Solid State Theory PDF

Solid State
Section (A): Basics of solid state

State of matter depends on:
(i) Tendency of relative motion at a particular temperature.
(ii) Intermolecular forces.
Tab-1
Properties Solid Liquid Gases
Random motion to
(i) Motion of No free motion
a limited extent is Totally random.
particles only vibration allow.
allowed.
(ii) Inter molecular
Very strong Intermediate strength Very weak ( zero)
forces
(iii) Average Average separation is
Average separation is fixed so
separation almost constant so No fixed volume.
volume is fixed
(volume) almost fixed volume.
Average separation is
Definite shape as the
fixed but location of
(iv) Shape location of particles are No fixed shape.
particle is not fixed so no
fixed.
definite shape.
(v) Effect of change
Liquid are also almost
in pressure & Are incompressible. Highly compressible.
incompressible.
temperature.
Heat capacity is Heat capacity is
(vi) Heat capacities almost independent Same as solid. dependent on
of process. process.
Types of Solid:
Tab-2 Classification on the basis of forces among constituting particles
Constituent Force of Physical Melting
Type of solid Example
partical interaction state point
(i) Non polar 
dispersion
Very
(i) Molecular force. I2, Xe(s), C6H6, CCl4, Very soft
low
solid (non Molecules (ii) Polar  dipole- H2, HCl, SO2, SF4, Soft
Low
conducting) dipole. H2O(s), H3BO3(s) Hard
Low
(iii) Polar & H-
bonding.
(ii) Ionic solid.
solid 
Coulombic non
insulator NaCl, ZnS, Very hard Very
Ions directional
Molten & CaF4, CsCl Brittle high
long range.
aqueous
 conducting.
(iii) Metallic
Metal ion at fixed Soft  Hard
solid good
locations in sea of depending Low 
conductor Metallic bond. Cu, Al, Zn, Ag, etc.
delocalised on metallic High
in solid &
electrons. bond.
molten state.
(iv) Covalent or
Very hard
network.
C(diamond), SiC, Graphite  Very
Insulator Atoms Covalent bond.
SiO2, AlN, graphite. Soft only high
except C
conducting.
(graphite).
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ADVSST - 1
Solid State
Ex-1 Identify molecular solid, covalent solid, ionic solid: P4(s), S8 (s), SiC (s), Al2O3(s), He (s), Al2Cl6(s).
Sol. Molecular solid  P4(s), S8 (s), He (s), Al2Cl6(s)
Covalent solid  SiC
Ionic solid  Al2O3(s).
Th-1 General Characteristics of Solids:

(i) Solids have definite mass, shape and volume.
(ii) There are least intermolecular distances in solids as compared to liquids and gases.
(iii) There are strong intermolecular forces of attraction between particles in solids.
(iv) The particles of a substance cannot flow in their solid state but can flow in molten state.
(v) The constituting particles (atoms/ions/ molecules) have fixed positions. They can oscillate only about
their mean position, i.e., they have vibrational motions only.
(vi) They are rigid and incompressible.
Th-2 Types of SOLIDS on the basis of arrangement of particles:

On the basis of arrangement of particle in the solid, these can be classified into crystalline & amorphous
solids.
Tab-3
Crystalline solid Amorphous solids
True solid Pseudo solids, super cooled liquid [In
between solid & liquid]
1 The constituent practical (atoms, molecule, 1 No particular pattern is followed particle are
ion) follow a definite repeating arrangement. random arranged.
2 These have long range order. 2 They have short range order no long range
order are found.
3 These are produced by slow cooling under 3 Rapid or suddenly cooling of the liquid
controlled condition of liquid. The crystalline generate the amorphous solid.
structure is also dependent on conditions.
Same substance can have different
crystalline structure in different condition.
Different crystalline structure of the same
substance are called its polymorphic forms
& this is known as polymorphism.
4 These have fixed or sharp melting point and 4 These have a range of temperature in which
enthalpy of fusion. they melts as. There melting point and
Cooling Curve : enthalpy of fusion is not fixed.
5 These are anisotropic: Physical properties 5 These are isotropic:

will have different values in different All different physical properties are same in
direction. all different direction.
Reason : Due to random arrangement
of partical.
Ex. : Ag, Fe, Cu, NaCl, H2O (s), Dimond,

Quartz, Sucrose (Sugar)
Ex. : Glass, Plastic, Amorphous silica,
Rubber, Starch.
ADVSST - 2
Solid State
Th-3 Internal arrangement of particle in crystalline solid:
Each constituent particle (Molecule of any shape, atom, and ions) will be represented by a dot (.) and
this dot is called a lattice point.
D-1 Lattice: The 3-D regular and repeating arrangement of constituent particle represent by dots in solid is
called lattice.
D-2 Unit Cell: Unit cell is the smallest portion of a crystal lattice which, when repeated in different
directions, generates the entire lattice.
Th-4 Characteristics of a Unit Cell:
(i) Its dimensional along the three edges, a, b and c. These edges may or may not be mutually
perpendicular.
(ii) Angles between the edges,  (between b and c)  (between a and c) and  (between a and b).
(iii) Each unit cell has characteristic relation between a, b and c or , , and  to give rise different types
of unit cell.
Thus, a unit cell is characterised by six parameters, a, b, c, ,  and . These parameters of a typical
unit cell are shown in figure.
Illustration of parameters of a unit cell

Th-5 A unit cell may also be defined as a1D, 2D, 3D three dimensional group of lattice points that generates
the whole lattice by repetition or stacking.

  Generally most symmetrical and smallest volume unit cell is selected.

D-3 1-Dimensional Space Lattice: Uniformly separated lattice point in 1-D
only one parameter is required  distance between two lattice point.

D-4 2-Dimensional Space Lattice: Regular arrangement of point in plane 3 parameter required  Two
edge lengths & angle between these two edge.
ADVSST - 3
Solid State
Th-6 We can only shift the unit cell parallel not rotate it.
(i) Square unit cell   a = b,  = 90º
(ii) Rectangle unit cell   a  b,  = 90º
(iii) Hexagonal unit cell   a = b,  = 120º
(iv) Rhombic unit cell   a = b,   90º,   60º &  120º
(v) Parallelogram  a  b,   90º
Most symmetrical  square unit cell.
Square unit cell:
D-5 Primitive unit cell: Unit cell having lattice point only at the corner.
D-6 Non Primitive or centered unit cell: Unit cell having lattice point at corner as well as with in the unit
cell.
3-Dimensional Space Lattice:
Seven Primitive unit cells in crystals
c
b a c
Cubic b ; Tetragonal ; Orthorhombic c ;
b
a g b
a
a
(a = b = c,  =  = = 90º) (a = b  c,  =  = = 90º) (a  b  c,  =  = = 90º)
c
Monoclinic ; Hexagonal ;
c
b
a
b
a
(a  b  c,  = = 90º,   120º, 90º,  60º) (a = b  c,  = = 90º,  = 120º)
c
c
Rhombohedral ; Triclinic
b b
a
a
(a = b = c,  = =   90º) (a  b  c,      90º)
Th-7 The type of unit cells found in different types of crystals.

