Beruflich Dokumente
Kultur Dokumente
CHEMISTRY
SOLID STATE
LECTURE # 1 TO 7
[1]
Lecture # 1
Section (A) Basics of Solid State
(1)
Definition type of solid (Ionic/Covalent/Metallic/Molecular) + Properties.
(2)
Definition of lattice + Unit cell + Coordination Number + density.
(3)
1D & 2D lattice Square and Hexagonal packing.
(4)
Classification of unit cells in 3D ; 7 Crystal system + 14 Bravis lattice.
(1)
[10 Mins]
[15 Mins]
[15 Mins]
[20 Mins]
Solids
Particles have fixed
locations they can
only vibrate.
Forces b/w
particles
Forces of attraction
is zero
Intermediate value
Interparticle
Separation
Small Interparticle
separation
Separation is close
to zero.
Volume/Shape
No fixed volume, no
definite shape.
Response to
external
changes
Compression and
expansion can be
done to large
extent.
Small extent of
compression and
expansion
Compression /
expansion least
possible.
Constant heat
capacity
Heat capacities
depend on process
Whether a given system would exist as solid, liquid or gas depends upon two universal opposing tendencies
associated with the particles:
(i) Tendency of mutual attraction.
(ii)Tendency to escape from each other.
Gases: Escaping tendency much higher than Attraction
Liquids: Escaping tendency higher than attraction but limited.
Solids: Attraction much higher that escaping tendency
Classification on the basis of forces among constituting particles:
Solid
Constituent
particles
Molecular
Molecules
Metallic
Atoms
(kernels in
e sea)
Atoms
Network
Or
Covalent
Ionic
Ions
Bonding/
Attractive
forces
i)Dispersion
ii)Dipole-dipole
interaction
iii)H-bonding
Positive ions
and electrons
(delocalized)
Covalent(short
range)
B.E.
(kJmol-1)
Coulombic(infinit
e range)
400-4000
Examples Physical
nature
mp
(K)
Electrical
Nature
0.05-40
5.25
Argon
HCl
Soft
Soft
84
158
Insulator
Insulator
10-40
70-1000
H2O(ice)
Ag. Cu,
Mg
Hard
Hard
273
~800
To
1000
~4000
Insulator
Conductor
150-500
SiO2,SiC,
Hard
diamond,
graphite
NaCl,
Hard but High
MgO
Brittle ~1500
KCl,BsCl2
Insulator
Insulator
[2]
Crystalline solids
(True solids)
1. Constituent particles
(ions, molecules, atoms)
will be arranged in a particular
fashion having long range order.
Ag. Fe,Cu,NaCl, HO(s)
2
id
liqu
T1
Temp T2
4. Anisotropic
Physical property (mechanical strength,
Refractive index, electrical conductance)
will have diff.
value in different directions.
(diff. prop. in
diff. direction)
t1
d
oli )
s
n
+
id sitio
u
n
liq tra
(
solid
only
t2
time
Isotropic
Same value in all directions.
Reason : Random arrangement of
molecules.
(same property
in all direction)
[3]
Characteristic of solids : Solids are characterized by their high density and low compressibility compared
with those of the gas phase. The values of these properties for solids indicate that the molecules (or ions)
in them are relatively close together. Solids can very easily be distinguished from liquids by their definite
shape, considerabla mechanical strength and rigidity. These properties are due to the existence of very
strong froces of attraction amongst the molecule (or ions) of the solids. It is because of these strong forces
that the structural units (atoms, ions, etc.) of the solid do not possess any translatory motion but can have
only vibrational motion about their mean positions.
Crystals and amorphous solids : Solids can generally be classified into two broad categories : crystals
and amorphous substances. The outsanding characteristics of a crystals are its sharp melting point and
its flast faces and sharp edges which, in a well developed form, are usually arranged symmetrical. These
properties are the result of a high degree of internal order which extends throughout the crystal (a definite
pattern constantly repeating in space), i.e. there exists what is known as the long range order. The pattern
is such that having observed it in some small region of the crystal, it is possible to predict accurately the
positions of particles in any region of the crystal, however far it may be from the region under observation.
But amorphous solids, such as glass, do not have this ordered arrangement. In many ways they are more
closely related to liquids than to crystalline solids and are, therefore, regarded as supercooled liquids with
high viscosity. In this chapter, we shall discuss the subject of crystalline structure.
In-Text Questions (NCERT)
1.1
Why are solids rigid?
Ans.
In a solid, the constituent particles are very closely packed have fixed positions and can only oscillate
about thier mean positions.The forces of attraction among these particles are very strong. Hence,they are
rigid.
1.2
Ans.
1.3
Classify the following as amorphous or crystalline solids: Polyurethane, naphthalene, benzoic acid, teflon,
potassium nitrate, cellophane, polyvinyl chloride, fibre glass, copper.
Amorphous : Polyurethane , teflon , cellophane , polyvinyl chloride , fibre glass
Crystalline solids : Benzoic acid , potassium nitrate , copper.
Ans.
1.4
Ans.
1.5
Refractive index of a solid is observed to have the same value along all directions. Comment on the nature
of this solid. Would it show cleavage property?
As the solid has same value of refractive index along all directions, this means that it is isotropic and hence
amorphous. Being an amorphous sloid, it would not show a clean cleavage when cut with a knife. Instead,
it would break into pieces with irregular surfaces.
Ans.
1.6
Ans.
1.7
Ans.
