Solid State
Solid State
Solid State
CHEMISTRY
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THE SOLID STATE
THEORY SHEET
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SOLID STATE
General characterishics of solid states
The following are the characteristic propeties of the solid state
1. They hare definite mass, volume and shape.
2. Intermolecular distance are short.
3. Intermolecular forces are strong.
4. Their constituent particles (atoms/molecules/ions) have fixed positions and can only oscillate
about their mean position .
5. They are incompressible and rigid.
Such solids which hare difinite volume and structure and do not lose their shapes are called true solids
eg. NaCl,KCl, sugar, Fe, Ag, Cu etc.
Whereas solids which lose shapes on long standing and flows under its own weight and get distorted
are called pseudo solids super cooled liquids. e.g. glass.
Ordered arrangement :
In solids there is ordered arrangement of the particles of the solid (atoms/molecules/ions).
This ordered arrangement is of two types
1. Long range order, and 2. Short range order.
Long range order
In long range order there is a regular pattem of arrangement of particle which represents itself
periodically over the entire solid.
Short range order :
In short range order the regular arrangement is periodically repeated over short distances only. On the
basis of the nature of the order, solids can be classified as crystalline solids and amorphous solids.
Crystalline solids - In such solids there is a definite arrangement of particles throughout the
entire there dimentional network of a crystal. These solids thus have long range order. This three
dimentional arrangement of particle is called crystal lattice (or) space laltice eg. NaCl, KCl, Sugar,
quartz etc.
Amorphous solids - In such solids, particles do not have definite arrangement and thus are
short range order i.e. portions of regular arrangement are scaltered and in between them
arrangement is disordered. eg. glass
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Difference between crystalline and Amorphous solids
1. Characteristic geometry- In the crystalline solids the partides are definitely and orderly arranged
thus these have characteristic geometry while Amorphous solids do not have definite arrangement of
particles thus do not posses characteristic geometry thus called Amorphous (A Not, morphous
structure)
2. Melting points- As crystalline solids posses a definite arrangement of constitutent particles thus
there is fixed value of bond length or bond energy between to neighbouring particles, thus a crystalline
solid have a sharp melting point value i.e. it changes into liquid state at a define temeperature. On the
contrary an amorphous solid have irregular arrangement of particles thus various values of bond length
or bond energy therefore shows a range of temperatures where it melts. For example, when glass is
heated, it softens and then starts flowing without under going any abrupt change from solid to liquid
state. crystalline solids are thus classified as true solids while amorphous solids are pseudo solids.
3. Isotropy and Anisotropy :- Amorphous solids differe from crystalline solids and resemble liquids
in many respects. The properties of amorphous solids, such as electrical condutivity, thermal
conductivity, mechanical strength, refractive index, coefficient of thermal expansion etc. are same in
all directions. Such solids are known as Isotropic solids. Gases and liquids are also isotropic.
On the other hand, crystalline solids show these physical properties different in different direction .
Therefore crystalline solids are called Anisotropic in nature.
Anisotropy in crystolline solid is a consequence
of their orderly particle arrangement in crystals.
AB Consist of one type of particles.
CO Consist of two type of particles.
Due to this variation, properties are different
along different directions in crystalline solids.
While in amorphous solids there is short range order
i.e. regularity is upto small distances that one randomly
scattered throughout volume of the solid, thus the resultant
value of any physical property is same along all directions.
Classification of crystalline solids :
Crystalline solids can be classified, on the basis of nature of intermolecular forces operating in them,
into four categories.
Ionic solids, covalent solids, metallic solids and Molecular solids.
1. Ionic solids :- Ionic solids consist of ions (cation & anion) that are arranged in three dimensional
space bounded by strong electrostatic forces.
A
B
C
D
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Ionic solids are :-
Hard, briltle
Possesing high melting point and boiling point.
Bad conductor of electricity in solid state while furnishes the ions in aqueous (or) molten state
thus become conducting.
e.g. NaCl, KCl, KF, CsCl, Na
2
SO
4
, Zns etc.
2. Covalent solids :- These are formed by sharing of valence electrons between two atoms resulting
in the formation of a covalent bond. The covalent bonds extend in two and three dimensions forming a
giant interlocking structure called Network. Thus covalent solids are also called Network solids.
As the covalent bonds are directonal thus the atoms are bounded tightly, this imparts rigidity and
hardness to covalent solids. These solids also have high melting point.
As all the valence electrons take part in bond formation thus covalent solids are insulators and do
not conduct electricity. eg. diamond and silicon carbide (SiC).
In graphite, the carbon atoms are arranged is layers, one over other. In these layers each carbon
atom is covalently bonded to three other neighbouring carbon atoms. The fourth valence electron of
each carbon atom is present between the layers and is free to move about. These electrons are
responsible for conducting nature of graphite.
