S.K. Pandey (M.Sc. B.Ed.) G.E.A. and Jr. College Contact no.

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Standard: ISC Chapter # 1. Solid State (For private circulation only) Student: ……………….
The Solid State: A solid is that form of matter that possesses rigidity and hence possesses a definite shape and
a definite volume.
Crystalline Solids Amorphous Solid
They have a regular three dimensional arrangement of They do not have regular arrangement of particles,
atoms, ions or molecules due to which they have well therefore do not have well defined particles.
defined geometrical shape.
They have long range order They have short range order
They have sharp melting point i.e., they melt at a They do not have sharp melting point i.e., they melt
particular temperature. over a range of temperature.
They have high and fixed heat of fusion, i.e., high They do not have fixed heat of fusion.
energy is required to melt 1 mole of crystalline solid.
They are anisotropic, i.e., they have different optical They are isotropic, i.e., they have same properties in
and electrical properties in different directions. all directions.
They are true solids, i.e., they show all the They are pseudo – solids, i.e., they do not show all the
characteristic properties of solids. characteristic properties of solids.

Space Lattice and Unit Cell: A regular arrangement of the

constituent particles of a crystal in a three dimensional space is called
crystal lattice or space lattice.

Unit cell
The unit cell is defined as the smallest repeating unit in space lattice
which when repeated over and over again generates the complete
crystal lattice. The crystal can consist of an infinite number of unit
cells.
Types of Unit Cells
The types of unit cells in which particles are present only at the corners are called primitive unit cell or simple
unit cells. These simple unit cells are further divided into different types: - Face centered and Body centered and
end centered.
Body Centered: -The particles are available at the corners as well as one particle is present at the center of the
body of the unit cell.

Face centered cubic: - The particles are present not only at the corners but also at the centre of each face of the
unit cell.

On the basis of the external appearance the known crystals can be classified into seven types. These are called
crystal systems. In terms of the internal structure also the crystal lattices contain only seven types of unit cells.
The seven crystal systems and the definition of their unit cells in terms of their unit distances and the angles are
compiled in Table

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Calculation of Number of Particles per Unit Cell of a Cubic Crystal System.
Keeping the following points in mind we can calculate the number of atoms in a unit cell.
An atom at the corner is shared by eight unit cells. Hence an atom at the corner contributes 1/8 to the unit cell
An atom at the face is a shared by two unit cells. Contribution of each atom on the face is 1/2 to the unit cell.
An atom within the body of the unit cell is shared by no
other unit cell.
An atom present on the edge is shared by four unit cells
Contribution of each atom within the body is 1 to the unit
cell.
Contribution of each atom on the edge is 1/4 to the unit
cell.
By applying these rules, we can calculate the number of
atoms in the different cubic unit cells of monoatomic
substances.

Simple cubic: In this type of unit cell, there are

eight atoms at the corners and each such atom
makes contribution to the unit cell.
Hence a simple cubic unit cell has 8 (at corners) ×
1/8 = 1 atom
This type of unit cell has eight atoms at corners
and one at the body center. Each corner atom
makes 1/8 contribution and the atom at the body
center belongs only to the particular unit cell.
Hence, a body centered cubic unit cell has, 8(at corners) × 1/8 + 1 (at body center) × 1 = 2 atoms
Face centered cubic: A face centered cubic unit cell has one atom at each corner and one atom at each face
center, being shared by two unit cells and making a contribution of only ½ to a particular unit cell.
Hence, a face centered cubic unit cell has 8(at corners) × 1/8 + 6 (at face centers) × ½ = 4 atoms
Cubic Close Packing: When the third layer spheres are placed on the voids a layer different from layers A and
B is produced leading to ABC ABC ....... type of arrangement or cubic close packing (CCP) similar to face
centered cubic. It is similar to face centered cubic packing.
Examples of HCP - Mg, Zn, Cd
Examples of CCP - Na, K, Fe, Cr;
In both the above patterns of arrangements the maximum occupied shape is 76% of the available volume.
In both HCP and CCP the coordination number is 12 because a sphere is in contact with 6 spheres in its own
layer. It touches three spheres in the layer above and three in the layer below.

