenter of 1/2
Body Center of cube 3
Edge centre of hexagonal [only voids] 1/3
C
B
a
A
r
D
G
E
a
A
F
h/2
3 / a
E
a 2r =
c
Type of
UNIT
CELL
Lattice
point
Effective no. Atoms
[Z]
Coordinatio
n number
Relation
b/w a and
r
Packing
effeicency
Atoms in
contact
Primitive 8 [1/8X8]=1 6 2r =a 52 On
corner
Body
centred
9 [1/8X8]+[1X1]=2 8
4r=
68 On body
digonal
Face
centred
14 [1/8X8]+[1/4 X12]=4 12
4r=
74 On face
digonal
Hexagonal
primitive
17 [1/6X12]+[1/2X2]+3=6 12 Shortest
a=2r
74 In
hexagonal
plane
Different distances
Distance B/W nearest neighbour in primitive unit cell [two corner atom ]
2r =a
Distance B/W 2
nd
nearst neighbour in primitive unit cell [two face diagonal atom ]
Distance B/W 3
rd
nearst neighbour in primitive unit cell [twocube diagonal atom ]
Distance B/W nearest neighbour in FCC [corner to face cetre atom]
2r=
Distance B/W nearest neighbour in BCC [corner to body cetre atom] =
DistanceB/W 1
st
and4
th
layer of FCC [corner to corner on body diogonal]
DistanceB/W1
st
and2
th
layerofFCCanytwosuccessivelayer
Distance B/W atom and tetrahedral void in FCC
Distance B/W octahedral void and tetrahedral void in FCC
Distance B/W atom and octahedral void in FCC
BY MUKESH SHARMA ,DPS JODHPUR
Illustration 1: A solid has a cubic structure in which X atoms are located at the corners of the cube, Y atoms
are at the cube centres and O atoms are at the edge centres. What is the formula of the
compound?
Solution: Atoms of X are present at all the eight corners of the cube. Therefore, each atom of X at the
corner makes 1/8 contribution towards the unit cell.
Number of atoms of X per unit cell =
1
8 1
8
=
Y atom is present at the body centre, thus contribution of Y towards unit cell
= 1 1 = 1
O atom is present at each of the edge centre (number of edges of cube = 12)
And each O atom present at edge centre will make 1/4 contribution towards the unit cell.
The number of O atoms per unit cell =
1
12
4
= 3
The formula of the compound is, therefore XYO
3
Illustration 2: Potassium crystallizes in a body centred cubic lattice. What is the approximate number of unit
cells in 4.0g of potassium? Atomic mass of potassium = 39.
Solution: There will be eight atoms at corners of the cube and one atom at the body centre.
Number of atoms per unit cell =
1
8
8
+ 1 1 = 2
Number of atoms in 4.0g of potassium =
23
4
6.023 10
39
Number of unit cells in 4.0g of potassium =
23
4 6.023 10
39 2
= 3.09 10
22
IQ 1:
In a solid, oxide ions are arranged in ccp. One sixth of the tetrahedral voids are occupied by the cations A
while one third of the octahedral voids are occupied by the cation B. What is the formula of the compound?
Voids and Radius Ratio Rules
Octahedral void tetrahedral void
Radius Ratio Rules: The structure of many ionic solids can be accounted by considering the relative sizes
of the cation and anion, and their relative numbers. By simple calculations, we can work out as how many ions
of a given size can be in contact with a smaller ion. Thus, we can predict the coordination number from the
relative size of the ions.
Calculation of some limiting radius ratio values
a) Coordination Number 3: The adjacent figure shows the
smaller positive ion of radius r
+
in contact with three larger
anion of radius r
.