(Total number of atoms in unit cell)
1
1. Primitive /simple unit cell: =8× =1
8
ADVSST - 4
Solid State
2. Non primitive:
1
(a) Body centered (B.C.): =8× +1×1=2
8
1 1
(b) Face centered (F.C.): =8× +6× =4
8 2
1 1
(c) End centered (E.C.): =8× + ×2=2
8 2
Note: (1) Which particular type of unit cell will be found in a particular crystal class is decided on the basis of
‘’the surroundings of each & every lattice point in a particular lattice which is exactly identical.
(2) In 3-d to specify any unit cell 6 parameter are required.
 3-egde length (a, b, c) and 3-angle between these. (,  , ), [a–b], b–c], [c–a–].
Tab-4 Seven Crystal System
Crystal Edge Unit cell
S.No. Angles Examples
System length found
SC, BCC, NaCl, ZnS, Fe, Al, Cu, C
1 Cubic a=b=c º FCC (diamond), CsCl, Na2O, CaF2, KCl,
(3) Pb, Alum.
SC, BC Sn (white tin), SnO2, TiO2, ZnO2,
2 Tetragonal a=bc º
(2) NiSO4, urea.
SC, BC, FC,
Rhombic sulphur, BaSO4, KNO3,
3 Orthorhombic abc º EC
PbCO3, , CaCO3 (aragonite)
(4)
º
SC, EC Monoclinic sulphur, PbCrO4,
4 Monoclinic abc º,
(2) Na2SO4, 10H2O, Na2B4O7.10H2O
º, º
º SC Graphite, ZnO, CdS, Mg, PbI2,
5 Hexagonal a=bc
º (1) SiC.
Rhombohedral
SC CaCO3 (Calcite), HgS(Cinnabar),
6 or a=b=c º
(1) NaNO3, ICl.
Trigonal
SC
7 Triclinic abc º K2Cr2O7, CuSO4.5H2O, H3BO3
(1)
Hint for memorise: CTOMHRT

Note: In 3-D 14 different types of unit cell are found and these are also known as 14 Bravais lattice.
Th-8 Properties of a cube:
ADVSST - 5
Solid State
Th-9 Contribution of different Lattice point in one Cubical unit cell:
1
(i) Contribution from one corner lattice point = th.
8
(shared in 8 identical cubes)
1
(ii) Contribution from one face centered lattice point = .
2
1
(iii) Contribution from edge centered lattice point = th.
4
(iv) Contribution from body centered lattice point = 1.
(it is present inside or at the centre of cube)
Ex-2 The lattice parameters of a given crystal are a = 5.62 Å, b = 7.41 Å and c = 9.48 Å. The three
coordinate axes are mutually perpendicular to each other. The crystal is:
(A) tetragonal (B) orthorhombic (C) monoclinic (D) trigonal.
Ans. (B)
Sol. a b c &  =  =  = 90° the crystal system is orthorhombic.
Ex-3 Tetragonal crystal system has the following unit cell dimensions:
(A) a = b = c and  =  =  = 90° (B) a = b  c and  =  =  = 90°
(C) a  b  c and  =  =  = 90° (D) a = b  c and  =  = 90°,  = 120°
Ans. (B)
Ex-4 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
Ans. (C)
1 1 1
Sol. A=7 = ; B=6 =3
8 8 2
Formula = A7/8B3 or A7B24
ADVSST - 6
Solid State
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 Å.
Given: Atomic mass of X = 40 amu, Y = 60 amu, Z = 80 amu.
1 3
Sol. (i) X= ×6=
8 4
1 1 7
Y= ×2+ ×3=
8 2 4
1 5 10
Z= ×3+1+1= =
2 2 4
X Y Z
For formula: 3 7 10 = X3 Y7 Z10
4 4 4
(ii) 1 amu = 1.67 × 10–24 gram

1
1 amu = gram.
6.02  1023
3 7 10
 40   60   80
Mass 335  1.67  1024
Density = = 4 4 4 amu/cc = = 69.8 gram/cc.
Volume (2  108 )3 8  1024
Some Definitions
D-7 Coordination number: The number of nearest neighbours sphere in a packing is called coordination
number.
D-8 Density of unit cell: It is the ratio of mass of the spheres present in unit cell and total volume of unit
cell.
Massof total atoms present in aunit cell
Density of the unit cell =
Volume of that unit Cell
Z(M/ NA ) ZM
d 30
gcm3  d  gcm3
a  10
3
NA (a  1030 )
3
Where Z = no. of atoms in a unit cell

M/NA = mass of a single atom in grams (1 amu = 1/NA gram)
M = molar mass
NA = Avogadro number (6.023 × 1023)
D-9 Packing efficiency: The percentage of total space filled by the particles is called packing efficiency.
Different types of packing arrangements have different packing efficiency.
Volume of atoms in a unit cell
Packing efficiency =  100% For 3-D Crystal
Total volume of a unit cell
Th-10 Structure of Solids:

1-D Lattice:
d (d > 2R)  not close packing
  Arrangement of maximum stability.  Arrangement of minimum P.E.

  Arrangement of close packing.   Arrangement of maximum efficiency (100%).
2-D Lattice:
Can be considered to be made up of one dimensional array or lines.
ADVSST - 7
Solid State
Tab-5
Section (B): Simple Cubic Structure & BCC

Th-11 3-D Lattice:
When 2-D close packed layers are kept on each other 3-D close packing will be generated.
(A) Square packed sheets:
(1) Square packed sheets are kept on another such that -
atoms / spheres of one sheet are exactly above spheres of other sheet.
  A A A A ........... Pattern repeated.
 Simple cube can be taken as unit cell of this particular lattice:
(i) Relation between a & R.

Corner atoms are touching each other so, a = 2R.
(ii) Effective no. of atom (Z) (per unit cell).
1
Z = 8 [corner] × = 1 atom.
8
4
1 R3
3 
(iii) Packing efficiency: 3
 = 52.33%.
(2R) 6
Mass of unit cell  Z M 
(iv) Density =  .
volume of unit cell  NA  a3 
(v) Co-ordination number:
Number of nearest neighbour’s or (no. of sphere which are
touching any particular sphere). CN = 6.
(The * marked atom touches atom number 1, 5, 6 in its own

unit cell and 2, 3, 4 in other unit cells hence total number of
nearest atom = 6)
ADVSST - 8
Solid State
Tab-6
Type of neighbour Distance No. of neighbours
3  8 
(i) Nearest a (distance b/w 1 & 2)   6   6
 4 
3  8 
(ii) (next)1 2 a (distance b/w 1 & 3)   12  12
 2 
(2) Square packed layer are placed such that sphere of one layer occupy the depression of other layer.
  AB–AB type of arrangement of square sheet in 3-D.
a =edge length of cube; R = radius of sphere
Body centered cubic (BCC):
Not so close pack arrangement.