Co-ordination number in hcp and ccp (i) Hexagonal close packing

Now, in the triangle ACD, AD is body diagonal.

(AD)2 = (AC)2 + (CD)2 = 2a2 + a2 = 3a2
AD = 3 a
The tetrahedral void is present at the center of the body diagonal AD and the small spheres touches other
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Body diagonal AD = R + R + 2r = 2(R + r)

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In all closed packed structures there are always some voids or empty spaces. The percentage of the total space
that is filled by the constituent particles is called the packing efficiency. It is calculated from the following
relation:

In simple cubic lattice, the constituent particles occupy only the corner positions of the cubic unit cell. These
particles touch one another along the edge of the cube as shown in the Figure. Let a be the edge length of the
cube and r the radius of the particle then

The body centered cubic unit cell has constituent particles present at all its
corners as well as at its body center. The particle at the body-center touches
the particle at corner positions. Thus, the particles are in contact along the
body-diagonal of the cube. Consider the body-diagonal AF along which the
contact between the central particles with those at corners A and F has been
shown in Fig.

(Whole of the central particle (2r) and one-half of each of the two corner
particle (r + r) occupy the body-diagonal)
Length of the body-diagonal
In the triangle EFD on the face CDEF, EF  ED.

Where a is the edge-length or side of the cube.

The number of constituent particles in a body-centered cubic unit cell = 2

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For cubic crystals of ionic compounds (NaCl, ZnS). The formula is the same except that now, Z is the Number
of formula units present in one-unit cell and M is Formula mass.
Ionic Radius: It is defined as the distance from the centre of the nucleus up to the last shell containing the
electrons.
Structure of Simple Ionic Compounds Rock Salt (or NaCl)
Summary of Main Characteristics of Ionic Solids: -

Defects in Crystals: Presence of impurities also adds to disorder.

"Any departure from perfectly ordered arrangement of atoms/ions in crystal is called imperfection or crystal
defect".
These imperfections modify the properties of the crystal and also sometimes impart new properties to the solids.
There are two types of imperfections: 1. Electronic imperfections 2. Atomic or point imperfection
1. Electronic Imperfections: At zero K (absolute zero) electrons in covalent or ionic crystals (e.g., Si or NaCl)
occupy the lowest energy level.
Above zero K in pure silicon or germanium electrons are released thermally from the covalent bonds. This leads
to the presence of free electrons and electron deficient bonds called holes, which are responsible for intrinsic
conduction.
These free electrons and the holes in solid give rise to electronic imperfections.
Types of defects in Crystals: The defect, which arises due to the irregularity in the arrangement of atoms or
ions are called point defects. Point defects are of three types:

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Based on their conductivity solids can be divided into three categories. (a) Conductors (b) Semiconductors (c)
Insulators.
Conductors: These are the solids with conductivities ranging from 104 to 107 S m–1. Thus through them
electricity can flow to a larger extent.
Depending upon the type of charge carriers, the conductors are further classified as metallic and electrolytic
conductors. In metallic conductors, electrons are the charge carriers. In electrolytic conductors, ions are the
charge carriers. Therefore, electrolytic conductors conduct only when there are mobile ions i.e., in molten state.
However, in solid state they conduct electricity only to a small extent, which is due to the presence of defects
(holes, electrons etc)
Examples: NaCl, KCl as electrolytic and metals as metallic.

Insulator: The solids, which almost do not allow the electricity to pass through them are called insulators.
These are the solids with extremely low conductivities ranging from 10–20 to 10–10 S m–1.
Ex: S, P, plastics, wood etc.
Semiconductors: The solids whose conductivity lies between metallic conductors and insulators are called
semiconductors. These are the solids with intermediate conductivities ranging from 10–6 to 104 S m–1. The
electrical conductivity of semiconductors is due to the presence of impurities and defects. Their conductivity
increases with increase in temperature as the defects increase with the increase in temperature.

In metals the atomic orbitals from

molecular orbitals, which are so close in
energy to each other as to form a band. If
conduction band is not completely full or
it lies very close to a higher unoccupied
band, then electrons can flow easily under
an electric field thereby showing
conductivity.

