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SOLID STATE
Subjective Questions
1. How can you convert NaCl structure into CsCl structure and vice-versa?
2. AgI crystallizes in cubic close packed ZnS structure. What fraction of tetrahedral sites
are occupied by Ag
+
ions?
3. What is Frenkel defect?
4. What type of crystal defect is produced when sodium chloride is doped with MgCl2?
5. A compound AB2 possesses the CaF2 type crystal structure. Write the co-ordination
number of A
++
and B

ions in its crystals.


6. A solid between A and B has the following arrangement of atoms
(i) Atoms A are arranged in ccp array
(ii) Atoms B occupy all the octahedral voids and half the tetrahedral voids. What is
the formula of the compound?
7. In corundum, oxide ions are arranged in hcp array and the aluminium ions occupy two
thirds of octahedral voids. What is the formula of corundum?
8. Calculate the ratio of the alkali metal bromides on the basis of the data given below and
predict the form of the crystal structure in each case. Ionic radii (in pm) are given below
Li
+
= 74, Na
+
= 102, K
+
= 138
Rb
+
= 148, Cs
+
= 170, Br
-
= 195
9. In the close packed cation in an AB type solid have a radius of 75 pm, what would be the
maximum and minimum sizes of the anions filling the voids?
10. NH4Cl crystallizes in a body centered cubic lattice, with a unit cell distance of 387 pm.
Calculate (a) the distance between the oppositely charged ions in the lattice, and (b) the
radius of the NH4
+
ion if the radius of the Cl
-
ion is 181 pm.
11. Copper has the fcc crystal structure. Assuming an atomic radius of 130pm for copper
atom (Cu = 63.54):
(a) What is the length of unit cell of Cu?
(b) What is the volume of the unit cell?
(c) How many atoms belong to the unit cell?
(d) Find the density of Cu.
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12. The density of CaO is 3.35 gm/cm
3
. The oxide crystallises in one of the cubic systems
with an edge length of 4.80 . How many Ca
++
ions and O
2
ions belong to each unit cell,
and which type of cubic system is present?
13. A metal crystallizes into two cubic system-face centred cubic (fcc) and body centred
cubic (bcc) whose unit cell lengths are 3.5 and 3.0 respectively. Calculate the ratio of
densities of fcc and bcc.
14. Copper crystal has a face centred cubic structure. Atomic radius of copper atom is 128
pm. What is the density of copper metal? Atomic mass of copper is 63.5.
15. The first order reflections of a beam of X rays of wavelength of 1.54A from the (100)
face of a crystal of the simple cubic type occurs at an angle 11.29. Calculate the length
of the unit cell.
16. X- rays of wavelength equal to 0.134 nm give a first order diffraction from the surface of
a crystal when the value of u is 10.5. Calculate the distance between the planes in the
crystal parallel to the surface examined.
17. What is the difference in the semi conductors obtained by doping silicon with Al or with
P?
18. Non stoichiometric cuprous oxide, Cu2O can be prepared in the laboratory. In this oxide,
copper to oxygen ratio is slightly less than 2:1 can you account of the fact that this
substance is a p type semiconductor
19. Classify each of the following as being either a p type or n type semiconductor.
(i) Ge doped with In
(ii) B doped with Si
20. If NaCl is doped with 10
-3
mole% SrCl2 what is the concentration of cation vacancies?
21. The composition of a sample of wustite is Fe0.93O1.00. How much percentage of Fe(III)
is present?
22. A solid AB crystallises as NaCl structure. If the cation radius is 100 pm, determine the
probable range of radius of the anion.
23. Aluminium has cubic unit cell with an edge length of 405 pm. The density of Aluminium
is 2.70 g cm_3. Classify the type of unit cell of Al crystal.
24. The edge length of a cubic unit cell of calcium oxide crystal is 4.80 A. Its density is
3.35 g cm_3. Which type of cubic system is this? How many calcium and oxide ions are
present in each unit cell?
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25. The effective radius of an atom of iron is 124.0 pm. If the cubic unit cell of metal is FCC
and BCC type, what would be the density of Fe in both arrangements?
26. The face-centerd cubic lattice of potassium metal has a unit cell of dimension 0.574 nm.
What is the shortest distance between two potassium atoms?
27. Silver chloride has the same structure as sodium chloride. The edge length of a unit cell
of silver chloride is 535 pm and the density is 5.561 g cm_3. Find the percentage of
empty sites. Assume that lattice vacancies are the only defects.
28. Molybdenum forms body-centered cubic crystals whose density is 10.3 g cm_3.
Calculate
(a) the edge length of the unit cube
(b) the distance between the (110) and (111) planes. (Molar mass of Mo = 95.94 g
mol_1)
29. Cesium chloride has a cubic structure. Its density is 3.99 g cm_3. Taking atomic mass of
cesium as 133, calculate the distance between Cs+ and Cl_ ions.
30. The unit cube length of lithium chloride (sodium chloride like structure) is 5.14
A.Assuming anion-anion contact, calculate the ionic radius of chloride ion.

