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Solid State

Page.2.

Exercise-I
1.(C)

2.(A)
3.(A)

4.(A)

5.(A)

8.(C)

1
2
Since each atom at face centre is shared by two unit
cell.
X atom in corners , Y at face centres in the lattice
In unit cell
Contribution of face centre

ZX 7

ZY

ABBAABBA dont produce close packing

Pseudo means false or pretending. Those materials


which appear like solids but are not completely solids
are called pseudo solids. Rubber and solid cake left
after distilation of coal tar appear like solid but are not
completely solid in nature.
Unit cell of periodic lattice lie on a Bravais lattice
equivalent points are present in Bravais lattice.
Rhombohedral system
a=b=c
r 90o

A type
B type

9.(C)

(For FCC)

a4 2 A

Volume = a3

(4 2)3 (1010 )3 m3
(4 2)3 1030 m3

1 7
(Since 1 atom at corners is missing)
8 8

1
6 3 (Since 6 faces are present)
2

a 2 2 r 2 2 2

10.(B)

Molecular formula X 7 Y3

a 3 1.80 1022 cm3


In fcc lattice each atom touches 4 others in same
layer, 4 in layer above and 4 in layer below. Hence the
coordination number is 12.

6.(B)

Simplest molecular formula X 7 Y24


X atoms are present at corners , Y atoms at face
centres in the lattice
In unit cell we have,
ZX 7

1 7
(1 atom of X type is missing)
8 8

1
ZY 6 3 (6 faces are there in a unit cell)
2
Z Z 1

1 1
(since 1 atom of X is replaced by Z)
8 8

Molecular formula X 7 Y3 Z 1
8

Simplest molecular formula X 7 Y24 Z


7.(B)

Body centre atom 11 1 ( Na atom)


1
Atoms located corners 8 1 (W atoms)
8

1
Atoms located at edges 12 3 (O atoms)
4
Molecular formula = NaWO3

11.(C)
12.(C)

Cations occupy only 2/3 octrahedral void and


number of octrahedral void in h.c.p. = 6
2
4
3
Number atoms in hcp = 6 anion (A)
the general formula = C4A6 = C2A3

Number of cations = 6

13.(A)
14.(A) A spinel structure (AB2O4), one cation occupies oneeight of the tetrahedral holes and B cation occupies
one-half of octahedral holes.
15.(D) In a closed packed structure if there is N number of
atom then N number of octahedral voids.

16.(A) In a planar triangle

In a square planar

r
r
r

= 0.155

= 0.414

In a Body centred cubic


In a tetrahedral

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r
r

r
r

= 0.732

= 0.225

Solid State
17.(C) If AB have coordination number 6 then it is in a
octahedral void then 0.44 <

r
r

Page.3.
32. (B) No. of atom A from the corner of unit cell =

< 0.732

No. of atom B from the face of unit cell = 3

or Structure is rock salt structure


18.(D)

In a rock salt structure tetrahedral voids is vacant.

23.(B)

rRb 1.46 rI 2.16


1.46
r

0.675 0.414< 0.732


rI
2.16
r
Structure is rock salt (NaCl) structure
Schottky defect because equal number of Cations (2)
and Anions (2) are missing hence General formula
remains same but density decreases.
According to Schottky defect equal number of
cations and anions are missing. hence
option B is appropriate.

25.(B)

26.(D)
27.(A) F-centres are the sites where anions are missing and
electrons are trapped in anionic vacancies.
28.(B) Since frenkel defect is dislocation effect and smaller
ion will migrate in AgCl, Ag+ is smaller then Cl ,
whereas in CaF2, F is smaller than Ca2+.
29. (C) Total strength of H-bond
= 30.8 14.3 = 16.5 kJ mol1
There are 6 nearest neighbours, but each H-bond
involves 2 molecules.
Thus, total H-bond =

H-bond energy =

6
3
2
16.5
5.5 kJ mol 1
3

A : B :: 7 : 24
Formula is A7B24

33. (B) The

r
for NaCl = 0.414 to 0.732
r

(due to f.c.c. structure)


r = 241.54 to 136.6 pm.

