12 Chemistry Ch-1 The Solid State

Chapter - 1

The Solid State

1. Classification of solids on the basis of arrangement of atoms in the lattice →

It can be of two types:-

A. Amorphous

B. Crystalline

Crystalline Solids Amorphous Solids

1. Definite and regular arrangement of Irregular or random arrangement of the constituent

constituent particles. particles.

2. They have definite and regular shape. They have irregular shape.

3. Sharp (at a particular sudden melting They melt over a certain range of temperature.
point).
4. Undergo clean cleavage(regular).[cut Undergo irregular cleavage. Cut in to piece with
is regular] irregular surface.

5. They are true solids. They are super cooled liquids or cooled liquids or
pseudo-solids.

6. Have a definite heat of fusion.(solid Indefinite heat of fusion.

liquids)
7. They are anisotropic in nature. They are isotropic in nature.
i.e. the properties like electrical
conductivity, the molar conductivity (Same prop due to random arrangement
refractive index are different in i.e. Show similar properties in diff. direction.
different direction because of their
regular arrangement Ex→ glass, rubber polymer etc.
Ex→ ZnS (Zn blend) NaCl, LiCl.

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2. Classification based on the nature of force binding the constituent particles ->

A. Ionic

B. Covalent

C. Molecular

D. Metallic

• Ionic Solids: -

1) Constituent particle are ions

2) They have 3-D arrangement of cations and anions.

3) Strong electrostatic forces of attraction.

4) High melting and boiling points due to strong forces binding then.

5) They are insulators in solid state but good conductors in molten or aqueous
state.(dissociation)

6) They have high enthalpies of fusion.(NaCl, ZnS, CaF 2 ,Na 2 O)

• Covalent Solids (Network solids)

1) Constituent particle are covalently bonded molecules (atoms)

2) High melting point, comparatively lower than ionic solids.

3) They are insulators, except-graphite (one e- is left, sp2-hyb.)

4) High enthalpy of fusion.

5) They are hard because of 3-D Network, ex-Diamond, Graphite.

• Molecular Solids

They are of three types

1) Non polar

2) Polar

3) Hydrogen

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Their properties are as follows:

1) Constituent particles are molecule.

2) Further categorized into non-polar, polar and H- bonded molecular solids

 Non-Polar:-
1) Comprise of atoms or molecules formed by non-polar covalent bond. Ex-CCl 4 , CO 2

2) They have weak dispersion forces (Vanderwaal/London force)

3) They are soft & non-conductors of electricity.

4) Exist as gases or liquids at room temperature.

 Polar molecular Solids:-

1) Formed by polar- covalent bonds.

𝑪𝒍𝟐 𝑵𝑯𝟑

Difference in Difference in
electronegativity elecronegativity value

Non-Polar Polar

2) Dipole -Dipole interactions. (Due to electronegative charge separation → charged

separations) [Nature of Force]
3) They are soft & non- conductors of electricity.

4) They are gases or liquids at room temp. Ex.-HCl, NH 3 , SO 2

 H-Bonded Molecular Solids;-

1) Contain Polar-Covalent molecular having elements F,O, N and Hydrogen.(free)

2) Non-conductors of electricity.

3) Generally exist as volatile liquids or soft solids. Ex. -ice.

• Metallic Solids:-

1) Contain positive kernels hold by a sea of free electrons.

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12 Chemistry Ch-1 The Solid State

2) Malleable & ductile

3) Good conductors of electricity.

4) Can conduct electricity in all states (As here free electrons are present) Ex.-All metals,
Cu, Fe, Ag, Al.

CRYSTAL LATTICE: -
A regular 3-D Repetitive arrangement of the constituent particles in which, each particle is
represented as a point also known as (lattice point/lattice site) is known as a crystal lattice/
Space Lattice.

Small- unit of lattice-Unit Cell

UNIT CELL:-

The smallest but complete unit in the space lattice which when repeated over & over again
in 3-Ds, generates the crystal of a given substance.

 Types of Unit Cell:-

1) Simple cubic/Primitive unit Cell.

8 Lattice points

Each particle shares (1/8) of space

1/8× (8 shaving) =1. (Rank of Unit Cell)×

‘1’ is the no. of atoms contributing the simple cubic.

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2) Body centered cubic unit cell (BCC)

Corners are shared by 1/8×8=1

And 1 in the center.

1+1=2 (Body Centre)

Z=2

Z= Rank (no. of atoms cont. a particular cell)

3) Face-Centred Cubic arrangement. (FCC)

1/8×8=1

1/2×6=3(face center)

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4) End Centered: -

1/8×8=1(we take any 2 faces)

1/2×2=1

So 1/2×2

Z=2

Q.1 Calculate the no. of atoms, in a cubic based unit cell having 1atom on each corner and 2
atoms of on each body diagonal.