Objective Questions
1. How much is the contribution in a unit cell of a particle at the corner of a simple cube?
(a) 1 (b) 1/2 (c) 1/4 (d) 1/8
2. An atom at the face centre of a face-centered cubic cell is shared by
(a) 4 unit cells (b) 2 unit cells (c) 1 unit cell (d) 6 unit cells
3. In a body-centered cubic cell, an atom at the body centre is shared by
(a) 1 unit cell (b) 2 unit cells (c) 3 unit cells (d) 4 unit cells
4. Which of the following cubic lattices has the maximum number of atoms per unit cell?
(a) simple cubic (b) body-centered cubic
(c) face-centered cubic (d) all have the same number of atoms
5. How many atoms are provided by the edge atom of a cube to the unit cell?
(a) 1/2 (b) 1/4 (c) 1/8 (d) 1
6. In a bcc unit cell, a metal atom at the centre of the cell is surrounded by how many other
metal atoms?
(a) 8 (b) 6 (c) 12 (d) 4
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7. How many number of atoms are there in a cubic unit cell having one atom on each
corner and two atoms on each body diagonal of the cube?
(a) 8 (b) 6 (c) 4 (d) 9
8. The coordination number in a hexagonal closed packed structure (hcp) is
(a) 12 (b) 10 (c) 8 (d) 6
9. The ABAB.... packing and ABC ABC.... packing are respectively called
(a) hexagonal close packing (hcp) and cubic close packing (ccp)
(b) ccp and hcp
(c) body-centered cubic close packing (bcc) and hexagonal close packing (hcp)
(d) hcp and bcc
10. Which of the following statements is not correct?
(a) the coordination number of each ion in CsCl crystal is 8
(b) a metal in bcc structure has a coordination number equal to 12
(c) a unit cell of an ionic crystal shares some of its ions with other unit cell
(d) the length of the unit cell in NaCl is 552 pm
11. Lithium selenide can be described as a closest packed array of selenide with lithium
ions in all the tetrahedral holes. The formula of lithium selenide is
(a) Li2 Se (b) Li Se (c) Li Se2 (d) Li3 Se
12. The mass of a unit cell of NaCl corresponds to
(a) 1 Na+ and 6Cl_ (b) 1 Cl_ and 6 Na+
(c) 1 Na+ and 1 Cl_ (d) 4 Cl_ and 4 Na+
13. 6 : 6 of NaCl coordination changes to 8 : 8 coordination on
(a) applying high pressure
(b) increasing temperature
(c) both
(d) no effect of changing pressure and temperature on coordination
14. A metallic element crystallises into a lattice containing a sequence of layers of AB
ABAB.... Any packing of spheres leaves out voids in the lattice. The empty space in
percentage by volume in this lattice is
(a) 26 % (b) 32 % (c) 20 % (d) 30 %
15. The point defect which lowers the density of a material is
(a) Schottky (b) Frenkel (c) both (d) none of the above
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16. LiBr, NaBr, KBr, and RbBr have the same crystal structure (cubic). Which of the
following is a simple cubic, whereas all others are fcc?
(a) Li Br (b) Na Br (c) KBr (d) Rb Br
17. Cs Cl has a body-centered cubic lattice. How many Cs+ and Cl_ are there in the unit cell?
(a) 2 Cs+ ions and 2Cl_ ions (b) 1 Cs+ and 8 Cl_ ions
(c) 1 Cs+ and 1 Cl_ ion (d) 1 Cl_ and 8 Cs+ ions
18. Noble gases crystallise in
(a) bcc (b) ccp (c) hcp (d) none of the above
19. The fraction of total volume occupied by atoms in a simple cube is
(a) /6 (b) /7 (c)/4 (d) /3
20. How many spheres surround an octahedral void?
(a) 6 (b) 4 (c) 8 (d) 12