34. (A) KBr have facc structure with co-ordination number

6 : 6.
35. (A)

rA
rB

0.50 and

rA rB

rB

and

rC rB
rB

1
1
+6 =4
8
2

1
3
4
Au atoms = 1 1 = 1
Formula is Cu4Ag3Au

rNa
rCl

rB

0.70

1 0.50 1.50
1 0.70 = 1.70

rA rB 1.50
r r 1.70
C
B
a AB 2(rA rB )

a CB 2(rC rB )
a AB 1.50

0.88
a CB 1.70
36. (A) Density =

zM
a3 N0

( z = 2 for bcc and MCsBr = 213)


2 213
=
(4.366 10 8 )3 6.023 1023
= 8.50 g/cm3
having N ions.
n
e E / 2kT
N

Ag-atoms = 12

31. (B)

rC

37. (B) Let the no. of Scottky defect be n in an ionic crystal

30. (D) In each unit cell,


Cu-atoms = 8

7 3
:
8 1

or

rRb

24.(B)

A : B ::

Thus

19.(A) In a NaCl unit (rock salt) cell rNa rCl a / 2


20.(A) In AB2 structure coordination number of A = 8, B
occupy tetrahedral void, and its coordination number
= 4 and 100% occupied.
21.(C) If we increase pressure the coordination number is
also increased and 6 : 6 changes into 8 : 8
22.(B) If we increase temperature, then coordination number decreases and 8 : 8 changes into 6 : 6.

7
8

95
181 = 0.524, i.e., between 0.414 to 0.732 and

thus co-ordination no. = 6.

21.61019

= e 21.381023 1000
= e116 = 9.17 106
Suppose the no. of Frenkel defects be n in an ionic
crystal having N ions and interstitial space N(i)
n=

N N (i) e E / 2kT

N(i) = 2N

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Solid State
Exercise-II

Page.4.

1.(BD) Because diamond & graphite are made up of


CC covalent bond while Fe is element and NaCl is

4.(C)
5.(C)

formed of ionic charges Na and Cl


2.(ACD)
(A) Co-ordination number of each type of ion in CsCl
crystal is 8.
(C) A unit cel of an ionic crystal shares same of its
ions with other unit cells.

6.(C)
7.(A)
8.(D)

(D) length a 2(rNa rCl ) 2(95 181)

2 27.6 552 pm
3.(AB)
4.(ABCD)
(A) cation (Cs+) and anion ( Cl ) is shared by 8 other
cubical units.
rcs
(B) r 0.732

Because as the temperature increases the space


between the atoms increases which results in decrease
in the number of atoms touching any
particular atom.
Because in F-centre unpaired electrons are present.
Conduction through electrons is n-type because
electrons are negatively charged and conductance
through positive holes is p-type because it is
positively charged.

Exercise-IV
1.

A s; B r; C p; D q
Here ,

r = radius of atom
a = edge length of unit cell

(A) Z 8

Cl

(C) As the temperature increases coordination


number decreases and at 760 K it changes to 6 which
is of NaCl type.

Packing fraction

(D) Cl is present at cubical sites.


5.(BD)
6.(ABCD)
7.(BC)

1
1 , a = 2r/2
8
Z Volume occupied by atoms
100
Volume of cube

4
4 r 3
3
(B) FCC packing fraction =
100 74%
a3
where r =

4
r3

100 52.33%
3
(2r)3

1
1
(B) Z 8 6 4 , 4r 2 a a 2 2 r
8
2

a
2 2

Packing fraction 4

4
6 r 3
3
100 74%
(C) Similarly for HCP =
3 2
6
a .C
4

4 2
C
3

where
a
r 2

4 r 3
100
3 Cl3

4 r 3
100
3 a3

4
r3
4
100 74.01%
3 (2 2r)3

8.(ACD)
9.(BCD)Frenkel defect arises due to movement of cation &
anion from their position.
10.(BC) (B) As the cation and anion leaves their native places
and moves to another position therefore it is
dislocation defect.
(C) trapping of an electron leads to formation of Fcentre.

1
(C) Z 8 1 2 ,
8

3 a 4r

Packing fraction 2

4 r 3
100
3 a3

4
r3
2
100 67.98 %
3 (4 / 3r)3
1
1
(D) Z 8 12 4 , a = 4r
8
4

Packing fraction 4

4 r 3
100
3 a3

Exercise-III
1.(D)
2.(C)
3.(A)

4
In hcp voids are called tetrahedral and octahedral
voids.

4 r 3
100 26.17 %
3 (4r)3

2.

A p,s; B p,q; C q; D q,r

3.

A p; B s; C q; D r

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Solid State
Exercise-V

Page.5.

Passage-1
1.(A)
Percentage of occupied space = 74%
Percentage of unoccupied space = 10074 = 26%
2.(C)
2n, n in a closed packed lattice number of
tetrahedral void is equal to 2 times the number of
atoms in a unit cell and number of octahedral void is
equal to number of atoms.
3.(B)

4.(C)
5.(A)

6.(C)

234
N A .4N A
58.5
Therefore no. of octahedral voids = No. of molecules
= 4NA.

Number of atoms of O in a hexagonal unit cell

neighbouring atoms and thus co-ordination no. is 6.


14.(C)

Anions being larger forms spece lattice.