Ans. Body diagonal =4

1/8×8=1

Q.2 A Unit Cell consists of a cube in which there are A’ atoms in the corner & ‘B’ atoms at
the face-centre. What would be its formula?

Ans. 1/8×8(A) =1’A’

1/2×6 (B) =3

2 ‘A’ atoms are missing from 2 corner of the unit cell

1/8×6 (A)

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A3/4, B 3

1/2×6 (B) = 3

3/4 AB 4

Q.3 If 3 elements P,Q,& R Crystalline in a unit cell with ‘P’-comes, ‘Q’-Body center &R’ atom
at the phase center.

Ans. P→1/8×8=1

Q→1

R→1/2×6=3

PQR3.

CLOSED PACKING IN 2 DIMESION:-

1. Here, each sphere is below the other

Coordination no. 4
Such alt.
(no. of atoms sphere
arrang.
touching a sphere)

C=4

(Square Close Packaging)

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2. Here the spheres are below the void.

C. N. = 6

Hexagonal Close Packing

CLOSE PACKING IN3-DIMENSION: -

One layer is A another B is placed over it. Over the voids of small layer B, newly developed
voids are ‘C’, old were ‘a’ & ‘b’, 2 options-3rd layer, so layer will become ABABAB. This is
called Hexagonal-Close Packing.

If ‘C’ is placed on voids of ‘A ‘then it will form ABCABC-cubical close packing.

A
𝒂 𝒂 𝒂𝒂
b 𝒃 → 𝑡𝑒𝑡𝑟𝑎 ℎ𝑒𝑑𝑟𝑑
CC B 𝒄 → Octahedral

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Types of Voids:-
Depending upon arrangement of spheres & voids, there are 2 types of voids. Voids are due
to sphere arrangement,

1. Tetrahedral void

2. Octahedral void

Tetrahedral: -

It is triangular, but when another sphere is placed to make it tetrahedral.

Tetrahedral

Tetrahedral Void

Octahedral: -

Equilateral ∆, opposite to each other. The no. of octahedral voids is equal to the no. of
atoms per unit cell,

Where as the no. of tetrahedral voids is twice the no. of atoms of present in a unit cell.

Octahedral Void

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Octahedral Void

PACKING EFFICIENCY:-
Closeness between spheres in lattice.

 The % of the total space which is occupied by particles in a certain packing is said to be
packing efficiency.

1. Simple Cubic:-

The distance between the centre of the spheres present on the corner of the edges of
the cube is called edge length. (a).

Edge
𝒂
length

 Distance between the center of the 2 nearest sphere is called the nearest neighbor distance
‘d’ & is equal to r + r = 2r, where r= radius of the sphere.

𝑟 𝒓

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% free volume =Volume of sphere/volume of cube× 100

Edge length = a=2r=d (here)

Volume of cube = 𝑎3 =(2𝑟)3 =8 𝑟 3

4
Volume of sphere = 3 𝜋𝑟 3 /8𝑟 3 × 100

4
3
π÷8

4
3
× 1/8 =π/6×100

1/6× 3.14 × 100

52.00

=52.4%

2. FCC: -

D 𝒂 C
𝒂

A B

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In Δ ABC
C
2
𝐴𝐶 = 𝐴𝐵 + 𝐵𝐶2 2 𝑟
𝑟
=𝑎2 +𝑎2 𝑟
𝑎
(4𝑟)2 = 2 𝑎2 𝑟

A 𝑎 B
A=2r √2
𝑎
R= 2 √2

3. BCC: -

A 𝒂 B
D
𝑟

𝑟
C

A 𝑟

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In Δ 𝐵𝐶𝐷

B𝐷2 = B𝐶 2 + 𝐷𝐶 2

𝐵𝐶 2 = 𝐴𝐵 2 +𝐴𝐶 2

𝐵𝐷2 = 𝐴𝐵 2 + 𝐴𝐶 2 + 𝐷𝐶 2

(4𝑟)2 = 𝑎2 + 𝑎2 + 𝑎2

16𝑟 2 = 3𝑎2
16 2
𝑎2 = 3
𝑟

A=�16/3𝑟 2

A=4r/√3

Packing efficiency= 2×4/3𝜋𝑟 3 ÷ (4𝑟)3× 100

=2×4/3 π𝑟 3 ÷64

=68%

Calculation of Density of unit cell:-

Density of unit cell= Mass of unit cell/Volume of unit cell

Volume of unit cell= (a×10−10 )3

Let the edge length be ‘a’ pm.