21. How many Cl
-
ions are there around the Na
+
ion in anNaCl crystal?
(a) 3 (b) 4 (c) 6 (d) 8
22. A pure crystalline substance on being heated gradually first forms a turbid liquid at a
constant temperature, and later at a higher temperature the turbidity disappears. This
is the characteristic of
(a) allotropic crystals (b) liquid crystals
(c) isomeric crystals (d) isomorphous crystals
23. When electrons are trapped into the crystal in anion vacancy, the defect is known as
(a) Schottky defect (b) Frenkel defect
(c) Stoichiometric defect (d) F-centres
24. A solid has a structure in which W atoms are located at the corners of a cubic lattice, O
atoms at the centre of edges and Na atom at the centre of the cube. The formula of the
compound is
(a) Na WO2 (b) Na WO3 (c) Na2 WO3 (d) Na WO4
25. Potassium crystallises with a
(a) face-centered cubic lattice (b) body-centered cubic lattice
(c) simple cubic lattice (d) orthorhombic lattice
26. A compound formed by elements `A' and `B' crystallises in the cubic structure where `A'
atoms are at the corners of the cube and `B' atoms are at the face centres. The formula of
the compound is
(a) AB3 (b) AB (c)A3B (d) A2B2
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27. The second-order Bragg diffraction of X-rays with l = 1.00 A from a set of parallel
planes in a metal occurs at an angle of 60. The distance between the scattering planes
in the crystal is
(a) 0.575 A (b) 1.00 A (c) 2.00 A (d) 1.15 A
28. Potassium has a bcc structure with the nearest neighbour distance of 4.52 A. Its atomic
weight is 39. Its density will be
(a) 910 kg m_3 (b) 804 kg m_3 (c) 852 kg m_3 (d) 968 kg m_3
29. A substance has a density of 1.984 g cm_3, and it crystallises in afcc crystal with edge
length equal to 630 pm. The molar mass of the substance in g/mole is
(a) 37.35 (b) 56.02 (c) 74.70 (d) 65.36
30. The number of formula units of ZnS in a zinc blende unit cell is
(a) 1 (b) 2 (c) 4 (d) 8
31. On the basis of the ratio of r+ and r_, predict which of the following has a tetrahedral
structure?
(a) CsBr, = 0.863 (b) Sr S, = 0.609 (c) MgO, = 0.472 (d) MgSe, = 0.333
32. The oxidation state of Cu in a mineral of the type CeBa2 Cu3O7 is
(a) + 2 (b) + 7/3 (c) + 1 (d) + 7
33. Copper crystallises with afcc lattice. Calculate the density of copper if the side length of
the unit cell is 3.615 A, atomic weight is 63.6, and Avogadro's number is 6.02 1023.
(a) 8.96 g / mL (b) 8.62 g / mL (c) 8.26 g / mL (d) 8.14 g / mL
34. The existence of a substance in more than one crystalline form is known as
(a) allotropy (b) polymorphism (c) amorphism (d) isomorphism
35. Nickel (atomic mass = 58.7) crystallises in a face-centered cubic lattice. If the edge of
the unit cell is 3.52 A, its density will be
(a) 8.94 g / cm3 (b) 0.894 g / cm3 (c) 0.0894 g / cm3 (d) 0.00894 g / cm3
36. An element having a bcc structure has 12.08 1023 unit cells. The total number of atoms
of the element in these cells will be
(a) 6.04 1023 (b) 12.08 1023 (c) 24.16 1023 (d) 36.18 1023
37. A substance whose resistance becomes almost zero at a very low temperature is called
(a) an electrical conductor (b) a hyperconductor
(c) a semiconductor (d) a superconductor
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38. In the fluorite structure if the radius ratio is

