Solid State

SOLUTION OF SOLID STATE

EXERCISE # 1

PART - I
A-1. On the basis of classification of solid.

A-2. Contribution on the basis of angle and diagram.

B-1. Contribution of atom

1
At face center =
2
At body center = 1

B-2. Coordination number of Li and Ag in given structure is 8. So it is a bcc arrangement.

B-3. We know for B.C.C. 4R = a 3

287  3
R= = 124.27 pm.
4
2  52
density = = 7.30 gm / cm3.
 
3
6.023  1023 287  10—10

C-1. (ccp) ABC–ABC .... Type

6  vol. of 1 atom
C-2. Packing efficiency of hcp =
Vol. of unit cell
ZM 6  24.31
Volume of unit cell = = = 13.9179 × 10–23 cm3.
NA  d 6.023  1023  1.74
Packing fraction  Vol. of unit cell 0.741  13.9179  10 23
So, volume of 1 atom = =
6 6
= 1.718 × 10–23 cm3.
4 3
Volume of 1 atom = r .
3
1/ 3
 Volume of 1 atom  3 
Radius of 1 atom = (r) =   = (0.41055 × 10–23)1/3 = 1.60 Å.
 4

C-3. Atom b,f and g are at equal distance from atom 1

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 Solid State
C-4. (i) distance between 1 and 2 = 2r
2 and 3 = 2r

 2 2r 
2
1 and 3 =  2r 2 = (2 3 )r

(ii) Shape = square and length of square = 2r

ZM 27 Z  27amu
C-5. We know d = = =
(a)3 16  4.0Å 3
Z = 4 Then unit cell f.c.c. and we know for f.c.c. 4r = a 2
4
r= 2 = 2 Å.
4

C-6.

ABAB............type arrangement (unit cell = HCP).

D-1. Rhombous. 60o and 120o

Whole available space not occupy.

No. of void = 2
Type of void = Triangular

3 R
Sin 60 = =  r = 0.155 R
2 R  r 
D-4. Number of octahedral voids in fcc = 4.
Number of tetrahedral voids in fcc = 8.
a
Distance between two octahedral voids =
2
a
Distance between two tetrahedral voids =
2

E-4. (a) KBr is NaCl type, so no. of K+ & Br– are 4 each.
 
(b) a = 2 rK   rBr  = 2(1.33 + 1.95) = 6.56 Å
4  119
(c) density = = 2.80 g/cm3
6.02  1023  (6.65  10 8 )3

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 Solid State
r
(d) for octahedral voids, = 0.414
r

PART - II
A-1. KCl & BaCl2.2H2O are ionic solids and not pseudo solids (amorphous solids).

A-2. Unit cell: Unit cell is the smallest portion of a crystal lattice which, when repeated in different directions,
generates the entire lattice.

A-3. Orthorhombic crystal system has a  b  c and  =  =  = 90º.

A-4. For rhombohedral system, axial distance and axial angles are a = b = c,  =  =  900

A-5. In Bravais lattices, each point has identical surroundings.

A-6. For hexagonal unit cell  a = b  c ;  =  = 90º ;  = 120º.

B-1. For bcc unit cell coordination number = 8 (In bcc crystal structure, the co-ordination no. is 8 because
each atom touches four atom in the layer above it, four in the layer below it and none in its own layers).

3a 1.732  286
B-2. For bcc structure 3 a = 4r, r= = = 123.8  124 pm.
4 4

3a 3  2 1.732  2
B-3. Distance between two nearest neighbours in bcc = = = = 4.503 Å.
2 2 2

1  207 23
B-4. Density of P0 = = Amu / Å3
 3 3
3
B-5. Number of next nearest neighbours of Li (in bcc) = 6.
(These atoms present at the corner of bcc unit cell).