The lattice point in 2-D array do not touch each other. The sphere start touching each other only upon
moving from 2-D to 3-D.
2-D array placed on top of each other such that sphere of next plane are into cavities of first plane of
sphere.
 (i) Relation between a & R:
3
Spheres are not touching along edge they touching along the body diagonal. So a = 2 R.
2
1
(ii) Effective no. of atom (Z) = 8 × [corner] × +1=2
8
4 3
2 R
3 3
(iii) Packing fraction = 3
= = 68%.
 4R  8
 
 3
(iv) Co-ordination No. (CN) = 8. (Body centered atom have only 8 nearest neighbouring atoms
so CN = 8)
ZM
(v) Density = where Z = 2.
NA (a)3
Tab-7
3a
(i) Nearest (distance b/w 1 & 2) 8
2
(ii) (next)1 a (1 & 3) 6
ADVSST - 9
Solid State
(Note: In bcc crystal structure, the co-ordination no. is 8 because each atom touches four atoms in the
layer above it, four in the layer below it and none in its own layers.)
Ex-6 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
Ans. (B)
Ex-7 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 in its own
layer.
(B) each atom touches four atoms in the layer above it, four in the layer below it and one in 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.
Ans. (A)
Ex-8 Potassium crystallizes in body centered cubic lattice with a unit cell length a = 5.2 Å
(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 has?
(E) What is calculated density of crystalline K.
Ans. (A) 4.5 Å, (B) 5.2, (C) 8 , (D) 6 (E) 0.92 g/mL
3a 3  5.2
Sol. (A) 2r = = = 4.5 Å (B) distance = a = 5.2 Å
2 2
(C) 8 (D) 6
2  39
(E) d = = 0.92 g/ml
(5.2  108 )3  6.02  1023
Section (C): HCP & CCP structures

Th-12 (B) Arrangement of hexagonal closed packed sheets:
 To generate close packing two dimensions arrangement
must be hexagonal.
 Sheet are arranged such that void or depressions of one

sheet are occupied by sphere of other sheet.
 Only 50% void of one layer can be occupied by sphere of

other layer (II layer).
 Now there will be two method to place III layer on the II layer.
(1) Hexagonal close packing (HCP) AB–AB–AB- - - -Type.
 Sphere of III layer occupy those voids of II layer under which there are sphere of I st layer. So
third layer is exactly identical to Ist layer.
That why this generate ABAB- - - -AB pattern.
One type of void always remain on occupied.
ADVSST - 10
Solid State
Unit cell: a = 2r = b;  = 120º

(i) Relation between a, b, c and R:
a = b = 2R
(a / 2) a 3 3
tan30 = So y= = a.
y 2 1 2
1 a 3 a 6 3a 2
Area = 6  ×  =
 2 2  4
calculation of c.
(a / 2) 2a a
cos30º = x= =
x 2 3 3
Applying pythogoras theorem: x2 + h2 = a2
a2 2
so h2 = a2 – x2 = a2 – = a2
3 3
2
h= a (h = distance between two consecutive layers A – B)
3
2
so c = 2h = 2 a
3
c = height of hexagonal unit cell (Least distance between two same layers A–A or Ist and IIIrd).
ADVSST - 11
Solid State
So volume of hexagon = area of base × height
6. 3 2 6. 3 2
= × a2 × 2 a= × (2R)2 + 2 × (2R) = 24 2 R3
4 3 4 3
1 1
(ii) Effective no. of atoms (Z) = 3 + 2 × + 12 × = 3 + 1 + 2 = 6.
2 6
4
6   R3
3 
(iii) Packing efficiency = 3
= = 74%.
24 2 R 3 2
(iv) Coordination number, (CN) = 12
(Each sphere touch 6 sphere in its layer 3 above and 3 below)
mass  ZM 
(v) Density (d) = =   (z = 6)
volume  NA  volume 
Th-13 (2) ABC–ABC arrangement (Cubic close packing (CCP) or Face centred cube (FCC))
Third layer sphere are placed such that these occupy those 50% voids of II layer under which there are
void of Ist layer.
 IIIrd layer will be different from Ist layer as well as IInd layer.
 ABC–ABC type of arrangement.
 It is also known as cubical close packing, unit cell chosen is face centered unit cell (FCC).
(i) Relation between ‘a’ and ‘R’:

a  2R  2a  4R (sphere are touching along the face diagonal)
1 1
(ii) Effective no. of atoms per unit cell (Z) = ×8+ ×6=4
8 2
ADVSST - 12
Solid State
4
4  R3
3 
(iii) Packing fraction: P.F.   2 2 = = 0.74(74%)
444 R 3
3 2
(iv) Coordination number, (CN) = 12
ZM
(v) Density (d) = g/cm3 (a = Edge length of FCC unit cell)
NA .a3
Tab-8
a
(i) Nearest a (1 & 2) 12
2
(ii) (next)1 a (1 & 3) 6
Note: HCP and CCP are the only two type of close packed lattice (because of their effective efficiency 74%).
Ex-9 A metal crystallizes in two cubic phases i.e., FCC and BCC whose unit cell lengths are 3.5Å and 3.0 Å
respectively. The ratio of their densities is:
(A) 3.12 (B) 2.04 (C) 1.26 (D) 0.72
Ans. (C)
ZM d1 4 (3)3
Sol. d= 3 =  = 1.26.
a NA d2 (3.5)3 2
Ex-10 In a ccp structure, the:

(A) first and third layers are repeated (B) first and fourth layers are repeated
(C) second and fourth layers are repeated (D) first, third and sixth layers are repeated.
Ans. (B)
Ex-11 Lithium borohydride crystallizes in an orthorhombic system with 4 molecules per unit cell. The unit cell
dimensions are a = 6.8 Å, b = 4.4 Å and c = 7.2 Å. 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 4  21.76
Sol. d= 3 = = 0.6708 g cm2–.
a NA 8
6.8  10  4.4  10 8  7.2 10 8  6.023 10 23
Ex-12 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  10–8)3 cm3
(4  10 8 )
volume of NA atoms =  6.023  1023 = 9.6 ml.
4
Section (D): Voids

Th-14 Types of voids found in close packings:
 Although the close packed structure have maximum packings efficiency, but there are some empty
space left in arrangement.
D-10 Voids (Interstitial Voids): Although the close packed structures have the maximum packing
efficiency, there are indeed empty spaces left in the arrangements. These empty spcesa are known as
voids or. Interstitial Voids.
 Maximum size of sphere which can be place in void space is depends on size of void.
R = Radius of sphere (Bigger atom or ion)
r = Radius of sphere placed in void. (Smaller atom or ion)
ADVSST - 13
Solid State
D-11 2-Dimensions void:
(i) Triangular void [2D–3 coordinate void]
 This type of void found in close packed structure of plane when three sphere are in contact.
 R  R  r  1 r
cos30° =     = = 0.155.
R r   R  cos30º R
D-12 3-Dimensions void:
Tetrahedral void [3D-4 coordinate void]
 If IInd layer sphere are placed over a triangular void then new void is tetrahedral.
 R 
sin54º44’ = 
 R  r 
r
= 0.225
R
D-13 3-Octahedral void: [3D–6 coordinate void]