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(vi) Magnetic properties: diamagnetic, paramagnetic, ferromagnetic, ferrimagnetic and antiferromagnetic.
Magnetic Properties of Solids: The magnetic properties of materials are a consequences of magnetic moments
associated
with individual electrons. The magnetic moment of an electron is due to its orbital motion and also due to its
spin around its own axis.

A moving electron may be considered to be a small current loop, generating a small magnetic field, which has a
magnetic moment along the axis and the magnetic moment due to electron spin is directed along the spin axis.

Materials can be classified depending on their response to external magnetic field.

Dimagnetic materials: (e.g., TiO2, NaCl, C6H6) are weakly repelled by external magnetic fields. This property
is shown only by those substances which contain fully-filled orbitals i.e., no unpaired electrons is present.

Paramagnetic materials: (e.g., O2, Cu2+, Fe3+) are attracted by a magnetic field but lose their magnetism in the
absence of the magnetic field. This property is shown by those substances whose atoms; ions or molecules
contain unpaired electrons.

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Ferromagnetic substances show permanent magnetism even when the magnetic field is removed. Ex: FeO and
CrO2
Fe, Co, Ni show ferromagnetism even at room temperature. CrO2 is used to make magnetic tapes for use in
cassette recorders.
The spontaneous alignment of magnetic moments due to unpaired electrons in the same direction gives rise to
ferromagnetism.

Anti-ferromagnetic substances: Anti-ferromagnetic substances are expected to possess paramagnetism or

ferromagnetism on the basis of unpaired electrons present in them but actually they possess zero net magnetic
moment.
This is because of the alignment of dipoles is in a compensatory way so as to give a net zero dipole moment,
then we get antiferromagnetic substances (MnO).

Ferrimagnetic substances: Ferrimagnetic substances are expected to possess large magnetism on the basis of
the number of unpaired electrons present in them, but actually have small net magnetic moment.
This is because the moments are aligned in parallel and anti-parallel directions in unequal numbers resulting in
a net dipole moment.
Example: Fe3O4, ferrites of formula M2+Fe2O4 where, M = Mg, Cu, Zn etc.

Piezoelectricity: When crystals are subjected to mechanical stress, electricity is produced due to displacement
of ions. The electricity thus produced is called piezoelectricity. But if an electric field is applied to these crystal
there will be atomic displacement causing mechanical strain. These crystals act as mechanical-electrical
transducers.
Uses: As pick-ups in record players.

Pyroelectricity: - On heating if the orderly arrangement of ions or atoms get displaced and produces
electricity, this property is called Pyroelectricity.

Short Answer Type Question

Q1. State the hybridization of Carbon in diamond and graphite. Ans. Sp3 and Sp2 respectively.
Q2. What are the coordination no. of Na +1 in NaCl and Cu in copper crystal? 6 and 12 respectively.
Q3. A metal crystallizes in a face centerd cubic structure. How many closest neighbours will an atom of the
metal have?
Ans. 12
Q4. What types of bonds are present between the particles in the crystals of NaCl, Cu, diamond and graphite?
Name of solid Type of bond present
NaCl Ionic bond
Cu Metallic bond
Diamond Covalent bond
Graphite Covalent bond
+
5. How many Na ions are present in a unit cell of NaCl crystal?
Ans. Four Na+ ions are present in a unit cell of NaCl crystal.

6. How many C – atoms are closest to any C- atom in each of the structures of diamond and graphite?
In diamond, each C – atom is attached to four other C – atoms by covalent bonds, while in graphite,
each C – atom is linked to three other C – atoms by covalent bonds.
7. How many spheres are required to form a FCC structure?
Twelve spheres are required to form a FCC structure.
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8. What are the coordination numbers of Na+ and Cl- ions in NaCl?
Na+ ions as well as Cl- ions have a coordination number of 6. Therefore, this structure has a 6:6 C.N.

9. How many atoms are present in a unit cell of Cu crystal?

FCC arrangement, therefore, it contains four Cu atoms per unit cell.