B-6.

de = a
dfd = 2a
3a
dbd =
2
 dfd > de > dbd

2 2
C-2. The shortest distance between Ist and Vth layer of HCP arrangement is = 2C = 2 × 4 r=8 r.
3 3

C-3. Volume of hexagon :

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 Solid State
a a 3 3 1a 3 a  6 3a2
tan30º = So, y = = a and area of hexagonal surface = 6    =
2y 2 1 2 2 2  4
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

C-4. P.F. of ABAB arrangement in 3D = 74%.

% of vacant space = 26% = 0.26.

C-6. Total number of atoms per unit cell in fcc structure = 4 atoms.

C-7. The arrangement of sphere is shown by body diagonal plane.

C-8. 4r = a 2
4r 4  1.28
a  Å = 3.62 Å
2 2

C-9. Packing efficiency of FCC or CCP = 74%.

C-10. Coordination number of sphere in fcc or ccp = 12.

C-11. In ABB AABB A, there is no close packing as there are repeated planes adjacent to each other.

D-1. No. of A atoms = 6.

2
No. of C atoms = 6 × = 4.  Formula = C4A6 or C2A3.
3

D-2.

D-3. It is a octahedral void.

D-4. For close packed structure of AB type solid

r+ / r– = 0.225 – 0.7342
Minimum value of r– = r+ / 0.732 = 75 / 0.732 = 102.5 pm
Maximum value r– = r+ / 0.225 = 75 / 0.225 = 333.3 pm

C C C
A A
B B B
D-5. A A Octahedral void, at edge center & body center.
C C C
 Tetrahedral voids on body diagonal.

D-6. Refer theory octahedral & tetrahedral voids about positions of P1, P2 and P3.

1
D-7. No. of tetrahedral voids = 8 × =1
8
No. of octahedral voids = 1×1 = 1 (at body center).

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 Solid State
r 126
E-1.  = 0.58, octahedral voids so C.N. = 6.
r 216

E-2. In rock salt structure, Cl– forms fcc (ccp) lattice & Na+ occupies octahedral voids, So tetrahedral voids
are vacant.

E-3. It is a fact.

E-4. Coordination number of Zn2+ ion in Zinc blende = 4.

Zn2+ ion present in half of tetrahedral void formed by S2– in fcc unit cells.

E-5. SrCl2 is AB2 type in which cation is of large size.

1 1
E-6. A × 8 = 1, B  4  = 2 and O2– = 4 so formula of spinal = AB2O4
8 2

E-7. Only two tetrahedral holes are occupied in diamond.

E-8. On increasing tempr C.N. decreases.

 CsCl (8 : 8) structure changes into (6 : 6) NaCl type structure.

F-1. In a solid lattice the cation has left a lattice site and is located at an interstitial position, the lattice defect
is called Frenkel defect.

F-2. Since Ag+ (cation) is smaller than Cl– (anion) & hence cation is present in voids.
–
In CaF2, Fanion is smaller.

F-3. F-centers are the electrons trapped in anionic vacancies.

F-4. p-type semiconductors acquire no charge because a 13 group atom replaces a 14 group atom.

PART - III

1. Covalent  Diamond ; Ionic  NaCl

Dipole-dipole  HCl ; Metallic  Al

2. Refer theory

3. (A) ZnS crystal

S2– ion are present in fcc lattice & Zn2+ ion occupy all the tetrahedral voids distance of tetrahedral voids
3a
from corner =
4
(B) CaF2  Fluorite structure
Ca2+ ion are present in ccp lattice & F– ion are present in all tetrahedral voids.
(C) NaCl  Rock salt Type structure
Cl– ion are present in ccp lattice & Na+ ion occupy all the octahedral voids.
(D) Diamond crystal  C atom present in fcc lattice in which alternate tetrahedral voids are occupied by
C atom.

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 Solid State
EXERCISE # 2

PART - I
1. Grey Cast Iron is metallic solid.

Z M 2  100
3. Density =  = 5.2 g/cm3
NA  a3 6  10 23  (400  10 10 )3

1 7 1 1
5. X = 7x = ; Y= x 6 = 3. ; Z=   X7/8 Y3 Z1/8 = X7 Y24 Z
8 8 2 8

6.
2 Square Voids (4)

2(r   r  )
7. For (bcc) = r+/r– = 0.732 and a =
3
and diameter of cubical void (2r+) = a( 3 –1) = 2.888 × 0.732 = 2.108 Å.