Octahedral void is formed when ever two sphere are placed, one on top and the other below a square
arrangement of sphere.
 This can also be obtained by placing two three ball arrangement on the top of each other.
r
2 a = 2[R + r] ; 2 2 R = 2[R + r]. = 0.414
R
ADVSST - 14
Solid State
D-14 Cubical void (3D-8-coordinate void)
Sphere are touch along body diagonal:
3 a = 2 [R + r] 
 2 3 R = 2 [R + r]
r
= 0.732
R
Th-15 Location of void:
(i) FCC or CCP unit cell:
(a) Tetrahedral void:
 FCC unit cell has 8 tetrahedral void per unit cell.
Just below every corner of the unit cell.
 As unit cell has 8 corner that’s why FCC unit cell
has 8 tetrahedral void per unit cell.
3a 3a
 Distance of tetrahedral void form corner is and distance between two tetrahedral void is = .
4 2
 FCC unit cell has 4 body diagonal and each body diagonal contain 2 tetrahedral void that’s why total
tetrahedral void = 8.
 If a large size cube is divided in 8 minicube than center of each minicube contain one tetrahedral void
3a
and distance of center of minicube from corner is .
4
 For FCC unit cell Z = 4 and tetrahedral void = 8 so tetrahedral void = 2 Z.
(b) Octahedral void (OV):
 Each edge center of FCC unit cell have one octahedral void and body center also contain 1
OV.
1
 Number of octahedral void per unit cell (Z) = 12 [Edge center] × + 1[Body center] = 4.
4
* For FCC unit cell (Z) = 4 and octahedral void = 4. So octahedral void = Z.
Th-16 Hexagonal close packing (HCP) unit cell:
(a) Tetrahedral void:
 HCP unit cell have total 12 tetrahedral void per unit cell.
 Out of which 8 are completely inside the unit cell and 12 are shared. Which are present on
1
cedge center and contribution of each sphere present on edge center is so.
3
1
Tetrahedral void (TV) = 8 [Inside the body] + 12 [at Edge center] × = 12.
3
For HCP unit cell (Z) = 6. So tetrahedral void = (Z × 2) = 12.
(b) Octahedral void:
* HCP unit cell have total 6 octahedral void, which are completely inside the unit cell.
So octahedral void = 6.
Note:
Tab-9
Unit cell Z Tetrahedral void = Z × 2 Octahedral void = Z × 1
CCP (FCC) 4 8 4
HCP 6 12 6
ADVSST - 15
Solid State
Ex-13(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)
rtetrahedral 0.225R
Sol. = = 0.543.
roctahedral 0.414R
(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-14 Copper has a face-centred cubic structure with a unit-cell edge length of 3.61Å.
What is the size of the largest atom which could fit into the interstices of the
copper lattice without distorting it?
(Hint.: Calculate the radius of the smallest circle in the figure)
Ans. 0.53Å
Sol. roctahedral = 0.414 R
For FCC 4R = 2 a
2a
R=
4
0.414 2 a 0.414 2  3.61
r= = = 0.53 Å
4 4
Section (E): Radius ratio rule and Type of ionic structures

Th-17 Structure of ionic compounds
Structure of compounds containing two different types of atoms.
The bigger atom or ion will form the lattice & smaller atom / ion will occupy the voids. Generally, bigger
ion is anion and smaller ion is cation.The type of void occupies by the cation is decided by radius ratio.
D-15 Radius Ratio Rule: Radius ratio = (r+/r–), the ratio of radius of cation to the radius of anion is known as
radius ratio of the ionic solid. This gives the idea about the type of void occupied.
Radius ratio = (r+/r–), this gives the idea about the type of void occupied.
Tab-10
Radius ratio Type of void occupied Coordination No. Ex. of ionic Compounds
r+/r– < 0.155 linear void 2
0.155  r+/r– < 0.225 triangular void 3 Boron oxide
0.225  r+/r– < 0.414 tetrahedral void 4 Zinc sulphide
0.414  r+/r– < 0.732 octahedral void 6 Sodium chloride
0.732  r+/r– < 1 cubical void 8 Caesium chloride
 NOTE: In ionic compounds for maximum stability.
(1) A Cation must be surrounded by maximum number of anions and vice versa.
(2) Anion-anion and cation–cation contact should be avoided
  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.
Considering a minicube
Mini
Cube
a/2
ADVSST - 16
Solid State
Cation will lie at the centre of the body diagonal of the mini cube of side a/2.
1
r– + r+ = × (body diagonal of minicube)
2
1 a
r+ + r– = × fcc 3
2 2
4
afcc = (r   r– )
3
Th-18 Structure of some ionic compound:

(1) NaCl type of structure (Rock salt structure):
rNa rNa
 Experimental = 0.51 (0.414 < < 0.732)
rCl– rCl–
(i) Cl– ions form the FCC lattice while Na+ ion occupy all the octahedral void.
(ii) Effective number of ion per unit cell
(iii) Effective number of Cl– ion per unit cell = 4
Effective number of Na+ ion per unit cell = 4
(iv) Formula of unit cell Na4Cl4
Formula of ionic compound = NaCl
Effective number of formula unit (Z) = 4
Z M
(v) Density (d) =
NA  a3
  Here 2 a  4 RCl  as anion–anion are not in contact.
  [ rCl  rNa ] = a/2
(vi) Coordination number:

Coordination number of Cl– = Number of Na+ ion touching it = 6.
Coordination number of Na+ = 6 [placed in octahedral void of Cl– ions].
Anion Cation
Tab-11
For Cl–:
a
(i) Nearest Na+ , 6
2
a
(ii) (next)1 Cl– , 12
2
ADVSST - 17
Solid State
Example: Halide of Li, Na, K and Rb, AgCl, AgBr, NH4Cl.
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 (Zinc blende) (AB type) (4: 4 coordination number compound):
Zinc blende type:

(i) S2– ion form the FCC lattice.
  Zn2+ ion occupy alternate (non adjacent) four tetrahedral void. Given below a face-view.
(ii) Effective number of ion

 Effective number of S2– ion per unit cell = 4.
  Effective number of Zn2+ ion per unit cell = 4.
(iii) Formula of unit cell = Zn4S4
Formula of ionic compound = ZnS
r 2 r 2
(iv) Experimental Zn = 0.3 (0.225 < Zn < 0.414)
rS2– rS2–
so anion–anion contact is not there.
3
so [ rZn2   rs2  ]=aFCC
4
 ZM 
(v) Density (d) =  3 
M = 97 gram/mole. (MZn = 65.3) + (MS = 32)
 NA  a 
(vi) Coordination number:
Coordination number of Zn2+ ions = 4.
Coordination number of S2– ions = 4.
Ex: ZnS, CuCl, CuBr, CuI, AgI.
Tab-12
For S2–
No. of
Type of neighbour Distance Ions
neighbours
3
(i) Nearest aFCC 4 Zn2+
4
a
(ii) (next)1 12 S2–
2
(3) CaF2 [Flourite structure] [AB2 type] (It is a different case)
Coordination number of compound
(i) Ca2+ ion form the FCC lattice.