Classify the following solids in different categories based on the nature of intermolecular forces operating in
them: Potassium sulphate, tin, benzene, urea, ammonia, water, zinc sulphide, graphite, rubidium, argon,
silicon carbide.
Potassium sulphate = Ionic ,
Tin = Metallic ,
Benzene = Molecular (nonpolar) ,
Urea = Molecular(Polar),
Ammonia = Molecular (Hydrogen bonded),
Water = Molecular (Hydrogen bonded) ,
Zinc sulphide = Ionic ,
Graphits = Covalent or Network,
Rubidium = Metallic ,
Argon = Molecular (Nonpolar) ,
Silicon carbide = Covalent or Network.
Solid A is a very hard electrical insulator in solid as well as in molten state and melts at extremely high
temperature. What type of solid is it?
Covalent Network Solid like SiO2 (quartz) or SiC or (diamond)
[4]
1.8
Ans.
Ionic solids conduct electricity in molten state but not in solid state. Explain.
In the molten state, ionic solids dissociate to give free ions and hence can conduct electricity. However, in
the solid state, as the ions are not free but remain held together by strong electrostatic forces of attraction,
they cannot conduct electricity in the solid state.
1.9
Ans.
(2)
Definition of lattice + Unit cell + Coordination Number & Density & Packing fraction
STUDY OF STRUCTURE OF CRYSTALLINE SOLIDS To study crystalline solids we need some mathematical
and geometrical tools.Lets get familier with them.
1.
Space lattice : It is the regular arrangement of points in space and forms the basis of classification of
all structures.This regular arrangement spread over whole space is the long range order.
2.
Unit cell: Unit cell is the smallest arrangement of points which on repetition generates the whole space
lattice. It is the building block of the whole structure.
(a)Unit cell contains the minimum information in terms of edge lengths and angles sufficient to
determine the structure of the lattice.
(b)Generally unit cell is the smallest element of the space lattice. But sometimes a slightly bigger
element can be taken as unit cell to make calculations easy which will be representing the symmetry of
the lattice i.e., the choice of unit cell depends entirely on our convenience.
Various types of unit cells can be chosen within a particular lattice:
(i) Primitive:When lattice points are found only at the corners of the unit cell.
(ii) Centered/Non-primitive:When lattice points are found at the corners and as well as inside the unit
cell.
Space Lattice
Unit Cell
3.
4.
Space Lattice : The definiotn of a space lattice is strictly a geometrical concept and represents a three-dimensional
tranlational repettion of the centres of gravity of the units of pattern in the crystal.
These units of pattern can be anything, for example :
(i) In metals or inert gases, each lattice point may represent the position of each atom.
(ii) In a crystal of methane, each lattice point many represent the centre of a methane molecule.
(iii) In ionic crystals, the lattice points may represent ions or ion-pairs.
Coordination number : It is defined as the number of nearest neighbours or touching particles with other
particle present in a crystal is called its co-ordination number. It depends upon structure of the crystal.
[5]
(3)
5.
6.
(Primitive Type)
90
(ii) Rectangle: a b, = 90
b
(Primitive Type)
90
(Primitive Type)
60
a
(Primitive Type)
(v)Parallelogram: a b, 90
(Primitive Type)
a
STRUCTURE OF SOLIDS
(a) Solids having only one type of particles : e.g. metallic, molecular, covalent network solids.
The particle of the solid will be represented by a sphere of radius r. We assume that there is only attraction
force existing between those spheres.Hence in order to to get maximum stable arrangement of these
particles the seperation between the particles should be minimum.
E.g. Water kept in a container ,on cooling,results in freezing with initially at the circumference of surface
(1D), then on the surface (2D) and then throughout the volume (3D).
ARRANGEMENT IN 1-D :
In one dimension it is possible to arrange the spheres in only one stable way.This is the position with
minimum separation and minimum PE of the system(most stable)
This is the predominant way of packing in one dimensions and as such most of the space lattices will
show such an arrangement in one dimensions along the planes of close packing.
[6]
1
r2 4 r2
4
r 2
4r
4 = 0.78( 78% )
2. Hexagonal arrangement(better arrangement) : If each one dimensional array is placed in the cavity
of the just preceding array, we get the hexagonal packing in two dimensions.
area of hexagon = 6
1
3 2
3
6r2 = 3r2
a =6
4r2 ; area of atoms = r2 +
3
4
4
3 r 2
6 3r
3
~ 0.91 ( 91% )
Better packing in 2d: Clearly more no. of spheres are in contact in the hexagonal arrangement, hence the
hexagonal arrangement is considered to be a better way of packing as compared to the square packing.
(4)
7.
Cubic
; Tetragonal
; Orthorhombic
b
a
c
a
[7]
Monoclinic
Hexagonal
a
a
Rhombohedral
Triclinic
b
b
a
Crystal
System
Axial
distances
Axial angles
Examples
Type of Unit
cells
Cubic
Tetragonal
Orthorhombic
Monoclinic
Hexagonal
Rhombohedral
Triclinic
a=b=c
a=bc
abc
abc
a=bc
a=b=c
abc
= = = 90
= = = 90
= = = 90
= = 90; 90
= = 90; = 120
= = 90
90
S,BC,FC
S,BC
S,BC,FC,EC
S,BC
S
S
S
Ways of choosing unit cells in 3-dimensions: Apart from unit cells with lattice points at the corners,
there are three other types of choosing unit cells called Non-Primitive/Centered unit cells.
Principle of choosing a particular type of unit cell:
"The surroundings of each and every lattice point in a lattice should be exactly identical."----(Very Imp.)