8. No. of octahedral holes = No. of close packed atoms

& No. of Tetrahedral holes = 2× No. of close packed atoms.

9. no. of oxide ions = 4

1 4
no. of A particles =  8 =
6 3
1 4
no. of B particles =  4 =
3 3
so formula is A4/3 B4/3O4 or ABO3

a 2
10. Distance between nearest neighbours is along the face diagonal = .
2

ZM 4  195
11. Density =  = 21.86 g/cm3
NA  a 3
6.02  10  (3.9231  10 8 )3
23

for fcc lattice, 4r = a 2

a 2 3.9231 2
so, r= = Å = 1.387 Å.
4 4

a 2 4.070  2
12. Closest distance is = = Å = 2.878 Å
2 2

13. In NaCl structure, C.N. of each cation & anion is six.

14. It is a fact.

15. On increasing pressure, C.N. increases.  6 : 6 changes to 8 : 8.

16. It is a fact.

18. Ions are displaced from one place to another.

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 Solid State

19. Some of O2– combine with each other forming O2 gas which is liberated learning behind electrons at the
site vacated by oxide ions.

PART - II
1. SiO2, Diamond, Si, AlN, SiC.

2. Number of atom effectively present in a cubic unit formed by arrangement of eight B.C.C unit cell =
1 1 1
8× + 12 × +6× + 1 + 8 = 16.
8 4 2

3. a = 2 × diameter of the ball.

number of balls = 2 × 2 × 2 = 8

5. 3+3=6

7. No. of oxide ions = 4
1 4
No. of A particles =  8 =
6 3
1 4
No. of B particles =  4 =
3 3
So formula is A4/3 B4/3O4 or ABO3
ABO3 = x + y + z = 1 + 1 + 3 = 5

8. Cation and anion in Fluorite CaF2 and Zinc blende ZnS are respectively x : y and a : b  8 : 4 and 4 : 4
8 + 4 + 4 + 4 = 20

9. Number of octahedral void in ccp = Z; Number of tetrahedral void in ccp = 2Z.

For A2B, Number of anion B = 4.
Cataion (A) present in all octahedral void (100% occupied) and half tetrahedral void (50% occupied),
1
then number of cation (A) in unit cell = 4 + 8 × = 8.
2
So, formula of compound = A2B.

PART - III
1. Randomness (entropy) in amorphous solids is more than that in crystalline solids.

3. Edge length = AB = AD = BC = CD = a
Also, AC = AB2  BC2 = a2  a2 = 2a
AG = AC2  CG2 = 2a2  a2 = 3a

3a
4. In bcc r =
4
also, edge length of unit cell = a
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 Solid State
radius of atom = r
 Edge length not covered by atom = a – 2r
3 2  3 
or a– .a = a  
2  2 
2  3 
a 
 2 
 Percentage fraction not covered = × 100 = 0.134 × 100 = 13.4%
a
 Percentage fraction of covered = (100 – 13.4) % = 86.6%

6. These are facts.

9. In bcc coordination number is 8.

10. These are facts.

11. When silcon 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 anyother group-14 element such as germanium). One excess electron is left on
them.
Since this electron is not involed in bonding it becomes delocalized and contributre to electrical
conduction. Silicon dped with group-15 element behaves as a n-type semconductor.

PART - IV
1. In FCC lattice each edge center act as octahedral void.

1 1
2. No. of X = 8 × +6× =4  4 XY unit per cell.
8 2
1
No. of Y = 1 + 12 × = 4
4

3. At edge center, there is octahedral void in f.c.c. lattice.

 C.N. of Y = 6
(6 : 6) C.N.  NaCl Structure.