3. Metallic solids :- Metallic solids consist of large number of positive metal ions embedded in sea of
free electrons. These electrons are the valence electrons of the metal atom that are contributed by
each metal atom in course of formation of metallic crystals. These electrons are responsible for high
electrical and thermal conductivity of metals. When an electric field is applied these electrons flows
through the network of massive positive metal ions.When heat is supplied to one portion of a metal,
the thermal energy is uniformally spread through out the solid by free electrons. Metallic lusture is also
due to these free electrons.When light rays are incident on the metal surface these free elctrons absorb
energy and get excited to higher energy levels, as the electron jumps back to ground state it emits
energy in the form of light and the surfce shines.
4. Molecular solids :- Molecules are the basic constitutient particles of molecular solids. There are
three types of molecular solids.
(i) Non-polar molecular solids :- These are solids of either atoms [eg. solidified Noble gases] (or)
of non polar molecules [eg. solid H
2
, N
2
, O
2
, CO
2
, I
2
] etc.
In these solids atoms (or) moleculars are held together by weak varder weals forces.
(ii) Polar molecular solids :- Solid SO
2
, solid NH
3
are some solids which constitute particles that
have atoms bounded by polar covalent bonds. Due to polarity in bonds these solids have higher
melting point than non-polar molecular solids. Polar molecular solids are also non-conductors of
electricity.
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(iii) Hydrogen-bonded molecular solids :- Solids like H
2
O (ice), C
6
H
5
COOH etc which shows polar
covalent bonds between H and strong electronegative elements like F, O, N are the hydrogen
bonded, molecular solids. These solids are also non-conductor of electricity.
Crystalline state :-
A crystal is a solid comporsed of atoms/ions (or) molecules arranged in an orderly repetitive array
The crystallinity of a crystal may be defined as a condition of matter resulting from an orderly,
cohesive, three dimensional arrangement of its constituting particles in space.
This three dimentional arrangement is called crystal laltice or space crystal laltice and the
constitutingatoms are called lattice sites or lattice points. The lattices are bound by surface that are
usually planner and known as faces of the crystal.
Unit Cell :- The unit cell of a crystal is the basic structural unit possesing the symmetry of the
crystal and which when repeated in all directions will develop the crystal lattice. Thus a unit cell is the
smallest picture of the whole crystal.
Law of constancy of interfacial angles or Law of crystallography. :-
The angle between the two perpendiculars to the two intersecting faces is formed as the interfacial
angle. It is same as the angle between the unit cell adges. Goniometer is used to measure the interfacial
angle. The interfacial angle of a substance remains the same although its shape may be different due to
conditions of formation. This is known as law of constancy of interfacial angle.
Characteristics of a unit cell :-
1. A unit cell is characterized by the edge lengths a, b and c along the
three edges of the unit cell. These edges may or may not be mutually
perpendicular.
2. The angles between the edges are as follows.
o Between edges b and c,
| Between edges a and c, and
o Between edges a and b.
Therefore there are six parameters of a unit cell. a, b, c, &o,| ans o.
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Types of unit cells
Primitive or simple cubic (PS/SC) unit cell: Spheres in one layer sitting directly on top of those in previous
layer, so that all layers are identical. Each sphere is touched by six other, hence coordination number is
6. 52% of available space occupied by spheres.
Example: Polonium crystallises in simple cubic arrangement.
Z = 1 ; C.N. = 6
1.2 Body Centered cubic (BCC) unit cell: Spheres in one layer sit in the depression made by first layer in
a-b-a-b manner. Coordination number is 8, and 68% of available space is occupied by atoms.
Example: Iron, sodium and 14 other metal crystallises in this manner.
Z = 2 ; C.N. = 8
1.3 Face centered cubic (FCC) unit cell:
Examples : Al, Ni, Fe, Pd all solid noble gases etc.
Z = 4 ; C.N. = 12
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Crystal systems :-
These are seven crystal systems viz cubic, tetragonal, orthorhombic, hexagonal, rhombohedral, Monoclinic
and triclinic.
A crtystal system may exist with more than one type of unit cells. In nature there exist 14 different
types of crystal lattices also called Bravias lattices these crystal laltices are orises due to different
possible combination of crystal systems and unit cells.
Number of atoms in a unit cell :
1. Primitive cubic unit cell :-
(i) Number of atoms in an isolated unit cell = 8
(ii) Number of unit cells that share a atom in un-isolated condition = 8
contribution of a atom in each unit cell =
1
8
(iii) Number of atoms in an un-isolated unit cell =
8
1
8
= 1
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2. Body-centred cubic unit cell :-