  F– ion occupies all tetrahedral voids.
(ii) Coordination number of F– ion = 4 It occupies tetrahedral void.
  Coordination number of Ca2+ ion = 8
ADVSST - 18
Solid State
(iii) Effective number of Ca2+ ion = 4.
 Effective number of F– ion = 8.
(iv) Formula of unit cell = Ca4F8
  Formula of ionic compound = CaF2.
(v) Effective number of formula unit cell (Z) = 4.
 ZM 
(vi) Density =  3 
 NA  a 
rF– 3a
(vii) 0.225 < < 0.414 ; [rCa2+ + rF–] =
rCa2 4
Other examples: CaF2, SrF2, BaF2, BaCl2.
Tab-13 For Ca2+
Type of neighbour Distance No. of neighbours Ions
3
(i) Nearest 8 F–
4
a
(ii) (next)1 12 Ca2+
2
Tab-14 For F—
Type of neighbour Distance No. of neighbours Ions
3
(i) Nearest 4 Ca2+
4
a
(ii) (next)1 6 F–
2
(4) Na2O [Sodium oxide] [A2B type]

 Anti-fluorite structure [4: 8 coordination compound]  (O2– ion at FCC lattice).
Na+ = All the tetrahedral void.
r 
(5) CsCl type of structure [8: 8 coordination compound]: Cs ~ 0.93
rCl–
(i) Cl– form simple cubic lattice.
 Cs+ ion occupies cubical void.
(ii) Effective number of ion:
  Effective number of Cs+ ion = 1. & Effective number of Cl– ion = 1.
(iii) Formula of ionic compound = CsCl. So Z = 1.
 ZM 
(iv) Density (d) =  3 
 NA  a 
 anion–anion contact is not there so,
3 aSC
[rCl– + rCs+] =
2
(v) Coordination number of Cs+ ion = 8. (vi) Coordination number of Cl+ ion = 8.
Other example: CsCl, CsBr, CsI.
Note: On increasing pressure  Coordination number tends to increase.
On increasing temperature  Coordination number tends to decrease.
P T
4: 4   6: 6 ; 8: 8   6: 6
ADVSST - 19
Solid State
STRUCTURES OF SOME CRYSTALS
S.No. Crystal C.N Z Structural arrangement E.g.
Total
Cation Anion formula
unit
Na+ = 4 Na+ = at all octahedral voids
1 NaCl 6 6 LiCl
Cl– = 4 Cl–  FCC
ZnS Zn2+ = 6 Zn2+ = At 1/2 TV
2. 4 4 AgI
(wurtizite) S2– = 6 S2– = HCP
CuCl
ZnS Zn2+ =4 Zn2+ = At 1/2 of TV CuBr
3. 4 4
(Blende) S2– = 4 S2– = FCC CuI,
Cds
CaF2 Ca2+ = 4 Ca2+ = FCC BaF2
4. 8 4
(Fluorite) F– = 8 F– = All TV SrF2
Na+ = 8 Na+ = All TV
5. Na2O 4 8
O2– = 4 O2- = FCC
CsCN
Cs+ = 1 Cr+ = Body centered void (Cubic void)
6. CsCl 8 8 CsI
Cl– = 1 Cl– = At corners
CaS
# Rutile (TiO2) CN
Cation 6
Anion 3
# Perovskite (CaTiO3) CN
At Body centre Ca++ 12
At corner Ti4+ 6
At Edge centre O2– 2
Th-19 Other important structure:

(1) Spinel structure [AB2O4]: Spinel is an oxide consisting of two type of metal ions with the oxides ion
arranged in CCP layers in normal spinel one eighth of the tetrahedral holes occupied by one type of
metal ion and one half of the octahedral holes occupied by another type of metal ion. eg: A spinel is
formed by Zn2+, Al3+ and O2– with Zn2+ ion in the tetrahedral holes. The formula of the spinel is ZnAl2O4.
(2) Perovskite structure [ABO3]: This structure may be described as a cubic lattice, with barium ions
occupying the corners of the unit cell, oxide ions occupying the face centers and titanium ions
occupying the centres of the unit cells. eg: BaTiO3 or MgTiO3.
(3) Lattice of diamond: ZnS types in which all S2– location and all Zn2+ location are occupied by C
atoms.
So, Z = 8 atom per unit cell
3
dC – C = aFCC
4
dC – C = 2rC – C where rC – C is radius of C-atom.
* Packing efficiency = 34%.

*In crystal lattice of diamond, carbon atoms adopt FCC arrangement with occupancy of 50%
tetrahedral voids.
2 2
Note: (1) Distance between two plane in FCC or HCP arrangement is 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 = x 3.
ADVSST - 20
Solid State
e.g.
Number of unit cell along one edge = 2, then total number of unit cell in cube = 23 = 8.
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.
Ex-16 CsBr has b.c.c. structure with edge length 4.3 A. The shortest inter ionic distance in between Cs + and
Br– is:
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3
Ans. (A)
3a 3  4.3
Sol. r+ + r– = = = 3.72 Å .
2 2
Section (F): Crystal defects and Properties of solids

Th-20 Crystal imperfections / defects
Imperfections can be because of:-
- Conditions under which crystals have been developed,
- Impurities,
- Temperature (because of thermal conductivity some atoms/ions can get displaced)
These imperfections can be
(a) Point defects: Defects will be only at certain lattice positions.
(b) Line defects: If atoms/ions are misplaced/missing/replaced by some other ions along a line.
(c) Plane (screw) defects: If atoms/ions are misplaced/missing/replaced by some other ions along a
line in a plane.
D-16 Point Defects:
1. Stoichiometric: The formula of compound remains same even after presence of these defects.
2. Non-stoichiometric: The formula of compound will get modified because of the presence of these
defects.
(i) Stoichiometric defects:
(a) Schottkey (b) Frenkel (c) Interstitial
Missing ions pairs dislocated cation Cation Anion Interstitial entity
Cation Anion Cation Anion
Schottky defect Frenkel defect Interstitial defect
D-17 Schottkey: When atoms/point are totally missing from the lattice.
Net density of crystal will get decreased
exp < theoritical
 th – exp 
% missing units =    100%
 th 
ADVSST - 21
Solid State
D-18 Frenkel: When atoms/ions displaced from normal lattice positions and are present in some interstitial
voids. Density remains same
D-19 Interstitial: When some small foreign atoms are trapped in interstitial voids of the lattice without any
chemical reaction. Formula remains the same exp > theortical
Th-20 (ii) Non-stoichiometric defects:
D-20 (a) Metal excess or cation excess defect:
- If no. of missing anion is more than no. of missing cations.
- To maintain electrical neutrality some electron are trapped at anionic vacancies.
Because of these extra electrons the electrical and optical (colour) properties of the compound get
modified.
So these locations of elecoron are also known as colour centres (F-centres).
ZnO - white in colour at room temperature.
- On heating some O2– ion get released in the form of O2 and e– are trapped at their locations. Because
of this it because yellow in colour.
D-21 (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 neutrality.
Cation Anion Sr+2 replacing Na+
F-centre
Na+ Cl- Na+ Cl- Na+ Cl-
-e Na+ Cl- Na+ Cl- Sr+2 Cl- Na+ Cl-
Na+ Cl- Na+ Cl- Na+ Cl-
Metal excess Cation Vacancy
Ex-17 Which of the following is incorrect
(A) The defect is known as Schottky defect