4. Some Cl– ions leave the lattice and combine with Li vapour to release electron, which is trapped into the
anion vacancy giving rise to metal excess defect Cl– + Li(g) LiCl(s) + e–

1
5. On heating, ZnO(s) dissociates reversibly as ZnO Zn2+ +
O2 + 2e–
2
Zn2+ ions occupy certain interstitial sites whereas the electrons released are present at the
neighbouring sites, which act as F-centers.

6. In the crystallization, some Ag+ ions will get replaced by as many half of Cd2+ ions. Thus the cation
vacancies will be the same as the number of Cd2+ is ions incorporated.

7. AgBr can show both shottky and frenkel defect.

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 Solid State
EXERCISE # 3

PART - I
1. In the figures given below draw the unit cell of the corresponding structure and identify these plane in
your diagram (out of fcc and simple cubic).
(i) Face plane (ii) Body diagonal plane (iii) Plane passing through the face diagonals.

1 1
2. The No. of atom of A for unit cell =   8  4   = 3
8 2
Then formula = A3B4.

3. Calculate no. of atoms of A & B per unit cell.

1
No. of atoms of A/ unit cell = 8 × = 1.
8
1
No. of atoms of B/ unit cell = 6 × = 3.
2
 Formula is AB3.

4. Again to have the maximum number of spheres the packing must be hcp.
Maximum number of spheres = 25

Area of the figure = 2 × Area of equiletral tringle of side = 4 cm

3
=2× × (4)2 = 13.856
4
25 marbel
= 1.804 marbles/cm2
13.856 cm2

1
a
5. (a)  Y3
2
1
a = 2Y 3
4  6.023  Y  10 —3
density (d) = = 5.0 Kg/M3
6.023  10 23
 2Y
1/ 3
 10 
—9 3

(b) Observed density of AB is 20 Kg/M3

Which is Higher then calculate density 5kg/m 3 thus AB has either interstitial impurity defect or
substitutional impurity defect.

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 Solid State
6. In cubic close packing no. of tetrahedral void = 2 × no of atom. As there are 4 S 2– ions at lattice point
r
and they need 4 Zn+2, which adjusted in alternate tetrahedral void (0.225 <  < 0.414).
r

r 
7. For f.c.c.  1  0.414 octahedral void
 2
r 
r1
= 0.225 tetrahedral void
r2
a 2
We know along face diagonal for f.c.c. 4r2 = a 2  r2 =
4
Required diameter of interstitial sites = 2r1 = 2 × 0.414r2
2  .414  2  a 2  .414  2  400
Diameter = = = 117.1 pm.
4 4

ZM
8. d=  Z = 20 × 10–1 = 2
NA a3
3
So its is a bcc unit cell. Hence 3 a = 4R so R= × 5Å = 216.5 pm.
4

9. (A) Simple cubics and fcc (i) have the cell parameters a = b = c &  =  =  (choice P) and belong to the
same crystal system (choice (s)).
(B) Cubic & rhombohedral (i) have the cell parameters a = b = c and  =  =  (choice P) and (ii) are
two crystal systems (choice (q)).
(C) Cubic and tetragonal are two crystal system (q).
(D) Hexagonal & monocubic (i) two crystal system choice (q) p (ii) have only two crystallographite
angles of 90º choices.

 1  1
10. Total no. of atoms in 1 unit cell =  12 x  + 3 +  2 x  = 6
 6  2

2
11. C= 4r = Height of the unit cell.
3
3
Base area = 6 × (2r)2.
4
2 2 2
Volume of the hexagon = Area of base x Height = 6. a × c = 4r 2  4r = 24. 2 r3
3 3

4 3
6
r
3 
12. Packing fraction = =  = 0.74 = 74%
24 2 r 2 3 2
 empty space = 100 – 74 = 26%.

13. Frenkel defect is a dislocation defect.

Trapping of an electron in the lattice leads to the formation of F-center.

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 Solid State

14.

4R = L 2
so, L = 2 2 R
Area of square unit cell = ( 2 2 R)2 = 8R2
 R2 
Area of atoms present in one unit cell = R2 + 4   = 2R
2
 4 
2R2 
so, packing efficiency = × 100 = × 100 = 78.54%
8R2 4

15.