In this figure, AB = BC = AC = 2r
BE = r
BD = r
+
+ r
=
r r
cos30 0.866
=
= 1.155r
r+ = 1.155r
r+ = 0.155r
r
r
+
= 0.155
b) Coordination Number 4: (tetrahedron)
Angle ABC is the tetrahedral angle
Z ABC = 109 28 Z ABD =
1
2
(109 28') = 54 44'
sin (ZABD) = 0.8164 =
AD r
AB r r
+
=
+
r r 1
r 0.8164
+
+
= = 1.225
r
r
+
= 0.225
A
B
C
D
c) Coordination Number 6: (Octahedron): A cross
section through an octahedral site is shown in the adjacent
figure and the smaller positive ion touches six larger negative
ions. (Only four negative ions are shown in the figure but there
is one sphere above and the below the plane of paper).
In this figure
AB = r
+
+ r
and BD = r
+
=
+
Solving, we get
r
r
+
= 0.414
A
B
C
D
Limiting radius ratio
r
r
+
| }
]
\
Coordination
number
Shape Examples
< 0.155 2 Linear BeF
2
0.155 0.225 3 Trigonal planar B
2
O
3
0.225 0.414 4 Tetrahedral ZnS, SiO
4
4
0.414 0.732 4 Square planar PtCl
4
2
0.414 0.732 6 Octahedral NaCl
0.732 0.999 8 Body centred cubic CsCl
Illustration 3: Iron crystallises in a body centred cubic structure. Calculate the radius of Fe atom if edge
length of unit cell is 286 pm.
Solution: Edge length, a = 286 pm
For BCC, radius of atom, r =
3
a
4
=
3
286
4
=
1.732 286
4
= 123.8 pm
IQ2:
Define coordination number, what is the coordination number of each sphere in
a) Cubic closepacked structures
b) Bodycentred closepacked structures
c) c) Hexagonal closepacked structures
Calculation of density of a cubic crystal from its edge: If we know the type of crystal
structure possessed by the cubic crystal, so that the number of particles per unit cell are known and the edge
length for it is known by XRay studies, the density of the crystal can be determined.
Case I: For cubic crystals of elements:
Let the edge of the unit cell = a pm
No. of atoms present per unit cell = Z
Atomic mass of the element = M
Volume of the unit cell = (a pm)
3
= a
3
pm
3
= a
3
10
30
cm
3
Density of the unit cell,
=
Mass of the unit cell
Volume of the unit cell
a
=
, ) , )
3 30
No. of atoms in its unit cell Mass of each atom
a 10
=
3 A
3 30
M
Z
N
g/ cm
a 10
(N
A
Avogadros number) =
3 30
A
Z M
N a 10
g/cm
3
Case II: For cubic crystals of ionic compounds: Here, Z is the number of formula units present in one
unit cell and M is the formula mass. The formula will remain the same viz.
Illustration 4: A facecentred cubic element (atomic mass 60) has a cell edge of 400 pm. What is its density?
Solution: For the facecentred cubic, Z = 4
=
3
3 30
0
Z M
g/ cm
a N 10
=
3 23 30
4 60
(400) (6.02 10 ) 10
= 6.23 g/cm
3
IQ3:
The unit cell in a crystal of diamond belongs to a cubic crystal system but doesnt correspond to the Bravais
lattice. The volume of unit cell of diamond is 0.0454 nm
3
and the density of diamond is 3.52 g/cc. Find the
number of carbon atoms in a unit cell of diamond?
Classification of Ionic Structures
Simple ionic compounds are of the type AB or AB
2
where A and B represent the positively and negatively
charged ions respectively. (In any solid of the type A
x
B
y
, the ratio of coordination number of A to B would be
y :x.
Structures of Type AB: Ionic compounds of the type AB means compounds having the positively and
negatively charged ions in the ratio 1:1. These compounds can have following three type of structures.
1. Rock salt (NaCl) type
2. Cesium chloride (CsCl) type
3. Zinc blende (ZnS) type
3
30
A
Z M
g./ cm
N 10
is
forming a FCC unit cell in which Na+ is in the octahedral
voids. The coordination number of Na+ is 6 and that of
Cl
ion is
surrounded by 8 Cs
+
ions i.e. this structure has 8:8
coordination. A unit cell of CsCl consists of only one
unit of CsCl i.e. One Cs
+
ion and one Cl
ion. Few
examples of compounds having CsCl structure are CsBr,
CsI, CsCN, TlCl, TlBr, TlI and TlCN.