(B) Density of compound in the defect decreases
(C) NaCl(s) is example which generally shows this defect
(D) Stoichiometry of compound will change slightly.
Ans. (D)
Ex-18 Ferrous oxide (FeO) is experimentally found to have the formula Fe0.93O. Find the %age of Fe ions in
+3 state.
Fe0.93O
Some Fe atom Some Fe atom

Sol. are in +2 state are in +3 state
Let there is xFe atom in +3 state
14 1400
3x + 2(93 – x) = 200  x = 14  % Fe3+ = × 100% = %  15.54%
93 93
Th-21 Properties of Solids:

(i) Electrical Properties (ii) Magnetic Properties
(i) Electrical Properties: Solids exhibit an amazing range of electrical conductivities, the range of
electrical conductivities from 10–20 to 107 ohm–1 m–1. Solids can be classified into three types on the
basis of their conductivities.
D-22 (1) Conductors: Metals are goods condcutors and have conductiveites in the order 107 (m–1).
D-23 (2) Insulators: Those solids which have very low conductivities ranging from 10 –20 to 10–10 (m–1) are
electrical insulators e.g.; MnO, CoO; NiO, CuO, Fe2O3, TiO2.
ADVSST - 22
Solid State
D-24 (3) Semiconductors: Those solids which have intermediate conductivities generally from 10–6 to
104(m–1) are termed as semiconductors.
D-25 Intrinsic Semiconductors: The conduction by pure substances such as silicon and germanium is
called intrinsic conduction and these pure substances exhibiting electrical conductivity are called
intrinsic semiconductors.
Th-22 Causes of Conductance in Solids:
1. In most of the solids, conduction is through electron movement under an electric field.
2. In ionic solids conduction is by movement of ions in molten state.
3. The magnitude of electrical conductivity strongly depends upon the number of electrons available to
take part in conduction process.
4. In metals, conductivity strongly depends upon the number of electrons available per atom. The
atomic orbitals form molecular orbitals which are too close in energy to each other so as to form a band.
5. If conduction band is not completely filled or it lies very close to a higher unoccupied band, then
electrons can flow easily under an electric field thereby showing conductivity.
6. In case of insulators, the gap between valence band conduction band is too large, so electrons
cannot jump from valence band to conduction band and very small conductivity is observed.
7. In case of semiconductors, the gap between valence band and conduction band is small and
therefore some of the electrons may jump from valence band to conduction and some conductivity is
observed.
8. Electrical conductivity of semiconductors increases, with increase in temperature. This is due to the
fact that with increase in temperature, large number of valence electrons from the valence band can
jump to conduction band. Pure substances like silicon and germanium that exhibit this type of
conducting behaviour are called intrinsic semiconductors.
9. For particle purpose, the conductivity of pure silicon and germanium is too low at room temperature,
therefore, there is need to increase the conductance by doping.
D-26 Doping: The conductivity of silicon and germanium can be increases by adding apporpirate amount of
suitable impurity. The process is called doping.
Th-23 Type of Semiconductors:
(1) n-Type Semiconductors: Metal excess compounds conduct electricity through normal electron
conduction mechanism and are therefore n-type semiconductors.
Th-24 n-Type Semiconductor:
1. When silicon is doped with small amount of group -15 elements such as P, As or Sb, its electrical
conductivity increases sharply.
2. In pure silicon each silicon atom uses its four valence electrons for the formation of four covalent
bonds with the neighbouring silicon atoms.
3. When silicon is doped with some group-15 element, the some of the positions in the lattice are
substituted by atoms of groups-15 elements have five valence electrons. After forming the four covalent
bonds with silicon (or any other group-14 element such as germanium). One excess electron is left on
them.
4. Since this electron is not involved in bonding it becomes delocalized and contribute to electrical
conduction. Silicon doped with group 15 element behaves as a n-type semiconductor.
ADVSST - 23
Solid State
(2) p-Type Semiconductors: Metal deficient compounds conduct electricity through positive hole
conduction mechanism and are therefore p-type semiconductors.
Th-25 p-Type Semiconductor:
1. Electrical conductivity of silicon or germanium can also be increases by doping with some group-13
element such as B, Al or Ga.
2. Goup-13 elements have only three valence electrons. They combine with group-14 elements to form
an electron deficient bond or electron vacancy or a hole. These holes can move through the crystal like
a positive charge giving rise to electrical conductivity.
3. Gorup-14 elements doped with group-13 elements behave as p-type semiconductors.
In the presence of electrical field the holes move in direction opposite to that of electrons.
Th-26 Application of n-type and p-type semiconductors.
1. Diode is a combination of n-type and p-type semiconductors used as rectifier.
2. They are used for making transistors which contains n-p-n and p-n-p junctions to amplify radio and
audio signals.
3. The solar cell is photo-diode used to convert light energy into electrical energy.
D-27 13-15 Compounds: The solid state materials are produced by combination of elements of groups 13
and 15 the compounds thus obtained are called 13-15 compounds e.g. InSb, AlP GaAs.
D-28 12-16 Compounds: The solid state compounds are obtained by combination of elements of groups 12
and 16 the compounds are called 12-16 compounds e.g. ZnS, CdS, CdSe and HgTe.
D-29 Super Conductivity: The electrical resistance of metals is found to depend on temperature. Electrical
resistance decreases with decrease in temperature and becomes almost zero near the absolute zero.
Materials in this state are said to possess. Superconductivity. The phenomenon of superconductivity
was first discovered by Kammerlingh Onners in 1913 when he found that mercury becomes
superconducting at 4.0 K temperature.
D-30 Transition Temperature: The temperature at which a substance starts behaving as super-conductor is
called transition temperature.
Th-27 (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.
Demonstration of the magnetic moment associated with (a) an orbiting electron and (b) a spinning electron.
On the basis of their magnetic properties, substances can be classified into five categories:
(i) paramagnetic (ii) diamagnetic (iii) ferromagnetic (iv) antiferromagnetic and (v) ferrimagnetic.
D-31 (1) Paramagnetic: When substances which are attracted by the external magnetic field are called
paramagnetic substances and the phenomenon is called as paramagnetic. Atoms ion or molecules
containing unpaired electron show this property, eg. O 2 Cu2+, Fe3+ etc. these substances lost their
magnetism in the absence of magnetic field.
ADVSST - 24
Solid State
D-32 (2) 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.
D-33 (3) 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.
D-34 (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 Anti-ferromatic 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.
D-35 (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
D-36 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.
D-37 Domain: In solid state the metal ions of ferromagnetic substances are grouped together into small
regions called domains.
Th-28 Effect of Temperature on Metal (Conductor) Semiconductor or Insulator:
1. The conductivity of semiconductors and insulators increases with increase in temperature
2. The conductivity of metal (conductors) decreases with increase in temperature.
Ex-19 What is a semiconductor? Name the two main types of semiconductors.