(i) Number of atoms in an isolated unit cell = 8 + 1 = 9
(ii) Number of unit cells sharing
an atom at any one corner = 8
an atom at body centre = 1
(iii) Number of atoms in an un-isolated unit cell =
8
1
8
+ (1 1) = 1 + 1 = 2
3. Face-centred cubic unit cell :-
(i) Number of atoms in an isolated unit cell = 8 + 6 = 14
(ii) Number of unit cells sharing
an atom at any one corner = 8
an atom at any face centre = 2
(iii) Number of atoms in an un-isolated unit cell
8
1
8
+ 6
2
1
= 1 + 3 = 4
Packing efficiency :-
P. E.
Volume Ocupied by atoms in crystal
Total volume of the crystal
=
1. For face centred cubic structure :-
r
2r
r
A
B
C
In AABC
B
2
= AC
2
= BC
2
+ AB
2
= 2a
2
b =
a 2
Radivs of sphere
r =
b a
4
2
4
9
2 2
= =
As number of particles in a FCC is four therefore
total volume occupied by particles =
4
4
3
3
tr
P. E. =
4
4
3
3
3
tr
a
=
t
3 2
= 0.74
Therefore packing efficiency of FCC is 74%
2. For body centred cubic :-
In AABC
B
2
= AB
2
= AC
2
+ BC
2
a
2
+ a
2
(2)
b
2
= 3a
2
or b =
a 3
as r =
b a
4
3
4
=
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Packing efficiency =
t 3
6
= 0.68
Therefore packing efficiency of BCC is 68%
3. For simple cubic structure :-
Hence b = a
and as r =
b a
2 2
=
a
Therefore P.E. = 0.524
Therefore packing efficiency of simple cubic is 52.4%
Calculation of density of a unit cells :-
(i) Volume of a cubic unit cell =a
3
[a = edge length]
(ii) Mass of a unit cell = no. of atoms in mass of each atom unit cell =z m.
as m =
Molar mass
N
A
[N
A
Avogadro Number] or m =
M
N
A
(iii) Density of the unit cell =
mass of unit cell
volume of unit cell
=
3
a
m Z
=
3
M Z
a NA
(iv) Density of unit cell of a solid compound is same as density of any amount of mass of that
compound.
Example1- The density of crystalline sodium chloride is 2.165 g cm
-3
. What is the egde length of the unit
cell? What would be the dimensions of cube containing one mole of NaCl.
Ans- Since density d =
3
M Z
a NA
a
3 =
A N d
M Z
=
23
10 023 . 6 165 . 2
5 . 58 4
= 1.794 10
-22
a = 5.64 10
-8
cm
Molar volume =
Density
Mass
=
165 . 2
5 . 58
Therefore, Edge length (a) =
3
1
165 . 2
5 . 58
= 3 cm
Coordination Number:- It is defined as the number of nearest neighbours that an atom has in a unit cell.
(a) Simple Cubic Struct)ure- C.N. = 6
(b) Face Centered Cubic structure - C.N. = 12
(c) Body Centered Cubic structure- C.N. = 8
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Closed packed structures :-
(i) Arrangment in One dimension:- The number of neasest neighbours of a particle is called its
coordination number. When th particles are arranged along a line i.e. in 1D arrangement the
coordination number of the particles is two.
(10 arrangement)
[C.N. = 2]
(ii) Arrangment in Two dimensions:-Now for 2D arrangement the second line of the particle can be
arranged in two manners.
I
st
Particles of second line align as it is in first line
II
nd
Particles of second line align in depressions between the particles of first line.
I
st
Case II
nd
Case
A
A
A
A
A
B
A
B
It is called AAA type arrangement joining the It is callled ABAB arrangement Joining the
centres of four nearest particles gives a square, centre of six nearest particles gives a hexagon,
thus it is also called Square, close packing. In thus it is also called Hexagonal close packing
square close packing the coordination number of In Hexagonal close packing 2D structure the
particles is 4. coordination number of particle is 6.
The triangular shaped vacant space (reated due to adjacent placement of three spheses in this
case) iscalled Triangular void. The adjacent triangular void in ABAB arrangement are pointing in
opposite directions (i.e. up and down).
(iii) Arrangment in 3 dimension:- To build up the third layer of spheres, there are two ways .
1. ABAB Type or HCP Type- In this arrangment the spheres are
placed in the voids between the spheres forming the bottom
layer, now the third layer is placed on the second layer in such
a way that the third layer lies exactly above the spheres of the
first layer. When this arrangment is continued it is found to
have hexagonal symmetry and is called hexagonal close packing.
2. ABCABC.. type or Cubic close packing- In this type of arrangment the spheres of the second
layers are placed on the hollow spaces between the spheres of the first layer. Now the third layer is
placed on the second layer in such a way that the third layer occupies the hollow positions between the
spheres of the second layer. Now the spheres of the fouth layer will be exactly above the spheres of the
first layer. This type of arrangment is thus called ABCABC.. arrangment. When this arrangment is
repeated contiinuously it is found to have cubic symmetry and is termed as CCP arrangment and also
referred as FCC arrangment.
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Note- FCC and CCP are the same arrangment.The Coordination number of each sphere in the
above two arrangment is 12.
Interstitial sites or voids:- In close packing of spheres there is always some vacant space between the
spheres, thesevacant spaces are called interstitial sites or holes or voids. Voids are of two types-
(i) Tetrahedral Voids- When a sphere is placed on the space between three spheres which are touching
each other , the centres of these four spheres are at the corners of a regular tetrahedron and the void is
called tetrahedral void.
In HCP and CCP each sphere is in contact with three spheres above and three spheres below. Thus
there are two tetrahedral voids associated with each sphere.
So if there are Z atoms in a unit cell than-
Number of tetrahedral voids = 2Z
Locating tetrahedral voids-In FCC structure, there are eight spheres in the corners of the
unit cell and each sphere is in contact with three groups giving rise to eight tetrahedral voids .