Cs
+
ion surrounded b
by 8 Cl
-
ions
Structure of Ionic Compounds of the Type AB2: These are the ionic compounds having
cations and anions in the ratio 1:2. Most of these compounds have calciumfluorite (CaF
2
) type structure. These
compounds have cubic close packing (CCP) arrangement in which Ca
2+
ions are present at the corners and the
centre of each face of the cube.
Each Ca
2+
ion is surrounded by 8F
ion is surrounded
by 4 Ca
2+
ions i.e. has a coordination number of 4. Thus this
structure has 8:4 coordination. Few examples of such
compounds having CaF
2
structure are BaF
2
, BaCl
2
, SrF
2
,
SrCl
2
, CdF
2
, PbF
2
and ThO
2
.
+ 2
Ca
F
In Na
2
O each oxide ion is coordinated to 8 Na
+
ions and each Na
+
ion to 4 oxide ions. Hence it has 4:8
coordination. This is called antifluorite structure. Others examples being Cl
2
O, K
2
O, Li
2
O, K
2
S, Na
2
S etc.
Ionic Radii: The internuclear distance B/Wthe ions at the adjacent corners of a unit cell can be taken as the
sum of the radius of the cation and the radius of the anion.
But its not simple to assign different values to constituting ions because its not possible to calculate the radius
of one ion without knowing the radius of other one.
It has been observed that radius of a cation is smaller than that of the corresponding atom. The reason is that
with the removal of one (or more) electrons from the valence shell of the atom, the effective nuclear charge
increases because now, it is acting on a smaller number of electrons, making the electron cloud pulled more
inward towards the nucleus than before.
On the other hand, the radius of an anion is larger than that of the corresponding atom, reason being, with
addition of one (or more) electrons to the valence shell, effective nuclear charge decreases because the same
+ 2
Zn
2
S
ions Zn
four by lly tetrahedra
surrounded ion S
2
2
+
nuclear charge is now acting on a larger number of electrons. Consequently, the force of attraction on the
electron cloud decreases and hence the ionic radius increases.
Ionic radius increases in a group with increase in atomic number as:
Li
+
< Na
+
< K
+
< Rb
+
< Cs
+
Similarly, in the halogens, the ionic radius increase as:
F
< Cl
< Br
< I
The reason for this increase is the increase in the principal quantum number though the number of electrons in
the valence shell remains the same. In the same period, the radius of isoelectronic ions (having same number of
electrons) decreases with the increase in charge of the ions. e.g. Na
+
<Mg
2+
< Al
3+
.
Illustration 5: If the close packed cations in an AB type solid have a radius of 75 pm, what would be the
maximum and minimum sizes of the anions filling the voids?
Solution: For closed packed AB type solid
r
r
+
= 0.414 0.732
Minimum value of r
=
r 75
0.732 0.732
+
= pm = 102.5 pm
Maximum value of r
=
r 75
0.414 0.414
+
= pm = 181.2 pm
IQ 4:
i) The radius of Na
+
ion is 95 pm and that of Cl
are 133 and 136 pm, respectively. Calculate length of the unit cell of KF,
KF has rocksalt structure.
Imperfection in Solids
An ionic crystal which has the same unit cell containing the same lattice points throughout the crystal is known
as ideal crystal but crystals tend to have a perfectly ordered arrangement at only absolute zero. This
arrangement corresponds to state of lowest energy. And as the temperature increases, the crystals start deviating
from the perfectly ordered arrangement. This defect may appear at a point, along a line or over a surface.
A point defect could arise due to the absence of a particle (vacancy), presence of some foreign particle at a
lattice site, presence of a foreign particle at the interstitial site or displacement of a particle to the interstitial site.