10. Why sodium chloride on heating with sodium vapours acquire yellow colour?
On heating sodium chloride with sodium vapours, the chloride ions diffuse to the surface of the crystal
and combine with sodium atoms which get ionized to the sodium ions by loosing electrons. These e-s get
trapped in anionic vacancies and act as F – centers which impart yellow colour to the crystal.

11. What are semiconductors? What is the effect of increasing temperature on the conductivity of
semiconductor?
It increases with increase in temperature.
Que: Fill in the blanks:
i) The crystal of diamond is made of ___ while that of sodium chloride is made of _____.
ii) In a crystal lattice, the number of nearest neighbours to each atom is called _____.
iii) Diamond and graphite are examples of _______ crystals.
iv) The unit cell of sodium chloride has _____ Na+ ions and _____ Cl- ions.
v) Crystals of _______ and ______ have fcc lattices.
vi) Each carbon atom in graphite is ____ hybridized.
vii) The crystal of diamond is made of ____.
Ans. i) atoms, ions ii) coordination number iii) atomic or covalent iv) four, four
2
v) NaCl / Cu, diamond vi) sp vii) atoms, ions

Que. Correct the following statements:

(i) Diamond is crystalline while graphite is amorphous.
(ii) Coordination number of bcc lattice structure is 12.
(iii) In the crystal lattice of copper, different copper atoms are bonded by covalent bonds.
(iv) Graphite has a two dimensional sheet like structure in which each carbon atom is sp3 hybridised.
(v) A tetrahedral void is formed by eight spheres.
Ans. (i) Diamond and graphite both are crystalline.
` (ii) Coordination number of bcc lattice structure is 8.
(iii) In the crystal lattice of copper, different copper atoms are bonded by metallic bonds.
(iv) Graphite has a two dimensional sheet like structure in which each carbon atom is sp2 hybridised.
(v) A tetrahedral void is formed by four spheres.

Que. Choose the correct answer for the following:

1. Potassium crystallises in bcc lattice, hence, the C.N. of K metal is
(a) 0 (b) 4 (c) 6 (d) 8
2. A substance AxBy crystallises in a fcc lattice in which atoms ‘A’ occupy each corner of the cube
and atoms ‘B’
occupy the centers of each face of the cube. Identify the correct composition of substance AxBy.
(a) AB3 (b) A4B3 (c) A3B (d) composition cannot be specified
3. The C.N. of hcp structure is
(a) 12 (b) 10 (c) 8 (d) 6
4. Cu has fcc structure. The coordination number of each ion is
(a) 12 (b) 4 (c) 8 (d) 14
5. A molecule contain atoms x and y so that x occurs at the corners of the cube while y at the face centre.
The formula of the molecule can be:
(a) xy3 (b) x1y (c) xy2 (d) x2y
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 6. In a face centered cubic lattice, atom (A) occupies the corner positions and atom (B) occupies the face
center positions. If one of atom (B) is missing from one of the face centered points, the formula of the
compound is:
(a) A2B5 (b) A2B3 (c) AB2 ((d) A2B

Que. Match the following:

(i) 74% space occupied (a) Body centered cubic lattice
(ii) CsCl (b) Diamond
(iii) HCP (c) Na2O
(iv) Covalent crystal (d) Face centered cubic lattice
(v) Antifluorite structure (e) ABAB…. type of close packing
Ans: (i) d (ii) a (iii) e (iv) b (v) c

LONG ANSWER QUESTIONS

Que. What is the number of closest neighbours of carbon atoms in diamond? How are these neighbours
oriented? What type of arrangement of atoms does the structure diamond belong to? How are the atoms
held together?
Ans. The number of closest neighbours of a carbon atom in diamond is four. These C atoms are oriented
towards the four corners of regular tetrahedron. Diamond has a fcc structure. The C atoms are held
together by covalent bonds.

Que. How are the sodium ions and chloride ions arranged in a crystal of sodium chloride? How many closest
neighbours of chloride ions does a sodium ion has? What is the kind of lattice arrangement of sodium
ions and chloride ions taken independently?
Ans. The sodium ions occupy the octahedral sites. They are present at the edge centre and body centre. This
arrangement of sodium ions is regarded as body centered arrangement.
The chloride ions are present at the corners and at the centre of each face of the cube. This arrangement
of chloride ions is regarded as fcc arrangement.
Each sodium ion is surrounded by six chloride ions.