Hence all the lattice points are indistinguishible.
1. Primitive /Simple: lattice points only at the corners only.
3. Face centered : Lattice points at corners & at each of the face centre.
[8]
4. End centered: Lattice point at corners & only at two oppsosite faces.
Observation : End centered unit cell are not found in Cubic system. It is found that each crystal class do
not have all the four different type of unit cells. For e.g. in cubic crystal class or system, only 3 types of unit
cells are found end centred is not found.
Total number of lattice arrangements in three dimensions = 14.These are called 14 BRAVAIS LATTICES
Ex.1
Sol.
Identify molecular solid, covalent solid, ionic solid : P4(s), S8 (s), SiC (s), Al2O3(s), He (s), Al2Cl6(s).
Molecular solid P4(s), S8 (s), He (s), Al2Cl6(s)
Covalent solid SiC
Ionic solid Al2O3(s).
Ex.2
The lattice parameters of a given crystal are a = 5.62 , b = 7.41 and c = 9.48 . The three
coordinate axes are mutually perpendicular to each other. The crystal is :
(A) tetragonal
(B) orthorhombic
(C) monoclinic
(D) trigonal.
(B)
a b c & = = = 90 the crystal system is orthorhombic.
Ans.
Sol.
Ex.3
Ans.
Lecture # 2
Section (B) Simple cubic structure, BCC and CsCl structure
Point
(1)
Definitions of SC, BCC & CsCl unit cell.
(1 + 2)
(2)
Contribution of an atom to a lattice point (formula of unit cell or compound for SC & BCC).
(3)
Relation between edge length and radius & volume of unit cell.
(3 + 4)
(4)
Coordination number in each case (SC, BCC), CsCl-Type.
(5)
Structure of section nearest neighbours atom.
(5 + 6)
(6)
Packing of fraction and density of SC & BCC & CsCl.
(1)
Time
[15 Mins]
[20 Mins]
[25 Mins]
Half
of
the
atom
1.11
Ans.
1.12
Ans.
[10]
1.13
Ans.
Ex.4
Explain how much portion of an atom located at (i) corner and (ii) bodycentre of a cubic unit cell is part of
its neighbouring unit cell.
(i) An atom at the corner is shared by eight adjacent unit cells. Hence, portion of the atom at the corner that
1
belongs to one unit cell = .
8
(ii) The atom at the body centre of a cubic unit cell is not shared by any other unit cell. Hence, it belongs
fully to the unit cell.
Ans.
In a face centered cubic arrangement of A and B atoms whose A atoms are at the corner of the unit
cell and B atoms at the face centres. One of the A atom Is missing from one corner in unit cell.
The simplest formula of the compound is
(A) A7B3
(B) AB3
(C) A7B24
(D) A2B3
(C)
Sol.
A=7
1
7
=
8
8
B=6
1
=3
2
Formula = A 7 / 8 B3 or A7B24
Ex.5
A compound has cubical unit cell in which X atom are present at 6 corner, Y atom are at remaining corner
& only at those face centers which are not opposite to each other & Z atoms are present at remaining face
center & body center then find.
(i) Formula of compound (ii) Density if edge length = 2 .
Given : Atomic mass of X = 40 amu, Y = 60 amu, Z = 80 amu.
Sol.
(i)
X=
1
3
6= ,
8
4
Y=
1
1
7
2+
3=
8
2
4
Z=
1
5 10
3+1+1= =
2
2
4
For formula :
(ii)
X 3 Y7 Z 10
4
= X3 Y7 Z10
1
6.02 10 23
gram.
3
7
10
40 60
80
Mass
335 1.67 10 24
4
4
4
Density =
=
amu/cc =
= 69.8 gram/cc.
Volume
8 10 24
(2 10 8 )3
[11]
1.5.1
Primitive Cubic Unit cell : Primitive cubic unit cell has atoms only at its corner. Each atom at a corner
is shared between eight adjacent unit cells as shown in Fig. 1.8, four unit cells in the same layer and
four unit cells of the upper (or lower) layer. Therefore, only 1/8th of an atom (or molecule or ion) actually
belongs to a particular unit cell. In Fig. 1.9, a primitive cubic unit cell has been depicted in three different
ways. Each small sphere in Fig. 1.9 (a) represents only the centre of the particle occupying that
position and not its actual size. Such structures are called open structures. The arrangement of
particles is easier to follow in open structures. Fig. 1.9 (b) depicts space-filling representation of the unit
cell with actual particle size and Fig. 1.9 (c) shows the actual portions of different atoms present
different atoms present in a cubic unit cell.
In all, since each cubic unit cell has 8 atoms on its corners, the total number of atoms in one unit cell is
8 1/8 = 1 atom.
1.5.2
Body-Centered Cubic Unit Cell : A body-centred cubic (bcc) unit cell has an atom at each of its corners
and also one atom at its body centre. Fig. 1.10 depicts (a) open structure (b) space filling model and (c) the
unit cell with portions of atoms actually belonging to it. It can be seen that the atom at the body centre
wholly belongs to the unit cell in which it is present. Thus in a body-centered cubic (bcc) unit cell :
face-Centered Cubic Unit Cell : A face-centred cubic (fcc) unit cell contains atoms at all the corners
and at the centre of all the faces of the cube. It can be seen in Fig. 1.11 that each atom located at the
face-centre is shared between two adjacent unit cells and only 1/2 of each atom belongs to a unit cell.