15.(B)

rA
rB

0.826
0.414 ;
1.994

i.e., octahedral arrangement.


16.(A) All these results justify that AB has NaCl structure.

2
Number of metal ions in a unit cell = 6 = 4 atoms
3
So, formula of the given oxide is M4O6 or M2O3
ABC ABC - - -

1.(6)

and one B ion like NaCl.

Exercise-VI

2.(4)

The ratio of

for the above passage is 0.414


r
because the value of radius ratio of octahedral
arrangement is 0.414 to 0.732.
Radius ratio : The ratio of the radii of the positive and
negative ions is called radius ratio.

Radius of positive ion r

Radius of negative ion r


Coordination number is 6 because atom is in octahedral void.

3.(4)

4.(6)
5.(4)
6.(6)

9.(B)
Passage-3
n at. wt.
10.(A) The density of solid =
Av. no. a 3

4 9.712 10 23 6.023 1023


=
6.023 1023 (0.564 10 9 102 )3

7.(0)
8.(4)

dA B

9.(2)

Density

Z M
NA a3

Z 40

0.53

2.82
A

In hexagonal closed packing (hcp) arrangement of


atoms, the co-ordination number of atoms in the midde
layer is 6 because each atom is touched by six more
atom.
Body centered cubic has no tetrahedral void so
answer is zero.
1
No. of A atoms x = 8 1
8

1
3
2
Total no. of A & B atoms = x + y = 4

= 2.16 g/cm

5.64 10 8 cm 5.64

2
2
= 2.82

In NaCl, each Na+ ion is surrounded by six Cl ions


and each Cl ion is surrounded by six Na+ ions. Thus,
both the ions have co-ordinates number is six.
Because tetrahedral void = No. of atoms &
no. of atoms in B.C.C. = 2
No. of tetrahedral void = 4
Z M
Density
NA a3
Z 40
1.9
6 1023 (520 1010 )3
Z=4
Atoms present at face centre are shared by only two
unit cells and number of such atoms are 6.

No. of B atoms y = 6

11.(B)

rA+ = 2.82 1.994 = 0.826


Simple cubic closed packed structure has six

17.(A) AB shows Schottky defect due to missing of one A+

Radius ratio =

8.(B)

13.(B)

1
1
= 1 3 2 12
2
8
= 6 O2 atoms
Number of octahedral void = 6

Passage-2
7.(C)

12.(C)

No. of molecules of NaCl

3.988
1.994
2
rAB = 2.82

rB

2.82

d B B (2.82)2 (2.82) 2 = 3.988

10.(6)

6 10 (3.5 108 )3
23

Z=2
No. of tetrahedral voids = 2 no. of atoms
No. of moles of tetrahedral voids = 2 no. of atoms
=23=6

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Solid State
Exercise-VII

3
4.29 = 1.86 .
4
In CsBr, the shortest inter ionic distance of two ions
is 3.72 . The ionic radius of Cs+ is 1.69 and Br is
1.96 .
= 1.69 + 1.96
Ionic distance between = 3.72
CrBr,
r=

2.(A)

3.

In h.c.p. unit cell, there are 6-atoms/unit cell. If r is teh


radius of the metal atoms, then volume occupied by
the metallic atoms :
4
22
6 r 3 6 1.33 r 3
3
7

25.08 r 3
Base area of h.c.p. unit cell :

3
4r 2
4

3
2
4r 2 4r
33.94 r 3
4
3
Volume of the empty space of one unit cell

4.

8.80 r

3
287
4

7 3

Z.M
N A .a

40 mm
B

N A (3)3

C
CD = 10 sin60o = 10 23
=5 3
Fig-2

13.
Fig-1

Area of square having spherical marbles in it


40 101 40 101 cm2 16 cm2
The maximum number of spheres of 10 mm diameter in
h.c.p. packing can be seen in Fig -1.
Total length covered by spheres
= 5 + 4 CD = 5 + 4 10 sin 60
= 5 + 4 5 3 40mm
Maximum number of spheres(s) = 14 8 13

14.

= 124.27 pm

g/cm3

2M

(Full)

24

3
In bcc, r =
a
4
a = 287 r =

23

2 51.99
(6.023 10 ) (23.610
= 7.31 g/cm3.

23

3
1
3
2
2 = 3.5 = 1.259
9.(A)
Co-ordination number for H.C.P is 12. Every atom is
touched by 12 other atoms.
10.
(i) Face plane , (ii) Face diagonal plane,
(iii) Diagonal plane.
11.(A) Na is NaCl has 8 corner and 6 face atoms. If we
remove face centered atom of one axis, two face
atoms are removed. Thus, A is 8 corner and B is at 4
faces.
8
4
A 1 and B 2

8
2
Thus formula is AB2.
12.(A) Number of atoms of A = 8 1/8 = 1
Number of atoms of B = 6 1/2 = 3
formula = AB3.