Two main defects in crystals which are discussed as follows are Schottky and Frenkel defects
Schottky Defect: This defect is caused when some of the lattice points are unoccupied and those points
are called vacancies or holes fig. (a). The number of missing positive and negative ions is the same so that the
crystal remains neutral in all. Schottky defects are more common in ionic compounds with high coordination
number, and where the sizes of positive and negative ions are almost equal for example, NaCl, KCl, CsCl and
KBr.
The number of defects increases with increase in temperature. The number of defects increases to one in 106
sites at 775 K and one in 104 sites at 1075K. The presence of large number of Schottky defects in crystal results
in significant decrease in its density.
Frenkel Defect: This defect is caused when some of the ions leave their lattice sites to occupy an
interstitial site fig. (b). Frenkel defects are more common in ionic compounds with low coordination number
and where there is large difference in size B/W positive and negative ions for example, ZnS, AgCl, AgBr and
AgI.
In pure alkali metal halides, these defects
are not very common because the ions
cannot get into interstitial positions due to
their large sizes.
Fig. (a): Schottky Defect
B
-
A
+
A
+
B
-
B
-
B
-
B
-
B
-
B
-
A
+
A
+
A
+
A
+
A
+
A
+
A
+
B
-
A
+
Fig. (b): Frenkel Defect
B
-
B
-
B
-
B
-
B
-
B
-
A
+
A
+
A
+
A
+
B
-
A
+
B
-
A
+
A
+
Metal Excess Defect: This may occur in two different ways
F-Centres: A negative ion may be absent from its lattice site leaving a hole which is occupied by an electron,
thereby maintaining the electrical balance. This type of defect is formed by crystals which would be expected to
form Schottky defects. When compounds such as NaCl, KCl, are heated with excess of their constituent metal
vapours, or treated with high energy radiation, they become deficient in the negative ions and their formulae
may be represented by AX
1o
, where o is a small fraction. The crystal lattice has vacant anion sites which are
occupied by electrons. Anion sites occupied by electrons in this way are called F centres (F is an abbreviation
Farbe, the German word for colour).
Interstitial ions and electrons: Metal excess defects also occur when an extra positive ion occupies an
interstitial position in the lattice and electrical neutrality is maintained by the inclusion of an interstitial electron.
Their composition may be represented by general formula A
1+o
X. This kind of metal excess defect is much
more common than the first and is formed in crystals which would be expected to form Frenkel defects.
Examples include ZnO, CdO, Fe
2
O
3
.
Crystals with either type of metal excess defect contain free electrons, and if these migrate they conduct an
electric current. These free electrons may be excited to higher energy levels, giving absorption spectra and in
consequence their compounds are often coloured e.g. non-stoichiometric NaCl is yellow, non-stoichiometric
KCl is lilac.
F Centre
e
Na
+
Cl
A
+
B
A
+
B
A
+
B
A
+
B
A
+
B
A
+
B
A
+
B
A
+
A
+
B
A
+
B
A
+
B
A
+
B
ions.
8. CsCl has cubic structure of ions in which Cs
+
ion is present in the body centre of the cube. If density is
3.99g cm
3.
a) Calculate the length of the edge of a unit cell.
b) What is the distance between Cs
+
and Cl
ions?
c) What is the radius of Cs
+
ion if the radius of Cl
ions in NaCl
crystal = 281 pm
3. In a cubic close packed structure of mixed oxides, the lattice in made up of oxide ions, oneeighth of
tetrahedral voids are occupied by divalent ions (X
2+
) while one half of octahedral voids are occupied by
trivalent ions (Y
3+
). What is the formula of the oxide?
4. Sodium crystallizes in b.c.c. lattice of side length 4.30 . How many atoms are present in a unit lattice?
What is density of the metal? Atomic weight of Na = 23.
5. Sodium metal crystallises in body centred cubic lattice with cell edge, 4.29. What is the radius of
sodium atom?
6. Potassium crystallises in a BCC lattice, (edge length, a = 5.20)
a) What is the distance between nearest neighbours?
b) How many neighbours does each K atom have?
c) What is the density of crystalline K?
7. KBr crystallises in the FCC unit cell (NaCl type)
a) How many K
+
ions and how many Br