Fig. 1.12 depicts (a) open structure (b) space-filling model and (c) the unit cell with portions of atoms
actually belonging to it. Thus, in a face-centred cubic (fcc) unit cell :
(i) 8 corners atoms 1/8 atom per unit cell= 8 1/8 = 1 atom
(ii) 6 face centered atoms 1/2 atom per unit cell = 6 1/2 = 3 atoms
Total number of atoms per unit cell = 4 atoms.
[12]
a3 N0
a N0 10 30
g / cm 3
The density of the substance is same as the density of the unit cell.
Packing fraction (P.F.) : It is defined as ratio of the volume of the unit cell that is occupied by spheres of the unit
cell to the total volume of the unit cell.
Let radius of the atom in the packing = r
Edge length of the cube = a
4
Volume of the atom (spherical) = r3
3
V
a3
(Note that
, hence crystal thus formed will belong to the cubic crystal class, and as the
lattice points are only at the corners, hence the unit cell will be simple, therefore what we get is the simple
cubic )
(i) Relation between a and r
a = 2r (because atoms along the edge are touching each other)
(ii) effective no. of atoms per unit cell Z:
1
Z 8 1
8
(iii) packing fraction :
4 3
r
4
4 r 3
3
3
r
=
= 0.52( 52% )
a3
3 (2r )3
3 8 r3
(Note:This is not a very efficient way of packing as the packing fraction is very low)
[13]
Type of neighbour
nearest
Distance
a
no.of neighbours
6
(shared by 4 cubes)
(next)1
a 2
12
(shared by 2 cubes)
(next)2
a 3
(unshared)
(i)Relation b/w a and r: a 2r (as atoms along the edge are not touching each other)
they touch along the body diagonal, hence
(ii) Effective no-of atoms (f) = 1 +
4 3
r
3
(iii) Packing fraction =
4 4 4r3
3 a = 4r..
1
8 = 2.
8
3 3 3 =
3
~
0.68 ( 68% )
8
(iv)Coordination No. CN: 8 (the sphere at the body centre will be touching the spheres at the eight corners)
ZM
(v) Density =
Na a
2M
Na a 3
[14]
BCC :
Type of neighbour
Distance
nearest
2r = a
no.of neighbours
3
2
(next)
=a
(next)2
= a 2
12
(next)3
= a
(next)4
= a 3
11
2
24
8
NCERT Ex.1.3
1.3
Sol.
An element has a body-centred cubic (bcc) structure with a cell edge of 288 pm. The density of the
element is 7.2 g/cm3. How many atoms are present in 208 g of the element?
Volume of the unit cell = (288 pm)3
= (2881012 m) = (2881010 cm)3
= 2.391023 cm3
Volume of 208 g of the element
208 g
mass
=
= 28.88 cm3
density
7.2 g cm 3
Number of unit cells in this volume
28.88 cm3
Ex.6
Ans.
Ex.7
Ans.
Ex.8
Sol.
How many 'nearest' and 'next nearest' neighbours respectively does potassium have in b.c.c. lattice
(A) 8, 8
(B) 8, 6
(C) 6, 8
(D) 8, 2
(B)
If a metal has a bcc crystal structure, the coordination number is 8, because :
(A)
each atom touches four atoms in the layer above it, four in the layer below it and none i n
its own layer.
(B)
each atom touches four atoms in the layer above it, four in the layer below it and one i n
its own layer.
(C)
two atoms touch four atoms in the layer above them, four in the layer below them, and none
in their own layer.
(D)
each atom touches eight atoms in the layer above it, eight in the layer below it and
none in its own layer.
(A)
Potassium crystallizes in body centered cubic lattice with a unit cell length a = 5.2
(A) What is the distance between nearest neighbours
(B) What is the distance between next nearest neighbours
(C) How many nearest neighbours does each K atom have
(D) How many next nearest neighbours does each K have
(E) What is calculated density of crystalline K.
(A) 4.5 ,
(B) 5.2,
(C) 8 , (D) 6 (E) 0.92 g/mL
(A) 2r =
(C) 8
3a
=
2
3 5.2
= 4.5
2
(E) d =
2 39
(5.2 10
8 3
) 6.02 10 23
= 0.92 g/ml
[15]
Lecture # 3
Section (C) Closest packing.
(1)
Voids and their geometry and coordination number (2D).
(2)
Voids and their geometry and coordination number (3D) closest packing.
(3)
Radius of biggest and smallest atom that may fit in these voids only.
(4)
ABAB.........type and ABC.........ABC type closest packing.
(5)
Locating tetra and octahedral void in ccp and hcp, Number of voids per atom
in closest packing.
(1)
[10 Mins]
[10 Mins]
[10 Mins]
[20 Mins]
[10 Mins]
2R
2R
30
2
R
Rr
3
=
=
r = 0.155 R
3
Rr
R
2
where, R= Radius of the sphere, r = rmaximum radius of a sphere that can be placed inside the void.
cos30 =
Rr
(2) Square void (2-Dimensional 4-coordinate void) The square voids are found in the planes of the
close packed structures, whenever three speres are in contact in such a fashion.
AC2 = AB2 + BC2 [2(R + r)]2 = (2R)2 + (2R)2
2(R + r) = 2 2 R r = ( 2 1) R = 0.414 R
(2)
Voids and their geometry and coordination number (3D) closest packing.
(3)
Radius of biggest and smallest atom that may fit in these voids only.