1
16. No. of M atoms = ×4+1=1+1=2
4
1 1
No. of X atoms = ×6+ ×8=3+1=4
2 8
so formula = M2X4 = MX2

17. The given arrangement is octahedral void arrangement.

rA
  0.414  rA  0.414  250
rx –
pm.
rA
& < 0.732  rA < 183 pm
rA
So, we have to choose from 104 pm and 125 pm. As no other information is given, we consider exact
fit, and hence 104 pm is considered as answer.

18. In ccp, O2– ions are 4.

Hence total negative charge = –8
Let Al3+ ions be x, and Mg2+ ions be y.
Total positve charge = 3x + 2y
 3x + 2y = 8
This relation is satisfied only by x = 2 and y = 1.
Hence number of Al3+ = 2.
and number of Mg2+ = 1.
2 1
 n = fraction of octahedral holes occupied by Al3+ = =
4 2
1
and m = fraction of tetrahedral holes occupied by Mg2+ =
8
Hence, answer is (A)
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ADVSST - 11
 Solid State
19. (A) For any atom in top most layer, coordination number is not 12 since there is no layer above top
most layer
(B) Fact
(C) Fact
(D) 2 a = 4R
So a=2 2R

M0
Z
NA
20. d  (d = density)
a3
M0
4
8= 6  1023
(4  10–10 )3
1
M0 =
8  6  1.6
256 10
Number of moles in 256 g = 
8  6  1.6 3
10
Number of atoms =  6  1023  2  1024
3

21. As per given information cation form FCC lattice and anion occpy all the octahedral void.
So M+ X– & Formula MX
4 ion 4 ion
After step I 4 ion 1 ion
After step II 1 ion 4 ion
After step III 0 ion 4 ion
After step IV 1 ion 3 ion
No. of anion 3
So ratio of =
No. of cation 1

PART - II
5. Substances which are expected to possess para-magnetism or ferro-magnetism on the basis of
unpaired electrons but actually they possess zero net magnetic moment are called anti ferromagnetic
substance.

6. LiCl, NaCl and RbCl have rocksalt structure CsCl has simple cubic structure of Cl – ions.

7. Piezoelectric material are those that produce an electric current when they are placed under
mechanical stress

ZM 4  63.55 422

8. d= 3
or, d = 23 8 3
or, d = g/ml.
NA  a 6  10  ( x  10 ) x3

9. Factual

10. B forms HCP  No. of B = 6

1 1
A occupies TV  No. of A = ×12 = 4
3 3
 Formula = A4B6 = A2B3

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ADVSST - 12
 Solid State
ZM
11. d=
NA  a3
M0
4
9 × 103 = 6  1023
(200  2  10–12 )3
M0
4
9 × 103 = 6  1023
3
2  2  2  10 –30
9  103  6  1023  24  2  10–30
M0 = = 9 × 6 × 10–4 × 4 × 2 = 0.03 kg
4

a
12. =R+r
2
3a = 4R
0.5 a = 0.433 a + r
r = 0.067 a

13. Effective number of A = 4

1
Effective number of B = 4 × 2
2
Effective number of O = 8
Formula is A4B2O8 or A2BO4

14. 3a  2r  2(2r )  6r
6r
a= 2 3r
3
4 3
4 3 4
r  (2r )3 (r  8r 3 )
3 3 3 4  9r 3 
P.F. = =  =  0.906
a3 (2 3r )3 3  8  3 3r 3 2 3
% of packing efficiency = 0.906 × 100 = 90.6%

15. Nearest distance between two nearest tetrahedral voids in a FCC lattice is a/2.

1
16. In sc a, Z = 8 × =1Z=1
8
1
In bcc a Z = 8 × + 1 = 2 Z = 2
8
1 1
In fcc, Z = 8 × + 6 × =4 Z = 4
8 2

17. Only AgBr can exhibit both Schottky and Frenkel defect.

18. CCl4  Non-conductor in solid and liquid phase.

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