Circles labelled T are the tetrahedral voids.
Radius Ratio or size of tetrahedral voids
sphere
void
r
r
= 0.225
(ii) Octahedral voids- This type of void is formed by the combination of two triangular voids. Each
octahedral void is created by superimposing two equilateral triangles with apices in opposite directions.
There is one octahedral site associated with each sphere(atom).
So if there are Z atoms in a unit cell than-
Number of octahedral voids = Z
Locating octahedral voids- In closed packed structures the octahedral voids are present at the
centres of the edges of the cube.
Radius Ratio or Size of octahedral voids-
sphere
void
r
r
= 0.414
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Circles labelled as O represents octahedral voids.
Example- In a solid, oxide ions are arranged in ccp. Cations A occupy one sixth of the
tetrahedral voids and cations B occupy one third of the octahedral voids. What is the formula
of the compound?
Solution: Let there are N atoms in CCP arrangment than
No. of tetrahedral voids = 2N and No. of Octahedral voids = N
No of A atoms =
6
1
2 N
=
3
N
and no. of B atoms =
3
1
N
So the formula of oxide will be
3
1
3
1
B A
= AB
Example- In a crystalline solid, having formula AB
2
O
4
, oxide ions are arranged in cubic close packed lattice
while cations A are present in tetrahedral voids and cations B are present in octahedral voids
(i) What percentage of the tetrahedral voids is occupied by A?
(ii) What percentage of the octahedral voids is occupied by B?
Solution: In a cubic close packed lattice of oxide ions there would be two tetrahedral voids and one octahedral
void for each oxide ion.
For four oxide ions there would be 8 tetrahedral and four octahedral voids two are occupied by B.
Percentage of tetrahedral voids occupied by A = 1/8 100 = 12.5%
Percentage of tetrahedral voids occupied by B = 2/4 100 = 50%
STRUCTURE OF CRYSTALS
1. Ionic Crystals:- In ionic crystals, the coordination number depends on the relative sizes of the ions. The
ratio of the radii of cation and anion is called radius ratio. The coordination number varies with radius ratio.
Radius ratio Coordination Number Arrangment of Example
(r
+
/r
-
) anions round the cation
0.155 0.225 3 Planer triangular B
2
O
3
0.225 0.414 4 Tetrahedral ZnS
0.414 - 0.732 6 Octahedral NaCl
0.732 - 1 8 Cubic(Body centred) CsCl
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Structure of Ionic Crystals
NaCl type :- In NaCl each Na
+
ion is surrounded by six Cl
-
ions. Cl
-
ions form the FCC lattice and Na
+
ions
occupy the octahedral holes. There are six octahedral holes around each Cl- ion. The coordination
number of each ion is 6 :6.
Radius ratio =
r
r
Na
Cl
+
= 0.524
No. of sodium ions = 12(at the edge centres)
1
4
+ 1(at body centre) = 4
No. of chloride ions = 8(at the corners)
1
8
+ 6(at face centres)
1
2
= 4
Example- most alkali metal halides like KCl, NaI, RbF, RbI, AgF,AgCl, AgBr, NH
4
Br and FeO.
CsCl Type
In CsCl, Cl
-
ions are at the corners of a cube whereas Cs
+
at the centre of the cube and
vice versa. Thus it has BCC structure. The cordination number is 8:8.
Radius ratio = 0.933
examples- CsBr, CsI.
Note- At 760K CsCl structure changes into NaCl structure and coordination number
changes from 8:8 to 6:6.
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ZnS or ZnOType structure
ZnS crystal has two type of structures
(i) Zinc Blende structure:- It has FCC or CCP structure. The S
2-
ions are at the corners of the cube
and at the centre of the each face . Zn ions occupy half of the tetrahedral voids. Each Zn ions is
surrounded by four sulphide ions tetrahedrally and vice versa. The coordination number is 4:4.
Radius ratio = 0.4
examples- CuCl, CuBr, CuI, AgI. Diamond also posses the same structure.
Zinc blende structure
S
2
Zn
+2
(ii) Wurtzite structure:- It has hexagonal close packed structure. S
2-
ions adopt HCP arrangment and
Zn
2+
ions occupy half of the tetrahedral sites. The coordination number is 4:4.
Fluorite structure:(CaF
2
) Ca
2+
forming ccp arrangement and F
have radii 88 and 200 pm respectively. In the closed packed crystal of compound
AB, predict the co-ordination number of A
+
.
Q.14 CsCl has the bcc arrangement and its unit cell edge length is 400 pm. Calculate the interionic distance in CsCl.
Q.15 Gold crystallizes in a face centered cubic lattice. If the length of the edge of the unit cell is 407 pm,
calculate the density of gold as well as its atomic radius assuming it to be spherical. Atomic mass of
gold = 197 amu.
Q.16 The density of KBr is 2.75 g cm
3
. The length of the edge of the unit cell is 654 pm. Show that KBr has
face centered cubic structure.
(N = 6.023 10
23
mol
1
, At. mass : K = 39, Br = 80)
Q.17 An element crystallizes in a structure having FCC unit cell of an edge 200 pm. Calculate the density, if
200 g of this element contains 2410
23
atoms.