Que. Why is graphite soft and why can it be used as a lubricant?

Ans. As the two adjacent layers in graphite are held together by weak Van der Wall’s force of attraction, they
can slide over one another. This is why graphite is soft and can it be used as a lubricant.

Que. For diamond, state the element present at the lattice sites, the number of nearest neighbours for each
atom and the type of unit cell. State the hybridization of the carbon atom in diamond.
Ans. In diamond, carbon atoms are present at the lattice sites. The no. of nearest neighbours (carbon) is four
and the type of unit cell is fcc. It has sp3 hybridisation.

Que. Describe the unit cell of NaCl stating the type of unit cell, nature of forces holding the particles together,
number of nearest neighbours around each sodium ion and geometry of sodium ions which are arranged
around a chloride ion.
Ans. The type of unit cell in NaCl is FCC. It is held together by strong electrostatic force of attraction. The
number of nearest neighbours around each sodium ion is six. The geometry of sodium ions which are
arranged around a chloride ion is octahedral.

Que. Compare crystals of copper and diamond and indicate one similarity and one difference.
Ans. Similarity: Both the crystals have very high melting points and are hard.
Difference: The copper crystal contains metallic bonds while diamond crystal contains covalent bonds.
Diamond is a nonconductor of electricity whereas copper is a good conductor of electricity.

Que. Account for the statement that graphite is anisotropic with respect to conduction of electricity.
Ans. In graphite, delocalized π – electrons are free to move within the layer, thus graphite conducts electricity
only in the plane of the layer and not in the direction perpendicular to its laminal layers. Hence, the
values of electrical conduction are different in different directions on graphite., therefore, its anisotropic
with respect to conduction of electricity.

Numerical
Que. Iron crystallises in a body centered cubic structure. Calculate the radius of Fe atom. Edge length of its
unit cell is 286 pm.

Que The radius of Na+ ion is 95 pm and that of Cl- ion is 181 pm. Predict whether the co - ordination number
of Na+ ion is 6 or 4.
Radius of Na+ = 95 pm
Radius of Cl- = 181 pm

The radius ratio lies between 0.414 – 0.732. Hence, Na+ ion prefers to occupy octahedral holes having
the coordination nuber 6.
Que. The compound CuCl has ZnS (cubic ) structure. It density is 3.4 g/cm3. What is the length of the edge of
the unit cell?
ZnS has fcc structure.
Molecular mass of CuCl = 63.5 + 35.5 = 99 g/mol
Ans: 578.2 pm
Que. The density of chromium metal is 7.2 g/cm3. If the unit cell is cubic with edge length of 289 pm,
determine the type of unit cell. (At weight of Cr = 52, NA = 6.023 × 1023)
Z = 2.01. Since the unit cell contains 2 atoms, it is body centered cubic.

Que. An element has a bcc structure with a cell edge length of 288 pm. The density is 7.2 g/ cm3. How many
atoms are present in 208 g of the element?
a = 288 pm = 288 X 10 -10 cm
Z = 2.01
Since the unit cell contains 2 atoms, it is body centered cubic.

Volume of unit cell = a3 = 2.39 × 10-23 cm3

Mass of element = 208 g
Density of element = 7.2 g/ cm3
Volume of 208 g of element = mass/ density = 28.89 cm3
No. of unit cells in this volume = Volume of element / Volume of unit cell = 12.08 × 1023 unit cells.
Z=2
Therefore, total number of atoms in 208 g of the element = 2 × 12.08 × 1023 = 2.416 × 1024 atoms.
Que. Cu has fcc arrangement. Its mass is 63.55 g mol -1. Its density is 8.925g/cm3. Calculate the atomic radius
of copper.
Ans: Cu has fcc arrangement. Therefore, Z = 4. M = 63.55 g mol -1