R+r
c
/2
D
C
= 109.28
[16]
1
r=R
1 r = 0.225 R
sin
R
R
sin
=
= sin 54 44
2
Rr
Rr
(3)
Octahedral void (3-Dimensional 6 coordinate void) The octahedral void is formed whenever two spheres
are placed, one on top and the other below a square arrangement of spheres.This can also be obtained by
placing two THREE-BALL arrangements on the top of each other such that a hexagonal view is obtained.
R
2
rr
R
6
x = 2R;
(4)
2(R + r) =
2x= 2 2R
r = ( 2 1) R = 0.414 R
2 3 R = 2 (R + r)
r
R
r = ( 3 1) R
r = ( 3 1) R r = 0.732 R
The cubical void is generally not found in closed packed structures, but is generated as a result of distortions
arising from the occupancy of voids by larger particles.
Ex.9(a) In a face centred cubic arrangement of metallic atoms, what is the relative ratio of the sizes of
tetrahedral and octahedral voids?
(A) 0.543
(B) 0.732
(C) 0.414
(D) 0.637
Ans.
(A)
Sol.
rtetrahedra l
0.225 R
=
roctahedral
0.414 R = 0.543.
(b) The numbers of tetrahedral and octahedral holes in a ccp array of 100 atoms are respectively
(A) 200 and 100
(B) 100 and 200
(C) 200 and 200
(D) 100 and 100
Ans.
(A)
Ex.10 Copper has a face-centred cubic structure with a unit-cell edge length of 3.61. What is the size of the
largest atom which could fit into the interstices of the copper lattice without distorting it?
Ans.
Sol.
Figure
(Hint. : Calculate the radius of the smallest circle in the figure)
0.53
roctahedral = 0.414 R
for FCC 4R =
2a ;
R=
2a
;
4
r=
0.414 2 a
0.414 2 3.61
=
= 0.53
4
4
[17]
Lecture # 4
Section (D) hcp structure
(1)
Derivation of unit cell from ABAB.............
(2)
Calculation of a, b and c (height) (ABAB) ; volume of unit cell.
(3)
Occupancy of unit cell.
(4)
Packing fraction, density and coordination number.
(5)
Next nearest neighbours.
(6)
Location of tetrahedral and octahedral voids in hcp structure
(formula of unit cell or compound).
(4)
Point
(1 )
(2, 3, 4)
Time
[10 Mins]
[30 Mins]
(5 + 6) [15 Mins]
found. To generate close packing we must start with best possible arrangements in two dimensions i.e.,
the hexagonal arranged sheets and spheres of IInd sheet must rest depressions/voids of 1st sheet hexagonal
close pached
All the voids of 1st sheet canot be occupied by shperes of 2nd sheet (because of same size of spheres)
Only 50% of the viods can be occupied. Out of six voids around anly sphere only three atternate voids can
be occupied by 2nd sheet of spheres. This arrangements is shown below.
a
b
a
b
a
b
CALCULATIONS
1. For c: For the estimation of c, consider the spheres marked 1,2,3,4 in the unit cell as shown.These
four spheres form a regular tetrahedron. The length of the perpendicular from 4 to the equilateral triangle 12-3 will be equal to c/2.
[18]
cos 30 =
a
2x
a2
a
a
x=
=
2 cos 30
2 3
3
apply pythagoras theorem.
2
4r
3
x2 + (C/2)2 = a2 C =
3 2
a c=6.
4
3
4
4r2
2
4r = 24
3
3
2.r
Z= 3 + 2
4 3
r
=
= 0.74 = 74%
2
3 2
24 2 r
6
3. Packing fraction : =
4. Coordination No. CN= 12( each spheres touches 6 spheres in its layer,3 above and 3 below)
5. Density =
ZM
6M
Mass
= N ( volume ) Na ( volume )
Volume
a
NOTE: In closest packings, whenever two consecutive layers are of different kind then packing efficiency
will always be 74%.
Illustration 10. Show by simple calculation that the percentage of space
ccupied by spheres in hexagonal cubic packing (hcp) is 74%
[19]
The centre sphere of the first layer lies exactly over the void of 2nd layer B.
The centre sphere and the spheres of 2nd layer B are in touch
So, In PQR (an equilateral triangle)
PR = 2r, Draw QS tangent at points
In QRS
QRS = 30, SR = r
Cos30 = SR/QR
QR = r / 3 / 2 = 2r /
PQ =
PR 2 QR2 =
4r 2 4r2 / 3
8r 2 / 3 = 2 2 /3r
h = 2h1 = 4 2 /3r
Now, volume of hexagon = area of base x height
h1 =
= 6 3 / 4 a2 h 6 3 /4 (2r)2 4 2 /3r
[ Area of hexagonal can be divided into six equilateral triangle with side 2r)
No. of sphere in hcp = 12 1/6 + 1/2 2 + 3 = 2+1+3 = 6
effectively 8 + 12
Lecture # 5
Section (E) ccp structure
(1)
Derivation of unit cell from ABCABC..........ABC..........
(2)
Relation between edge length (a) and radius (R) for (ABCABC);
volume of unit cell.
(3)
Occupancy of unit cell.
(4)
Packing fraction, density and coordination number.
(5)
Next nearest neighbours.
(6)
Location of tetrahedral and octahedral voids in ccp structure.
(7)
Formula of unit cell or compound
(B)
Point
(1)
Time
[10 Mins]
(2, 3, 4)
[30 Mins]
(5, 6, 7)
[20 Mins]
a
b
a
b
a
b
In the ABC ABC Pattem the spheres of 4th layer are vertically above the spheres of Ist layer then these
consecutive layers are different from each other, fourth layer will be idential to first layer so it will be called
ABC ABC repeat pattern.It is also called the ccp (cubical close packing) because a cubical type of unit
cell is used for the study of this arrangement.