Q.18 The effective radius of the iron atom is 1.42 . It has FCC structure. Calculate its density
(Fe = 56 amu)
Q.19 A crystal of lead(II) sulphide has NaCl structure. In this crystal the shortest distance between Pb
+2
ion
and S
2
ion is 297 pm. What is the length of the edge of the unit cell in lead sulphide? Also calculate the
unit cell volume.
Q.20 If the length of the body diagonal for CsCl which crystallises into a cubic structure with Cl
ions at the
corners and Cs
+
ions at the centre of the unit cells is 7 and the radius of the Cs
+
ion is 1.69 , what is
the radii of Cl
ion?
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EXERCISE II
Q.1 Iron has body centered cubic lattice structure. The edge length of the unit cell is found to be 286 pm.
What is the radius of an iron atom?
Q.2 Cesium chloride forms a body centered cubic lattice. Cesium and chloride ions are in contact along the
body diagonal of the unit cell. The length of the side of the unit cell is 412 pm and Cl
had NaCl type closed packed structure. If the anion has a radius of 250 pm, what
should be the ideal radius of the cation? Can a cation C
+
having a radius of 180 pm be slipped into the
tetrahedral site of the crystal of A
+
B
+
and
7 . 0
K
r
Na
r
=
+
+
Calculate:
(a) The ratio of the sides of unit cell for KCl to that for NaCl and
(b) The ratio of densities of NaCl to that for KCl.
Q.9 An element A (Atomic weight = 100) having bcc structure has unit cell edge length 400 pm. Calculate the
density of A and number of unit cells and number of atoms in 10 gm of A.
Q.10 Prove that the void space percentage in zinc blende structure is 25%.
Q.11 A unit cell of sodium chloride has four formula units. The edge of length of the unit cell is 0.564 nm.
What is the density of sodium chloride.
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Q.12 In a cubic crystal of CsCl (density = 3.97 gm/cm
3
) the eight corners are occupied by Cl
ions with Cs
+
ions at the centre. Calculate the distance between the neighbouring Cs
+
and Cl
ions.
Q.13 KF has NaCl structure. What is the distance between K
+
and F
ion is 1.36 .
Q.20 NaH crystallizes in the same structure as that of NaCl. The edge length of the cubic unit cell of NaH is
4.88 .
(a) Calculate the ionic radius of H
has the B
in KF
is :
(A) 269 pm (B) 13.5 pm (C) 136 pm (D) 3 pm
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Q.65. CsBr crystallises in a body centred cubic lattice. The unit cell length is 436.6 pm. Given that the atomic
mass of Cs = 133 and of Br = 80 amu Avogadros number being 6.02 10
23
mol
1
, the density of CsBr
is :
(A) 8.50 g/cm
3
(B) 4.25 g/cm
3
(C) 42.5 g/cm
3
(D) 0.425 g/cm
3
Q.66. The densities of NaCl crystal as measured by puknometer and X-ray method are 2.165 10
3
kg. m
3
and 2.178 10
3
kg. m
3
respectively. The fraction of unoccupied sites in soldium chloride crystal is :
(A) 5.96 10
3
(B) 5.96 (C) 5.96 10
2
(D) 5.96 10
1
Q.67. The compound formed by elements X and Y crystallizes in cubic structure in which X atoms are at the
corners of the cube and Y atoms are at the face centre. The formula of the compound is :
(A) XY
2
(B) XY (C) XY
3
(D) X
3
Y
Q.68. The density of a pure substance A whose atoms pack in cubic close pack arrangement is 1 gm/cc. If B
atoms can in gm/cc. [Atomic mass (A) = 30 gm/mol and atomic mass (B) = 50 gm/mol]
(A) 3.33 (B) 4.33 (C) 2.33 (D) 5.33
Q.69. In which type of voids magnesium and silicon is present respectively in asbestos [Mg
3
Si
2
O
5
] if
r
Mg
++ /
r
O
= 0.59 and r
Si
+4
/r
O
2 is 0.29
(A) Tetrahedral & octahedral (B) Both tetrahedral
(C) Octahedral & tetrahedral (D) Both Octahedral
Q.70. The composition of a sample of Wustite is Fe
0.93
O. What is the percentage of iron present as Fe
3+
?
(A) 15% (B) 25% (C) 35% (D) 45%
Q.71. In a compound AB the ionic radii of A
+
and B
ion will be
(A) 0.897
A (B) 3.72
A (C) 1.749
A (D) None of these
Q.77. The edge of face centred unit cubic cell is 508 pm. If the radius of the cation is 110 pm , the radius of the
anion is :
(A) 144 pm (B) 288 pm (C) 628 pm (D) 398 pm
Q.78. The number of atoms in 100 g of a fcc crystal with density 10.0 g/cc and edge length as 100 pm is
(A) 3 10
25
(B) 4 10
25
(C) 1 10
25
(D) 2 10
25
Q.79. The unit cell of aluminium is a cube with an edge length of 405 pm. The density of aluminium is 2.7 g/cc.