,how many ions does each cation


touch?
(A) 4 anions (B) 12 anions(C) 8 anions (C) No cations
39. In AB unit cell(rock salt type) assuming A
+
forming FCC:
(A)The nearest neighbor of A
+
is 6B
-
ion.
(B) The nearest neighbor of B
-
ion is 6A
+
.
(C) The nearest neighbor of A
+
is 12A
+
ion.
(D) The packing fraction of AB crystal is 0.74.
40. In FCC unit cell ,the atoms not touching each other are:
(A)3 & 4 (B)1 & 3 (C)1 & 2 (D) 2 & 4



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Hints & Solutions:
1. NaCl structure can be converted into CsCl structure by application of pressure while
reverse can be done by heating to 760 K.
2. In the face-centred unit cell, there are eight tetrahedral voids, of these, half are occupied
by silver cations.
3. When some ions (usually cations) are missing from the lattice sites and they occupy the
interstitial sites so that electrical neutrality as well as stoichiometry is maintained, it is
called Frenkel defect.
4. It is called impurity defect. A cations vacancy is produced. A substitutional solid solution
is formed (because 2Na
+
ions are replaced by one Mg
++
ion). This defect is also known
as metal deficiency defect.
5. Co-ordination number of A = 8
Co-ordination number of B = 4
6. In a close packing, the number of octahedral voids is equal to the number of atoms and
the number of tetrahedral voids is twice the number of atoms
Since all the octahedral voids and half the tetrahedral voids are filled there will be one
atom of B in tetrahedral void and one atom in octahedral void corresponding to each A.
Thus, there will be two atoms of B corresponding to each A.
Hence, formula of the solid is AB2
7. In ccp or hcp packing there is one octahedral void corresponding to each atom
constituting the close packing. In corundum only 2/3
rd
of the octahedral voids are
occupied. It means corresponding to each oxide are 2/3 aluminium ions. The whole
number ratio of oxide and aluminium ion in corundum is therefore 3:2 Hence formula of
corundum is Al2O3
8. The ratio of cation to that of anion i.e.
r
r
+

gives the clue for crystal structure


Li 74
0.379
195 Br
+

= = (tetrahedral)
Na 102
0.523
195 Br
+

= = (octahedral)
K 138
0.708
195 Br
+

= = (octahedral)
Rb 148
0.759
195 Br
+

= = (Body centered)
Cs 170
0.872
195 Br
+

= = (Body centered)
9. For close packed AB type solid
r
0.414 0.732
r
+

=
Minimum value of
r 75
r 102.5 pm
0.732 0.732
+

= = =
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Maximum value
r 75
r 181.2 pm
0.414 0.414
+

= = =
10. (a) In a body centered cubic lattice oppositely charged ions touch each other along
the cross - diagonal of the cube. Hence, we can write,
3a 3
2r 2r 3a, r r (387pm) 335.15pm
2 2
(b) Now, since r 181pm,
+ +

+ = + = = =
=

wehaver (335.15 181)pm 154.15pm.
+
= =
11. As we know
=
m
3
A
n M
N a

,
(a) for fcc structure
4r = 2 a
a =2 2 r
= 2 2 130 pm = 367.64 pm
(b) volume of unit cell = a
3
=
( )
3
10
367.64 10 cm


= 4.968 10
23
cm
3

(c) n = 4
(d) =
23 8 3 3
4 63.54
6.023 10 (3.67 10 cm )