1
1
8 6 4
8
2
4 3
r
3
p.f.
22 =
= .74( 74% )
3
3 2
444 r
4
3. Packing fraction :
4. Coordination number, CN = 12 ( each corner sphere touches three spheres per cube(each of them
being shared by two of the eight cubes surrounding that sphere) )
ZM
5. Density =
NA . a3
[21]
Type of neighbour
Distance
a
nearest
no. of neighbours
38
12 =
2
38
6=
4
(next)1
(next)2
3
2
24
(next)3
a 2
12
(next)4
5
2
24
3
4
(B) Octahedral voids :In an FCC unit cell, there are four octahedral voids. They are present at all the
1
edgecentres and at the body centre. The contribution of the edge centre is
4
1
Ans.
A metal crystallizes in two cubic phases i.e., FCC and BCC whose unit cell lengths are 3.5 and 3.0
respectively. The ratio of their densities is :
(A) 3.12
(B) 2.04
(C) 1.26
(D) 0.72
(C)
(3 )3
d1
4
=
2 = 1.26.
d2
a 3N A
( 3.5 ) 3
Ex.12 In a ccp structure, the :
(A) first and third layers are repeated
(C) second and fourth layers are repeated
Ans.
(B)
ZM
Sol.
d=
[22]
Ex.13 Lithium borohydride crystallizes in an orthorhombic system with 4 molecules per unit cell. The unit
cell dimensions are a = 6.8 , b = 4.4 and c=7.2 . If the molar mass is 21.76, then the density of
crystals is :
(A) 0.6708 g cm 2
(B) 1.6708 g cm 3
(C) 2.6708 g cm 3
(D) None of these.
Ans.
(A)
ZM
Sol.
d=
a NA
4 21.76
6.8 10
4.4 10
7.2 10 8 6.023 10 23
= 0.6708 g cm 2.
Ex.14 An fcc lattice has lattice parameter a = 400 pm. Calculate the molar volume of the lattice including all
the empty space:
(A) 10.8 mL
(B) 96 mL
(C) 8.6 mL
(D) 9.6 mL
Ans.
(D)
Sol.
Volume of 4 atoms = a3 = (4 108)3 cm 3
( 4 10 8 )
6.023 1023 = 9.6 ml.
4
volume of NA atoms =
Lecture # 6
Section (F) Radius ratio rule & type of Ionic structures :
(1)
Radius ratio rule
(2)
Rock salt structure
(3)
Anti fluorite structure
(4)
ZnS structure
(5)
Anion forms HCP & Cation in all octahedral void.
(6)
Anion forms HCP & Cation in all tetrahedral void.
(7)
Anion forms HCP & Cation in half tetrahedral void.
(8)
Fluorite structure
(9)
Perovskite structure
(10)
Spinal structure
(11)
Diamond structure.
(12)
Temperature & pressure effect on coordination number of compound.
Point Time
(1)
[5 Mins]
(2, 3, 4) [20 Mins]
r
Radius ratio rule: Radius ratio = r ,this gives the idea about the type of void occupied.
Radius ratio
Type of void occupied
Coordination No.
r
linear void
2
r < 0.155
r
0.155 r < 0.225
triangular void
3
r
0.225 r < 0.414
tetrahedral void
4
r
0.414 r < 0.732
octahedral void
6
r
0.732 r < 1
cubical void
8
Case I :
r
r < 0.155
It is unstable situation because cation is not touching any of anion and anions are in contact.
[23]
Case II :
r
r = 0.155
a
a = 2r
This is the perfect arramgement for triangular void.Here cation will be touching three anions hence C.N.
= 3 and anions will be in limiting contact.
r
Case III : 0.155 < r < 0.225
a
Here cation will be touching three anions hence C.N. = 3
a
but anions will not be in contact
= r+ + r ; a =
3 (r+ + r)
r
Case IV : r = 0.225
2 afcc = 4r
r
Case V : 0.225 < r
< 0.414
Here fcc lattice will expand now anion will no longer be in contact therefore
Considering a minicube
2 afcc > 4r
Mini
Cube
a/2
Cation will lie at the centre of the body diagonal of the mini cube of side a/2.
r + r+ =
1
(body diagrol of minicube)
2
r+ + r =
1 a fcc
2
2
afcc =
4
3
(r r )
r
Case VI : r = 0.414
+
a
[24]
r
Case VII : 0.414 < r < 0.732
FCC lattice undergoes symmetrical exapnsion. Anions loses contact 2 afcc > 4r
But the relative orientation of Cation and anions would remain same as in te case of perfect OV
situation.
afcc = r + 2r+ + r
r
Case VIII : r = 0.732 Cation is perfectly in cubical void C.N = 8 asc = 2r
r
Case IX : 0.732 < r < 1.00
Expansion undergoes and anions are not in contact.But relative orientation will remain same as that is
perfect cubic void.
3 asc = 2(r+ + r)
There will 2 different kind of atoms, cation & anion, so there will be two different coordination number
(C.N.). C.N. of cation = no. of anions surroundings any cation.
C.N. of anion = no. of cations surrounding any anion.