a = 3.616 × 10-8 cm = 361.6 pm r = 2 /4 x 361.6 = 127.8 pm

Que. In a cubic closed packed structure of mixed oxides, the lattice is made up of oxides of ions, one eighth of
tetrahedral voids are occupied by divalent ions (A+2) while one half of octahedral voids are occupied by
trivalent ions (B+3). What is the formula of the oxide?
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 In a closed pack structure, there is one octahedral and two tetrahedral voids corresponding to each atom
constituting the lattice.
Therefore,
Number of oxide ions (O-2) per unit cell = 1
Number of tetrahedral voids per oxide ion in the lattice = 1 × 2 = 2
Number of divalent ions (A+2) = 1/8 × 2 = ¼
Number of octahedral voids per oxide ion in the lattice = 1 × 1 = 1
Number of trivalent ions (B+3) = 1 × ½ = ½
Formula of compound = A1/4 B1/2O i.e. AB2O4.
12. Lead (II) sulphide has fcc crystal structure. The edge length of the unit cell of PbS crystal is 500 pm.
What is its density? (At wt. of Pb = 207, S = 32) (Ans. 12.697 g cm-3)

13. A compound has a cubic structure and molecular mass 99. Its density is 3.4 g cm-3. What is the edge of
the unit cell?
Solution: ccp = fcc, Z = 4, M = 99, d= 3.4 g cm-3 a=?
d = Z X M/ a3 x NA
a = 5.782 X 10-8 cm = 578.2 pm
Que. Mo forms bcc crystals and at 200C, the density is 10.3 g cm-3. Calculate the distance between the centers
of the nearest Mo atoms. (At mass of Mo = 95.94)
Ans. The distance between the nearest atoms, d = 2r = 2 × √3a/4 = √3a/2
For bcc a = 3.14 × 10-8 cm = 3.14 A0
d = √3a/2 = 2.72A0
Que. CsCl has arrangement and its unit cell edge length is 400 pm. Calculate the inter - ionic distance in
CsCl. Ans: Interionic distance = √3/2 a = 346.4 pm
Que. Niobium crystallizes in body centered cubic structure. If density is 8.55 gm cm-3, Calculate atomic
radius of Niobium. (atomic mass = 93 gm mol-1) Ans.a = 330.56 pm r = √3/4 × 330.56 = 143 pm

Que. A compound AB has a cubic structure and molecular mass 99. Its density is 3.4 g cm-3. What is the
length of the edge of the unit cell? Ans. a = 578.29 pm
Remember: Cubic structure means fcc or ccp and hence in that case Z = 4.

Que. Sodium chloride crystallizes in FCC. Its density is 2.165 g cm-3. If the distance between Na+ and its
nearest Cl- is 281 pm, find out the Avogadro’s number. (6.09 × 1023 /mol)
Ans. Hint: a= 2 × inter ionic distance

Que. An element ‘A’ crystallises in fcc structure. 200 g of this element has 4.12 × 1024 atoms. The density of
A is 7.2 g cm-3. Calculate the edge length of the unit cell. (299.9 pm)
Ans. Let edge length = a, Therefore Volume = a3 Mass of each atom = 200/4.12 × 1024
No of atoms per unit cell = 4 Mass of unit cell = 4 × Mass of each atom = 194.16 × 10-24 cm3
Now Density = Mass / volume

Que. FeO has a cubic structure and each edge of the unit cell is 50A. Assuming density of the oxide is 4
gm/cm3, what will be the number of Fe+2 and O-2 ions in each unit cell?
Ans. Find Z, Z =4 the number of formula units of FeO atom per mole is 4 or 4 Fe+2 or 4O-2 ions per unit cell.

Que. Aluminium crystallises in a cubic closed packed structure. Its metallic radius is 125 pm. Find the length
of the unit cell and how many unit cells are there in 1 cm3 of aluminium?
Ans. For a FCC structure 4r = a √2 therefore a = 353.55 pm
Volume of one-unit cell = a = 4.42 ×10 cm3
3 -23

No. of unit cells = Volume of element/ Volume of unit cell

No. of unit cells in 1 cm3 = 1/ 4.42 ×10-23 = 2.262 × 1022
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