The type of lattice Al has is :
(A) bcc (B) fcc (C) sc (D) End centred
Q.80. The face centred unit cell of nickel has an length 352.39 pm. The density of nickel is 8.9 g/cc. Avogadro
number is :
(A) 6.029 10
23
(B) 6.023 10
23
(C) 5.9 10
23
(D) 6.4 10
23
Q.81. An ionic compound AB has ZnS type of structure, if the radius A
+
is 22.5 pm, then the ideal radius of B
is :
(A) 54.35 pm (B) 100 pm (C) 145.16 pm (D) None of these
Q.82. Addition of CdCl
2
to AgCl yields solid solution where the divalent cations Cd
2+
occupy the Ag
+
sites.
Which one of the following statements is true ?
(A) The no. of cationic vacancies is equal to that of divalent ions added.
(B) The no. of cationic vacancies is one half of the no. of that of divalent ions added.
(C) The no. of anionic vacancies is equal in no. to that of divalent ions added.
(D) No cationic or anionic vacancies are produced.
More than one option is correct
Q.83. In the fluorite structure if the radius ratio is
2
3
- 1 , how many ions does each cation touch ?
(A) 4 anions (B) 12 cations (C) 8 anions (D) No cations
Q.84. TiO
2
(rutile) shows 6 : 3 coordination. Which of the following solids have a rutile-like structure ?
(A) MnO
2
(B) ZnS (C) KCl (D) SnO
2
Q.85. The intermetallic compound LiAg has a cubic crystalline structure in which each Li atom has 8 nearest
neighbour silver atoms and vice-versa. What is the type of unit cell ?
(A) Body - centred cubic
(B) Face - centred cubic
(C) Simple cubic for either Li atoms alone or Ag atoms alone
(D) None of these
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CHEMISTRY
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Q.86. Which of the following compounds represent a normal 2 : 3 spinel structure ?
(A) Mg
II
Al
2
III
O
4
(B) Co
II
(Co
III
)
2
O
4
(C) Zn(TiZn)O
4
(D) Ni(CO)
4
Q.87. Which of the following statements are correct ?
(A) The crystal structure of rock salt is an fcc array of anions in which the cations occupy all the
octahedral holes (or vice versa)
(B) The sphalerite crystal structure is an expanded fcc anion lattic with cations occupying one type of
tetrahedral hole.
(C) In the fluorite crystal structure, cations occupy half the cubic holes of a primitive cubic array of
anions
(D) None of these
Q.88. Which of the following crystals have 6 : 6 coordination ?
(A) NH
4
I (B) MgO (C) MnO (D) ZnS
Q.89. Which of the following statement is correct ?
(A) A rutile (TiO
2
) structure consists of an hcp anion lattice with cations occupying half the octahedral
holes
(B) The wurtzite structure is derived from an expanded hcp anion array with cation occupying one type
of octahedral holes
(C) In the fluorite structure (CaF
2
), anions occupy both types of tetrahedral holes in an expanded fcc
lattice of cations
(D) None of these
Q.90. The hcp and ccp structure for a given element would be expected to have
(A) The same coordination number (B) The same density
(C) The same packing fraction (D) All of these
Q.91. Which of the following statements are correct ?
(A) The coordination number of each type of ion in a CsCl crystal is eight
(B) A metal that crystallizes in a bcc structure has coordination number of twelve
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells
(D) The length of the unit cell is NaCl is 552 pm (given that
r
Na
+ = 95 pm and
r
Cl
= 181 pm)
Q.92. Pick up the correct statements :
(A) The ionic correct of AgBr has Schottky defect
(B) The unit cell having crystal parameters, a = b = C, o = | = 90, = 120 hexagonal
(C) In ionic comopunds having Frenkel defect, the ratior
+
/r
is high.
(D) The coordination number of Na
+
ion in NaCl is 4
Q.93. Select the correct statements (s)
(A) In NaCl crystal, each ion has an octahedral coordination.
(B) The C.N. of an atom in hcp structure is 12.
(C) Diamagnetic materials are attracted by the magnetic fields
(D) An octahedral hole is smaller than a tetrahedral hole.
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CHEMISTRY
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Q.94. Which of the following are not the characteristics of crystalline solids ?
(A) They are exhibit polymorphism (B) They are isotropic
(C) They do not have thermodynamic defects (D) After melting, they become crystalline
Q.95. Which of the following statements are false :
(A) The radius of a metal atom is taken as half the nearest metal metal distance in a metallic crystal
(B) One tetrahedral void per atom is present in hcp structure.
(C) In the fluorite structure (CaF
2
), the Ca
2+
ions are located at the lattice points and the fluoride ions fill
all the tetrahedral holes in the ccp crystal
(D) In the antifluorite structure (Li
2
O, Rb
2
S) the cations are located at the lattice points and anions fill the
tetrahedral holes in the ccp structure.
Q.96. If the radius of Na
+
ion is 95 pm and that of Cl
ions are present in the cubic voids (D) The close packed structure is formed by
Cs
+
ions.