Anion
Cation
[25]
C.N.Na+ = 6 ; C.N.Cl = 6
NaCl = 6 (cation) : 6 (anion) CN compound
For Cl :
Type of neighbour
Distance
Nearest
Na+,
(Next)1
Cl,
(Next)2
Na+ (B.C.),
(Next)3
Cl, a
No. of neighbours
a
2
a
6
12
2
3
a
2
8
6
Example :
Note :
Lattice of NaCl is FCC of Cl in which all octahedral void are occupied by Na+.
or FCC of Na+ in which octahedral void are occupied by Cl.
(2) ZnS type( AB-type ) of unit cell or 4 : 4 CN compound
Zns fcc (zinc blende) ;
Zns hcp (wurtzite)
r
experimental:
zn2
0.3
rs2
S2 will form fcc lattice. effective no. of S2 ions in one unit cell = 4.0
Zn2+ ions will occupy alternate (non-adjacent) four out of eight Tetahedral voids.
none of the face of the minicube should be common.
effective no. of Zn2+ ions = 4 formula of unit cell = Zn4S4 effective no. of formula units, Z = 4
ZM
mass = N
A
M = 97 gm/mole
ZM
4
a
1
3 fcc
(rZn2 rs2 ) density =
afcc =
2
2
N A a 3fcc
3
C.N. of Zn2+ ions = 4
C.N. of s2 ions = 4
Ex :
ZnS, CuCl, CuBr, CuI, AgI.
rzn2 rs2
For S2
Type of neighbour
Nearest
Distance
3
a
4 FCC
(Next)1
(Next)2
(Next)3
(Next)4
2
11
a
4
a
19
a
11 FCC
No. of neighbours
Ions
Zn2+
12
S2
12
Zn2+
S2
12
Zn2+
rF
< 0.414
rca
Effective no. of ca2+ ions = 4
Effective no. of F ions = 8
Effective no. of formula units, Z = 4
C.N of F = 4
[26]
For Ca2+
,
Type of neighbour
Distance
No. of neighbours
3
4
Nearest
(Next)1
Ions
12
Ca2+
(Next)2
11
16
24
(Next)3
Ca2+
For F
Type of neighbour
Distance
No. of neighbours
Ions
Nearest
3
4
Ca2+
(Next)1
a
2
12
Ca2+
(Next)2
2
11
16
(Next)3
Ex.15 A mineral having formula AB2 crystallize in the cubic close packed lattice, with the A atoms occupying
the lattice points. What is the co-ordination no. of A atoms? of the B atoms? what fraction of tetrahedral
sites is occupied by B atoms.
Ans.
8, 4, 100%.
It has fluorite (CaF2) structure.
4.
Na2O (sodium oxide) (A2B-type )or Anti - Fluorite structure or 4 : 8 coordination compound
O2 fcc lattice
Na+ all the tetrahedral voids
5.
ZM
Na
2
asc =
a 3sc
(r r )
rCs
rCl
0.93
Effective Cl ions = 1
Effective Cs+ ion = 1
Z = 1 [mistake in NCERT not BCC lattice]
C.N of Cs+ = 8 C.N of Cl = 8
r+ + r =
3a
=
2
3 4.3
= 3.72 .
2
2
2
a or a = 2R = 2
R.
3
3
(2) If number of unit cell along one edge are x then total number of unit cell in cube = x3.
[27]
e.g.
Figure
Number of unit cell along one edge = 2, then total number of unit cell in cube = 23 = 8.
BaTiO3 or MgTiO3.
ZnS types in which all S2 location and all Zn2+ location are occupied by C atoms.
So,
Z = 8 atom per unit cell
aFCC =
4
3
[dC C]
In crystal lattice of diamond, carbon atoms adopt FCC arrangement with occupancy of 50%
tetrahedral voids.
4:4
6:6
8:8
6:6
[28]
4
(dC C )3
3
3
= 0.34.
The edge length of the unit cube of diamond is 356.7 pm and this cube contains 8 carbon atoms.
Calculate: (a) the distance dC C between carbon atoms, assuming them to spheres in contact ; (b) the
fraction of the total volume that is occupied by carbon atom
Sol.
(a) Edge length of the cube = 356.7 pm ; Face diagonal of the cube = 2 (356.7 pm) = 504.3 pm
This distance is also given by
d = 4(dC C sin 5444') = 4dC C (0.8164)
504 .3 pm
d
154 .4 pm
= 154.4 pm
Hence, Radius of carbon = C C =
= 77.2 pm
4 0.8164
2
2
Volume of the unit cell = (356.7 pm)3 = 4.538 x 1029 m3
4
4
3
Volume occupied by 8 spheres = 8 (77.2 pm ) =
(154.4 X 1012 m)3 = 1.542 1029 m3
3
Thus, dC C =
1.542 10 29 m3
4.538 10 29 m3
= 0.34.
[29]
Lecture # 7
Section (G) Crystal defects & Properties of solid :
(1)
Definition
(2)
Stoichiometric defects
(3)
Point defects Schottky defect, Frenkel defect, Impurities defect
(4)
Non-stoichiometric defect
Metal excess defects (F-center)
Non metal excess defects (metal deficient defect)
(5)
Electrical Properties :
Conductors, Insulators, Semiconductors.
(6)
Doping : n-type semiconductors, p-type semiconductors, Superconductivity.
(7)
Magnetic Properties
(i) Paramagnetism
(ii) Diamagnetism
(iii) Ferromagnetism
(iv) Anti-Ferromagnetism
(v) Ferrimagnetism
(8)
Application of semiconductor
(9)
Effect of temperature on conductors, semiconductors, insulators.