Ans. Substances whose conductance lies in between that of metals (conductors) and insulators are called
semiconductors. Two main types of semiconductors are n-type and p-type.
Ex-20 Explain the following with suitable examples:
(i) Ferromagnetism (ii) Paramagnetism (iii) 12-16 and 13-15 group compounds.
Ans. (i) 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.
(ii) 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. O 2 Cu2+, Fe3+ etc. these substances lost their
magnetism in the absence of magnetic field.
(iii) 13-15 Compounds: The solid state materials are produced by combination of elements of groups
13 and 15 the compounds thus obtained are called 13-15 compounds e.g. InSb, AlP GaAs.
12-16 Compounds: The solid state compounds are obtained by combination of elements of groups 12
and 16 the compounds are called 12-16 compounds e.g. ZnS, CdS, CdSe and HgTe.
ADVSST - 25
Solid State
MISCELLANEOUS SOLVED PROBLEMS (MSPs)
1. Calculate the number of formula units in each of the following types of unit cells:
(a) MgO in a rock salt type unit cell
(b) ZnS in zinc blende structure
(c) platinum in a face-centred cubic unit cell.
Sol. (a) 4 (the same as in NaCl) (b) 4 (c) 4 (1 at the corner, 3 at the face-centres)
2. A mineral having the formula AB2 crystallises in the cubic close-packed lattice, with the A atoms
occupying the lattice points. What is the coordination number of the A atoms and B atoms? What
percentage fraction of the tetrahedral sites is occupied by B atoms?
Sol. C.N. of A atom = 8; C.N. of B atom = 4
tetrahedral sites occupied by atoms B = 100% (all tetrahedral voids are occupied).
3. (a) What is the C.N. of Cr atom in bcc structure ?
(b) Cobalt metal crystallises in a hexagonal closest packed structure. What is the C.N. of cobalt atom ?
(c) Describe the crystal structure of Pt, which crystallises with four equivalent atoms in a cubic unit cell.
Sol. (a) 8, (b) 12, (c) fcc or cubic close packed.
4. Titanium metal has a density of 4.54 g/cm3 and an edge length of 412.6 pm. In what cubic unit cell does
titanium crystallise? (Ti = 48)
zM
Sol. Density d = 3
a N0
d = 4.54 g/cm3 , M = 48g mol–1 , Z = ? N0 = 6.023 × 1023 mol–1
If value of z is known, structure can be decided
dN0 a3 4.54  6.023 10 23  (412.6 10 –10 ) 3
z= = =4
M 48
Thus, titanium has face-centred cubic structure.
5. MgO has a structure of NaCl and TiCl has the structure of CsCl. What are the coordination numbers of
ions in each (MgO and TiCl).
Sol. C.N. of Na+ in NaCl = 6
C.N. of Cl– in NaCl = 6
Hence C.N. of Mg2+ is also = 6 and that of O2– or O2– = 6 in MgO
We know in CsCl
C.N. of Cs+ = 8
C.N. of Cl– = 8
Hence, Ti+ and Cl–, in TiCl, have also C.N. 8 each.
6. A solid AB has the NaCl structure, If radius of cation A+ is 120 pm, calculate the maximum possible
value of the radius of the anion B–.
Sol. We know for the NaCl structure, for maximum of radius of B–, the ratio r+ / r– should be minimum for
octahedral void i.e. 0.414.
Radius of cation/radius of anion = 0.414
rA  r 120
= 0.414  rB– = A = = 290 pm.
rB– 0.414 0.414
7. The C.N. of the barium ion Ba2+, in BaF2 is 8. What must be the C.N. of F– ion ?
Sol. C.N. of barium ion tells us that it is surrounded by eight fluoride ions (charge 8 × (–1) = –8). In order to
balance out the eight negative charges, we need four barium ion (charge 4 × (+2) = +8). Hence, the
C.N. of F– ions must be 4.
8. The radius of calcium ion is 94 pm and of oxide ion is 146 pm. Predict the crystal structure of calcium
oxide.
r 94
Sol. The ratio  = = 0.644
r– 146
The prediction is an octahedral arrangement of the oxide ions around the calcium. Because the ions
have equal but opposite charges, there must also be an octahedral arrangement of calcium ions around
oxide ions. Thus CaO structure is similar to Rock Salt (NaCI) structure.
ADVSST - 26
Solid State
9. Sodium metal crystallises in body centred cubic lattice with cell edge = 4.29 Å. What is radius of sodium
atom?
Sol. In ‘BCC’ structure
body diagonal = 4 × rNa = 3  a
3
 4 × rNa = 3  4.29  rNa =  4.29 = 1.86 Å
4
10. CsCI crystallises in a cubic that has a CI– at each corner and Cs+ at the centre of the unit cell. If rCs =
1.69 Å and rCl = 1.81 Å, what is value of edge length a of the cube?
Sol. We assume that the closest Cs+ to CI– distance is the sum of the ionic radii of Cs  and Cl.
= 1.69 + 1.81 = 3.50 Å
a 3
This distance is one-half of the cubic diagonal =
2
a 3
 = 3.50 Å  a = 4.04 Å
2
11. Platinum (atomic radius = 1.38 Å) crystallises in a cubic closest packed structure. Calculate the edge
length of the face-centred cubic unit cell and the density of the platinum (Pt = 195).
a
Sol. r= (for fcc), a = 2 2 r = 3.9 Å
2 2
ZM 4  195
Density = 3 = 8 3
= 21.83 g/cm3.
a N0 (3.9  10 )  6.023 10 23
12. Calculate the edge length of the unit cell of sodium chloride given density of NaCI is 2.17 × 103 kg m–3
and molecular weight 58.5 × 10–3 kg mol–1.
Sol. NaCI is face-centred cubic lattice so that number of NaCI molecules in a unit cell (z) = 4.
zM
We know density d = 3
a N0
Where, a = length of the unit cell
Mz 4  58.8  10 3
Volume = a3 = = = 1.79 × 10–28 m3
dN0 2.17  103  6.02 10 23
a = 5.64 × 10–10 m = 5.64 Å = 564 pm.
13. The effective radius of an iron atom is 1.42 Å. It has a rock-salt structure. Calculate its density (Fe = 56).
Sol. Due to rock-salt (fcc) structure, number of atoms in a unit cell (z) = 4.
zM
Thus, d (density) = 3 a = 2 2 r = 2 2 × 1.42 × 10–8 cm
a N0
4  56
 d= = 5.743 g/cm3
6.02  10  (2 2  1.42  108 )3
23
14. In a CPS (close packed structure) of mixed oxides, it is found that lattice has O 2– (oxide ions), and one-
half of octahedral voids are occupied by trivalent cations (A 3+) and one-eighth of tetrahedral voids are
occupied by divalent cations (B2+). Derive formula of the mixed oxide.
Sol. Number of octahedral voids per ion in lattice = 1
1 1
Hence, Number of trivalent cations (A3+) = 1 × 
2 2
Number of tetrahedral voids per ion in lattice = 2
1 1
Hence, Number of divalent cations (B2+) = 2 × 
8 4
Thus, formula is A1/2 B1/4O or A2BO4.
15. An element crystallises as face-centred cubic lattice with density as 5.20 g/cm 3 and edge length of the
side of unit cell as 300 pm. Calculate mass of the element which contains 3.01 × 1024 atoms.
ADVSST - 27
Solid State
Sol. z = 4 in fcc lattice M = ?, d = 5.20 g/cm3
a = 300 pm = 3 × 10–8 cm
 a3 = 27 × 10–24 cm3
N0 = 6.02 × 1023
dN0 a3 5.20g/ cm3  6.02 10 23 mol 1  27 10 24 cm 3
 M= = = 21.13 g mol–1
z 4
Thus, 6.02 × 1023 atoms have = 21.13 g
21.13
 3.01 × 1024 atoms have = × 3.01 ×1024 g = 105.65 g
6.02  1023
16. Calcium crystallises in a face-centred cubic unit cell with a = 0.556 nm. Calculate the density if it
contained 0.1% vaccancy defects.
zM
Sol. Thus, density can be determined using d = 3
a N0
3.996  40
d(with vaccance defect) = = 1.5448 g/cm3
(0.556  107 )3  6.02  1023
CHECK LIST
Theories (Th) D-13: Octahedral Voids (3-Dimensional 6 coordinate void) 
Th-1: General Characteristics of Solids  D-14: Cubical void (eight coordinate void) 
Th-2: Types of SOLIDS on the basis of arrangement of particles D-15: Radius Ratio Rule 
Th-3: Internal arrangement of particle in crystalline solid  D-16: Point defects 
Th-4: Characteristics of a Unit Cell  D-17: Schottky Defects 
Th-5: Unit cell  D-18: Frenkel Defects 
Th-6: Types of unit cell  D-19: Interstitial Defects 
Th-7: The type of unit cells found in different types of crystals  D-20: Metal excess defects due to interstitial cations 
Th-8: Properties of a cube  D-21: Metal deficiency due to cation vacancies 
Th-9: Contribution of different Lattice point in one cubical unit cell D-22: Conductors 
 D-23: Insulators 
Th-10: Structure of Solids  D-24: Semicondutors 
Th-11: 3-D Lattice  D-25: Intrinsic Semiconductors 
Th-12: Arrangement of hexagonal closed packed sheets  D-26: Doping 
Th-13: ABC–ABC arrangement (Cubic close packing (CCP) or D-27: 13-15 Compouds 
Face centred cube (FCC))  D-28: 12-16 Compounds 
Th-14: Types of voids found in close packings  D-29: Super Conductivity 
Th-15: Location of void  D-30: Transition Temperature 
Th-16: Hexagonal close packing (HCP) unit cell  D-31: Paramagnetism 
Th-17: Structure of ionic compounds  D-32: Diamagnetic materials 
Th-18: Structure of some ionic compound  D-33: Ferromagnetism 
Th-19: Other important structure  D-34: Anti Ferro Magnetism 
Th-20: Crystal imperfections/defects  D-35: Ferrimagnetism 
Th-21: Properties of Solids  D-36: Curie temperature 
Th-22: Causes of Conductance in Solids  D-37: Domain 
Th-23: Type of Semiconductors  Table (Tab)
Th-24: n-Type Semicondcutor  Tab-1 : Properties of solid, liquid and gas. 
Th-25: p-Type Semiconductor  Tab-2 : Types of solid 
Th-26: Application of n-type and p-type semicondcutiors  Tab-3 : Crystalline and amorphoux solid 
Th-27: Magnetic Properties  Tab-4 : Seven Crystal system 
Th-28: Effect of Temperature of Metal (Conductor) Semiconductor Tab-5 : Close Packing in 2-Dimension 
or Insulator  Tab-6 : Nearest neighbour in SC 
Tab-7 : Nearest neighbour in BCC 
Definitions (D)
Tab-8 : Nearest neighbour in FCC 
D-1: Lattice 
Tab-9 : Relation between tetrahedral void and octahedral void
D-2: Unit cell 
Tab-10 : Ratio of voids. 
D-3: 1-Dimensional Space Lattice 
Tab-11 : Nearest neighbour in NaCl. 
Tab-12 : Nearest neighbour in S2– 
Tab-13 : Nearest neighbour in Ca2– 
D-6: Non Primitive or centered unit cell 
Tab-14 : Nearest neighbour in F– 
D-7: Coordination number 
D-8: Density of unit cell 
D-9: Packing efficiency 
D-10: Voids (Interstitial Voids) 
D-11: Triangular void (2-Dimensional 3-coordinate void) 
D-12: Tetrahedral Voids (3-Dimensional 4-coordinate) 
ADVSST - 28