Q.99. Which of the following statement (s) is (are) correct for CaF
2
:
(A) Ca
2+
ions are present only at the corners of a cube
(B) ccp type structure
(C) F
is
(A) 3.72 (B) 1.86 (C) 7.44 (D) 4.3 [1995]
Q.136. Chromium metal crystallizes with a body centred cubic lattice. The length of the unit cell edge is found to
be 287 pm. Calculate the atomic radius. What would be the density of chromium in gl/m
3
? [1997]
Q.137. Which of the following statement(s) is (are) correct ?
(A) The coordination number of each type of ion in CsCl crystal is 8.
(B) A metal that crystallizes in bcc structure has a coordination number of 12.
(C) A unit cell of an ionic crystal shares some of its ions with other unit cells.
(D) The length of the unit cell in NaCl is 552 pm. (
r
Na
+ = 95 pm,
r
Cl
= 181 pm) [1998]
Q.138. The coordination number of a metal crystallizing in a hexagonal close-packed structure is :
(A) 12 (B) 4 (C) 8 (D) 6 [1999]
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CHEMISTRY
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Q.139. A metal crystallises into two cubic phases, face centered cubic (fcc) and body centred cubic (bcc),
whose unit cell lengths are 3.5 and 3.0
A , respectively. Calculate the ratio of densities of fcc and bcc.
[1999]
Q.140. In solid AB having the NaCl structure, A atoms occupy the corners of the cubic unit cell. If all the face
centered atoms along one of the axes removed, then the resultant stoichiometry of the solid is :
[2001]
(A) AB
2
(B) A
2
B (C) A
4
B
3
(D) A
3
B
4
Q.141. Read the following statement and explanation and answer as per the options given bellow :
Assertion :In any ionic solid [MX] with Schottky defects, the number of positive and negative ions
are same. [2001]
Reason : Equal number of cation and anion vacancies are present.
(A) If both assertion and reason are correct, and reason is the correct explanation of the assertion.
(B) If both assertion and reason are correct, but reason is not the correct explanation of the assertion 2.
(C) If assertion is correct, but reason is incorrect
(D) If assertion is incorrect, but reason is correct.
Q.142. A substance A
x
B
y
crystallizes in a face centred cubic (fcc) lattice in which atoms A occupy each corner
of the cube and atoms B occupy the centres of each face of the cube. Identify the correct composition
of the substance A
x
B
y
.
(A) AB
3
(B) A
4
B
3
[2002]
(C) A
3
B (D) Composition cannot be specified
Q.143. You are given marbles of diameter 10 mm. They are to be placed such that their centres are lying in a
square bound by four lines each of length 40 mm. What will be the arrangements of marbles in a plane so
that maximum number or marbles can be placed inside the area ? Sketch the disgram and derive
expression for the number of molecules per unit area. [2003]
Q.144. A compound AB has rock salt type structure. The formula weight of AB is 6.023 Y amu, and the closest
A-B distance is Y
1/3
nm, where Y is an arbitrary number. [2004]
(A) Find the density of lattice
(B) If the density of lattice is found to be 20 kg m
3
, then peridict the type of defect.
Q.145. In which of the following crystals alternate tetrahedral voids are occupied ? [2005]
(A) NaCl (B) ZnS (C) CaF
2
(D) Na
2
O
Q.146. The edge length of unit cell of a metal having molecular weight 75 g/mol is 5A which crystallizes in cubic
lattice. If the density is 2 gm/cm
3
then find the radius of metal atom (N
A
= 6 10
23
). Give the anwer in
pm. [2006]
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CHEMISTRY
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Q.147. Match the crystal system/unit cells mentioned in Column-I with their characteristic features mentioned in
Column-II.
Column I Column II [2007]
A. Simple cubic and face centred P. Have these cell
Cubic parameters
B. Cubic and rhombohedral Q. Are two crystal systems
C. Cubic and tetragonal R. Have only two crystallo-graphic angles of 90
D. Hexagonal and monoclinic S. Belong to same crystal system
Passage :
In hexagonal systems of crystals, a frequently enocountered arrangement of atoms is described as a
hexagonal prism,. Here, the top and bottom of the cell are regular hexagons and three atoms are
sandwiched in between them. A spacefilling model of this structure, called hexagonal close-packed
(hcp), is constituted of a sphere on a flat surface surrounded in the same plane by six identical spheres as
closely as possible. Three spheres are then placed over the first layer so that they touch each other and
represent the second layer. Each one of these three spheres touches three spheres of the bottom layer.
Finally, the second layer is covered with a third layer that is identical to the bottom layer in relative
position. Assumed radius of every sphere to be r. [2008]
Q.148. The number of atoms on this hcp unit cell is
(A) 4 (B) 6 (C) 12 (D) 17
Q.149. The volume of this hcp unit cell is :
(A) 24 2
3
r (B) 16 2
3
r (C) 12 2
3
r (D)
64
3 3
3
r
Q.150. The empty space in this hcp unit cell is :
(A) 74% (B) 47.6% (C) 32% (D) 26%
Q.151. The figures given below show the location of atoms is three crystallographic planes in a fcc lattice. Draw
the unit cell for the corresponding structure and identify these planes in your diagroam. [2000]
A. B. C.
Q.152. Sodium metal crystallizes in body centred cubic lattice with the cell edge a = 4.29
A. What is the radius of
sodium atom ?