= 8.54 gm / cm
3
12. From equation
(density) = 3.35 gm/cm
3

a = 4.80
Mm of CaO = (40 + 16) gm = 56 gm CaO
=
m
3
A
n M
a N

where n = no. of molecules per unit cell


n =
8 3 23
3.35 (4.8 10 ) 6.023 10
56


= 3.98
or n ~ 4
So, 4-molecules of CaO are present in 1 unit cell
So, no. of Ca
+ +
ion = 4
No. of O

ion = 4
So, cubic system is fcc type.
13. fcc unit cell length = 3.5
bcc unit cell length = 3.0
Density in fcc =
1
1
n atomic weight
V Avogadro number


Density in bcc =
2
2
n atomic weight
V Avogardro number


fcc 1 2
bcc 2 1
D n V
D n V
=
n1 for fcc = 4; Also V1 = a
3
= (3.5 10
8
)
3

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n2 for bcc = 2; Also V2 = a
3
= (3.0 10
8
)
3

8 3
fcc
8 3
bcc
D 4 (3 10 )
D 2 (3.5 10 )


=

= 1.259
14. In face centred cubic arrangement face diagonal is four times the radius of atoms face
diagonal = 4128 = 512 pm
Face diagonal = 2 edge lengh
Edge length =
512
362 pm
2
= = 36210
-10
cm
Volume of the unit cell = (36210
-10
)
3
cm
3
= 47.410
-24
cm
3

In a face centred cubic unit cell, there are four atoms per unit cell
Mass of unit cell =
22
23
4 63.5
g 4.22 10 g
6.023 10


Density =
22
3
24
massof unit cell 4.22 10
8.9 gcm
volume of unit cell 47.4 10

= =


15. Applying Braggs equation
2 d Sinu = n
Given u = 11.29, = 1.54A = 1.5410
-8
cm
n = 1
d =
8 8
8
1.54 10 1.54 10
3.93 10 cm
2 Sin11.29 2 0.1957


= =


hkl
2 2 2
a
d a
h k l
= =
+ +

a = 3.9310
-8
cm (length of the unit cell)
16. Given = 0.134 nm, u = 10.5
n = 1
Applying Braggs equation
2d Sinu = n
d =
o
n 1 0.134 0.134
3.68 A
Sin 2 Sin10.5 2 0.1822

= = =
2 u

17. Silicon doped with Al produces P type semi conductors i.e. flow is due to creation of
positive holes whereas silicon doped with P produces n type semi conductors i.e. flow
is due to extra electrons carrying negative charge.
18. The ratio less that 2:1 in Cu2O show that some cuprous (Cu
+
) ions have been replaced
by cupric (Cu
+2
) ions. To maintain electrical neutrality, every two Cu
+
ions will be
replaced by one Cu
+2
ion. Thereby creating a hole. As conduction will be due to presence
of these positive holes, hence it is a p type semi conductor.
19. (i) Ge is group 14 element and In is group 13 element. Hence an electron deficient
hole is created and therefore, it is p type.
(ii) B is group 13 elements and Si is group 14 elements, there will be a free
electron. Henc, it is n type
20. Doping of NaCl with 10
-3
mol% SrCl2 means that 100 moles of NaCl are doped with
10
-3
mol of SrCl2
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1 mole of NaCl is doped with SrCl2 =
3
5
10
mole 10 mole
100

=
As each Sr
+2
ion creates one cation vacancy, therefore concentration of cation vacancies
= 10
-5
mol / mol of NaCl =10
-5
6.02310
23
= 6.02310
18
mol
-1

21. 15.05%
22. 136. 6 pm to 241.5 pm
23. Face-centered
24. 4 ions of each type and FCC
25. FCC 8.59 g cm
_3
and 7.88 g per cm
_3

26. 0.406 nm
27. 0.25%
28. 313.9 pm ; 222.0 pm ; 181.2 pm
29. 450 pm
30. 1.81 A

Answers:
1. d 2. b 3. a 4. c 5. B 6. a 7. d 8. a 9. a 10. B 11. a 12. d
13. a 14. A 15. a 16. d 17. c 18. b 19. A 20. a 21. C 22. b 23. d 24. B
25. b 26. a 27. d 28. A 29. c 30. c 31. a 32. B 33. a 34. b 35. a 36. c
37. D 38. (B, C) 39. (A, B, C, D) 40. (C)