100 25.93 %
33.94 r 3
Atomic radius = 124.27 pm ; Density = 7.30 g cm3.
Edge length = 287 pm = 2.87 108 cm
Volume of the unit cell = (2.87 108)3 = 23.6 1024 cm3
Z M
Density of crystal = N V
0
=

N A .a

For B.C.C.

33.94r 3 25.14r 3 8.80 r 3


Percentage void

4 58.5

Z.M.

(6.02 10 )(0.564 10 )
= 2.16 g/cm5.
7.(A,C) (A) Co-ordination number for CsCl crystal is 8. Both
Cs+ & Cl has C.N = 8 Cs+ in cubical void & Cl at
corner.
(C) Ions at corner is shared by 8 other symmetrical
unit cells.
Z.M
4.M
1
8.
For F.C.C
3 =
N A .a
NA (3.5)3

the height 4r

m
m
10

2
3
Volume of the unit cell = area height

and

6.

mm

3a
, as the
4
atoms touch each other along the cross diagonal of
the cube.
Given : a = 4.29
(1.86 ) In b.c.c, radius of the atom , r =

10

1.

Page.6.
5.(12)

(Half )

18
1.125
Number of spheres per cm2
16
AB has rock salt structure A : B = 1 : 1 i.e., f.c.c. structure (n = 4) and formula weight of AB is 6.023 Y g
having closest distance (A B)Y1/3 nm.
Therefore edge length of unit cell

2(A B ) 2 Y1/3 109 m

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Solid State

Page.7.

nm
nm

Av. No. V Av. no. a 3


4 6.023Y 10 3

5.0 kg m 3
23
1/3
9 3
6.023 10 (2Y 10 )
(ii) The observed density of AB is 20 kg m3 which is
higher than calculated density 5 kg m3 & thus AB
has either interstitial impurity defect or substitutional
impurity defect.
In ZnS cations are present in atternate tetrahedral
voids.
r1

Either octahedral voids r 0.414 or tetrahedral


2

r1

voids r 0.225 are occupied by interstitial sites


2

in f.c.c. where r1 is radius of atom in interstitial site


and r2 is radius of atoms arranged in f.c.c.
Since in f.c.c. atoms along face diagonal are
touching, thus 4r2 2 a
Required diameter of interstitial sites

(i) Density of AB

15.(B)

16.

1
to Z and 1 atm at body centre whose
4
contribution is 1 to Z]
General formulae M2X4
Empirical Formulae MX2.
(a) p , s ; (b) p , q ; (c) q ; (d) q , r
Intercepts and interfacial angles for various crystal
systems are given below:
Cubic
a=b=c
= = = 90o
Rhombohedral a = b = c
= = 90o
Tetragonal
a = b c
= = = 90o
Hexagonal
a = b c
= = 90o , = 120o
Monoclinic
a b c
= = 90o , 90o
Total no. of atoms in 1 unit cell of h.c.p.
= ( 12 1/6 ) + 3 + ( 2 1/2 ) = 6

bution is

21.

22.(B)

120o

2r1 2 0.414 r2

17.(B)
18.(B,C)

2
1

Base area of h.c.p. unit cell 6

14

14

= 6

1
14

14

L=a

1
2
4
If radius of particle is r, then total are a covered by
particles = 2r2
Total area of unit cell = L2 (or a2)
Number of particles in one unit cell 1 4

But,

3
4r 2
4

23.(A) Volume = Base area height

19.(D)

h/2

2 0.0414 2 a 2 0.414 2 400

4
4
117.1 pm
ZnS

a2 2 r

and Packing efficiency

2r 2
(2 2r )

20.(B)

1
1
Zx = 8 6 [ 8 atoms are at corner where
8
2

a
2

4 2
3

r = 24 2r
3

- packing fraction
4
6 r 3
8
3
74%
packing fraction =
=
3 2
24 2r 3
Empty space = 26%

24.(D)

3 3
(4r 2 )
2
Empty space = 100%

25.

Density

4 2r

Volume =

Area covered by particle


Total area

22
100 78.54 %
74

3 2
3 3 2
a h
a h
4
2

n mol.wt.
V Av.no.

a 5 108 cm, d 2g / cm3 , mol.wt. 75

1
to Z and 6 atoms are at face centre
8
whose contribution is 1/2 to Z].

contribution is

1
Zm = 4 1 2 [ 4 atoms are at edge where contri4

n 75
8 3

(5 10 ) 6 1023

n=2

i.e., the metal crystallizes in b.c.c., thus


radius

o
3
3
a
5 2.165 A
4
4

2.165 108 cm 216.5 pm

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