Point Time
(1, 2, 3) [20 Mins]
(4)
[20 Mins]
(5, 6)
[10 Mins]
Schottky defect
Cation Anion
dislocated cation
Frenkel defect
Cation Anion
Interstitial entity
Interstitial defect
th
FRENKEL : When atoms/ions displaced from normal lattice positions and are present in some
interstitial voids.Density remains same
exp < theoritical
[30]
INTERSTITIAL :
When some small foreign atoms are trapped in interstitial voids of the lattice without any chemical reaction.
Formula remains the same exp > theortical
NON-STOICHIOMETRIC DEFECTS :
(a) metal excess or cation excess defect :- If no. of missing anione is more than no. of missing cations.
- To maintain electrical neutrality some electron are trapped at anionic vacancies.
Because of these extra e the electrical and optical (colour) properties of the compound get modified.
So these locations of es are also known as color centres (F - centres) .
ZnO - white in color at room temperature.
- on heating some O2 ione get released in the form of O2 and e are trapped at their locations. because
of this it because yellow in color.
(b) metal deficiency (cation deficiency) defects
- no. of missing cations should be more than no. of missing anions.
- oxidation no. of cation will get modified to maintain electrical mentrality.
Cation Anion
F-centre
-e
Cation Vacancy
Metal excess
Sol:
Some Fe atom
are in +2 state
Some Fe atom
are in +3 state
14
1400
100% =
% 15.54%
93
93
[31]
PROPERTIES OF SOLIDS :
(i) Electrical Properties
(i) Electrical Properties : Solids exhibit an amazing range of electrical conductivities, the range of electrical
conductivities from 1020 to 107 ohm1 m1. Solids can be classified into three types on the basis of their
conductivities.
(1) Conductors : Metals are goods condcutors and have conductiveites in the order 107 (m)1.
(2) Insulators : Those solids which have very low conductivities ranging from 1020 to 1010 (m)1 are
electrical insulators e.g.; MnO, CoO; NiO, CuO, Fe2O3, TiO2.
(3) Semicondutors : Those solids which have intermideidate conductivities generally from 106 to 104
(m)1 are termed as semicondcutors.
Intrinsic Semicondcutors : The conduction by pure subtances such as silicon and germanium is called
intrisic conduction and these pure substances exhibiting electrical condcutivity are called intrinsic
semicodcutors.
Figure
Doping : The conductivity of silicon and germanium can be increases by adding apporpirate amount of
suitable impurity. The process is called doping.
Type of Semiconductors :
(1) n-Type Semiconductors : Metal excess compounds conduct electricity through normal electron
conduction mechanism and are therefore n-type semiconductors.
[32]
(2) p-Type Semiconductors : Metal deficient compounds conduct electricity through positive hole conduction
mechanism and are therefore p-type semiconductors.
(ii) Magnetic Properties : Every substance has some magnetic properties associated with it. The origin
of these properties lies in the electrons. Each electron in an atom behaves like a tiny magnet.
Its magnetic moment originates from two types of motions.
(i) its orbital motion around the nucleus.
(ii) its spin around its own axis.
[33]
(i) paramagnetic (ii) diamagnetic (iii) ferromagnetic (iv) antiferromagnetic and (v) ferrimagnetic.
.
(1)
(2)
(3)
Paramagnetism : When substances which are attracted by the external magnetic field are called
paramagnetic substances and the phenomenon is called as paramagnetism. Atoms ion or molecules
containing unpaired electron show this property, eg. O2 Cu2+, Fe3+ etc. these substances lost their magnetism
in the absence of magnetic field.
Diamagnetic materials : Those materials which are repelled by magnetic field are called diamagnetic
materials e.g. Cu+, TiO2, NaCl and C6H6. They do not have unpaired electrons.
Ferromagnetism : When substances show permanent magnetism even in the absence of the magnetic
field this phenomenon is called as Ferromagnetism and such substances as called as Ferromagnetic
substances e.g. Fe Ni Co and CrO2.
This type of magnetism arise due to the spontaneous alignment of magnetic moments due to unpaired
electron in the same direction.
(4)
Anti Ferro Magnetism : Substances which are expected to possess paramagnetism or ferro magnetism
on the basis of unpaired electrons but actually they possess zero net magnetic moment are called Antiferromatic substances and the phenomenon is called as Anti-ferromagnetism. eg. MnO, Anti-ferromagnetism
is due to the presence equal number of magnetic moments in the opposite direction.
(5)
Ferrimagnetism : Substances which are expected to possess large magnetism on the basis of unpaired
electrons, but actually have small magnetic momentum are called ferrimagnetic substances eg. Fe3O4,
ferrites of the formula M2+, Fe2O4 where M = Mg, Cu, Zn etc. Ferrimagnetism arises due to the unequal
moments in opposite direction resulting in same net magnetic moment. On heating these substance loss
their magnetism and convert in to paramagentic substance
Curie Temperature : The temperature at which a ferromagnetic substance loses its ferromagnetism and
becomes only paramagnetic. For iron the curie temperature is 1033 K and for nickel 629 K, for Fe3O4 850
K. Below this temperature paramagnetic solid becomes ferromagnetic.
Domain : In solid state the metal ions of ferromagnetic substances are grouped together into small
regions called domains.
.
Ex.19
Ans.
Ex.20
Ans.
12-16 Compounds : The solid state compounds are obtianed by combination of elements fof groups 12
and 16 the compounds are called 12-16 compouds e.g. ZnS, CdS, CdSe and HgTe.
[35]