[1994]
Q.153. A unit cell of sodium chloride has four formula units. The edge length of the unit cell is 0.564 nm. What
is the density of sodium chloride ? [1997]
Q.154. An element crystallises in fcc lattice having edge length 400 pm. Calculate the maxium diameter which
can be placed in interstitial sites without distrubing the structure.
[2005]
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CHEMISTRY
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Q.155. The correct statement(s) regarding defects in solids is/are [2009]
(A) Frenkel defect is usually favoured by a very small difference in the sizes of cation and anion
(B) Frenkel defect is a dislocation defect
(C) Tapping of an electron in the lattice leads to the formation of F-center
(D) Schottky defects have no effect on the physical properties of solids
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CHEMISTRY
Reconstruct Your Chemistry With Prince Sir
EXERCISE I
Q.1 A-B Q.2 AuCu
3
Q.3 A
4
B
2
C
2
Q.4 59.95%, +4
Q.5 ZnAl
2
O
4
Q.6 267 pm, 534 pm, 378 pm
Q.7 267 pm, 231.2 pm, 188.8 pm Q.8 3.5 g cm
3
Q.9 3.472 10
24
atoms Q.10 FCC
Q.11 0.24% Q.12 438.5 pm, 219.25 pm
Q.13 6 Q.14 346.4 pm
Q.15 19.4g/cm
3
, 143.9 pm Q.17 41.67 g cm
3
Q.18 5.74 g cm
3
Q.19 a =5.9410
8
cm, V=2.09610
22
cm
3
Q.20 1.81
EXERCISE II
Q.1 123.84 pm Q.2 175.8 pm
Q.3 AB
2
O
4
Q.4 103.4 pm, No
Q.5 6.0110
23
Q.6 4, 6, 8
Q.7 7.887 g/cc , 8.59 gm/cm
3
Q.8 (a) 1.143, (b) 1.172
Q.9 5.188 gm/cm
3
, 6.02310
22
atoms of A, 3.011510
22
unit cells
Q.11 2.16 gm/cm
3
Q.12 3.57
Q.13 2.685 Q.14 15.053
Q.15 (a) octahedral, (b) 1/4 Q.16 4.34
Q.17 6.02 10
18
mol
1
Q.18 0.414 r, 79.3%
Q.19 (a) MnF
3
, (b) 6, (c) 4.02 Q.20 (a) 1.49 , (b) 1.37 g/cm
3
Q.21 (a) 2.88 , (b) 12 , (c) 19.4 g/cc Q.22 4 molecules of H
2
O
Q.23 for Fe is bcc, for V is bcc, for Pd is face centered
Q.24 (a) 4.5 , (b) 5.2 , (c) 8, (d) 6, (e) 0.92 g/cm
3
Q.26 XY
3
, 4.38 g/cm
3
Q.27 (a) 3.52 ,(b) 1.24
Q.28 Mg
2
SiO
4
, Fe
2
SiO
4
, 59% Q.29 (i) 3.90, (ii) 0.120 g/cc
Q.30 2.376%
OBJECTIVE QUESTION BANK
1. D 2. D 3. C 4. B 5. B 6. D 7. B
8. B 9. D 10. B 11. D 12. A 13. B 14. A
15. C 16. C 17. C 18. C 19. B 20. B 21. A
22. A 23. D 24. C 25. C 26. C 27. B 28. B
29. A 30. B 31. B 32. D 33. B 34. C 35. C
36. C 37. B 38. A 39. B 40. C 41. C 42. D
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CHEMISTRY
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43. A 44. A 45. D 46. D 47. A 48. C 49. D
50. C 51. C 52. B 53. D 54. D 55. B 56. D
57. C 58. D 59. C 60. A 61. B 62. A 63. B
64. A 65. A 66. A 67. C 68.B 69. C 70. A
71. A 72. C 73. A 74. D 75. C 76. B 77. A
78. B 79. B 80. A 81. B 82. A 83. B,C 84.
A,D 85. A,C 86. A,B 87. A,B,C 88. A,B 89.
A,B,C 90. A,C 91. A,C 92. B,C 93. A,B 94.
B,C 95. B,D 96. A,C 97. B,D 98. A,B
99. B,D 100. A,B,D 101. A,B,C,D 102. A,B,D 103. A,B,C,D 104. C 105.
B 106. A 107. B 108. B 109. C 110. C 111. B
112. B
113. A 114. B 115. C 116. B 117. C 118. B 119. A
120. A 121. A 122. B 123. C 124. B 125. B 126. A
127. A 128. A-S B-R C-P D-Q 129. A-Q B-P C-S D-R
130. A-U B-S C-P D-Q E-T F-R
131. A-P B-S C-Q D-R
132. A-R B-Q C-P D-S
133. A-P,Q,R,S B-P,R,S C-P,S D-P,R,S
134. A-Q B-R C-P D-R 135. A 137. A,C,D 138.A 140. D
141. A 142. A 145. B 147. A-P,S B-PQ C-Q D-Q,R
148. B 149. A 150. D 155. B,C
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