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Solid State

Section (A): Basics of solid state

Th-1 General Characteristics of Solids:

Th-2 Types of SOLIDS on the basis of arrangement of particles:

5 These are anisotropic: Physical properties 5 These are isotropic:

Ex. : Ag, Fe, Cu, NaCl, H2O (s), Dimond,

Illustration of parameters of a unit cell

  Generally most symmetrical and smallest volume unit cell is selected.

only one parameter is required  distance between two lattice point.

Square unit cell:

3-Dimensional Space Lattice:

Seven Primitive unit cells in crystals

Th-7 The type of unit cells found in different types of crystals.

Hint for memorise: CTOMHRT

Th-9 Contribution of different Lattice point in one Cubical unit cell:

(shared in 8 identical cubes)

(shared in 2 identical cubes)

(shared in 4 identical cubes)

(iv) Contribution from body centered lattice point = 1.

(it is present inside or at the centre of cube)

(ii) 1 amu = 1.67 × 10–24 gram

Where Z = no. of atoms in a unit cell

Th-10 Structure of Solids:

d (d > 2R)  not close packing

  Arrangement of maximum stability.  Arrangement of minimum P.E.

Section (B): Simple Cubic Structure & BCC

(i) Relation between a & R.

(The * marked atom touches atom number 1, 5, 6 in its own

a =edge length of cube; R = radius of sphere

Body centered cubic (BCC):

Not so close pack arrangement.

(ii) (next)1 a (1 & 3) 6

Section (C): HCP & CCP structures

 Sheet are arranged such that void or depressions of one

 Only 50% void of one layer can be occupied by sphere of

Unit cell: a = 2r = b;  = 120º

(i) Relation between ‘a’ and ‘R’:

(ii) (next)1 a (1 & 3) 6

Ex-10 In a ccp structure, the:

Section (D): Voids

D-13 3-Octahedral void: [3D–6 coordinate void]

(b) Octahedral void (OV):

Section (E): Radius ratio rule and Type of ionic structures

Th-18 Structure of some ionic compound:

  [ rCl  rNa ] = a/2

(vi) Coordination number:

Zinc blende type:

(ii) Effective number of ion

(i) Ca2+ ion form the FCC lattice.

(4) Na2O [Sodium oxide] [A2B type]

Th-19 Other important structure:

* Packing efficiency = 34%.

Section (F): Crystal defects and Properties of solids

Schottky defect Frenkel defect Interstitial defect

-e Na+ Cl- Na+ Cl- Sr+2 Cl- Na+ Cl-

Na+ Cl- Na+ Cl- Na+ Cl-

Metal excess Cation Vacancy

Ex-17 Which of the following is incorrect

(A) The defect is known as Schottky defect