Edge of (length) ‘a’ pm= a×10−10cm

Mass of unit cell =Rank of crystal * Mass of one atom

Rank of crystal atoms

Present in a particular unit cell

𝑀
Mass = 𝑍 × 𝑁
0

6.023 × 1023 → 𝑀

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𝑀
1→𝑁
0 (𝑎𝑢𝑜𝑔𝑎𝑑𝑟𝑜 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)

𝑍 ×𝑀
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝑒) = 𝑎3 ×10−30 ∙𝑁
0

Approx

Z = 1 2 4

Simple cubic BCC FCC

• Question on finding N0 Can be asked it should always be calculated.

Q. An element crystallizes in a FCC unit cell with edge length of 200pm.Cal.its density if
400g of this element contains 48× 1023 atoms.

Ans. 400g→ 48× 10^23 atoms

1 mole= 6.022× 1023 atoms

400
1 atom=48×1023

=50→ at. Mass

Q. A metal of atomic mass 50 has BCC structure density= 5.96g/cc. Calculate the volume

50×2
Ans. 5.96 =
𝑣×6.023×1023
100
5.96× 6.023 × 1023 =
𝑣
100
31.04× 1023 =
𝑣
100
V= × 1023
31.04

= 3.1× 10 −23

Imperfection/Defects in solids:-
Ideal crystal →a crystal is said to be ideal if the entropy of its constituents at absolute zero
temperature is 0.

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Any disordered arrangement or dislocation of the constituent particles from these normal
positions gives rise to certain defects or imperfections in solids.

There are of 2 types:-

1. Electronic imperfection

2. Atomic imperfection (point defects).

Electronic defects:-
These defects arise due to irregularity in the arrangement of e-s, as the e-s are free to move
in the crystal lattice, and are responsible for electrical conductivity.

The points from where they move become e- deficient and are called “holes”

Electrical conductivity also arises due to movement of these hole from one place to
another.

Si (4 e-s in valance shell)

(Tetrahedral)

Addition of impurities to said either of group 13 or group 14 or group 15.

When group 13 is impurities, 1 space is left as group 14 is tetrahedral. This is a hole. It is p-

type semi-conductor.

If group 15 (1 free 𝑒 − );-pentagonal e- conductivity =n-type of semi- conductor.

P-type semi-conductor
(𝐼𝑛. 𝐺𝑎, 𝑇𝑙)
Doping
𝑺𝒊

N-type semi-conductor
(𝑃, 𝐴𝑟, 𝑆𝑏)

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Atomic defects:-
Ions dislocate, occupy some other place. [Arises due to dislocation of the ions from their
original site]

Atomic Defects

STOICHIIOMETRIC NON-STOICHIOMETRIC
DEFECTS DEFECTS
IMPURITY DEFECTS
(Arise in crystals in (No. of cations is not
which no. of cat ions & equal to no. of anions)
no. of anions)

STOICHIOMETRIC DEFECTS

Vacancy defects

Interstitial defects

Schottkey defects

Frenkel defects

• Vacancy defects (as a result of heating)

When some lattice site in the crystalline solids are vacant in gives rise to vacancy defects.
ex..-

Vacancy

This defects is arises as a result of heating & it lowers the density of the crystal.

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• Interstitial defects:-
Density ↑

Constituent in
interstitial sites

When some constituent particle in a solid occupy interstitial sites, then this defects is
created and it increases the density of the crystal.

• Schottkey Defects:-

Equal no. of cations & anions are missing

𝑨+ 𝑨+ 𝑩−

𝑩− 𝑨+ 𝑨+ move to
𝑩− 𝑨+
defiant

𝑩− 𝑨+ 𝑩−

More specifically → Vacancy defects

When Equal no. of cations and anions are missing from the lattice then this defect is
created which result in formation of vacancies or holes, these by lowering the density of the
crystal.

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The lattice crystal or the solid remains electrically neutral due to equal no. of positive or
negative charges.

Condition for Schottkey defects:-

 This defect is shown by the ionic compounds with high coordination numbers.

 In which the cations & anions are of same size.

Example - Alkali metal halides such as-NaCl, KCl, KB 4 etc.

CONSEQUENCES:-

 The density of crystal is lowered.

 Due to presence of holes.

 Migration: - this defect increases the electrical conductivity due to movement of ions &
holes from one place to another.
 Due to presence of holes, stability is less.

 Lattice energy is low ( as energy required to break bonds in ions and hole is lower)

• FRENKEL DEFECTS: -

(Types- Interstitial)

𝑨+ 𝑨+ 𝑩−

𝑩− 𝑨+ 𝑨+ move to
𝑩− 𝑨+
defiant

𝑩− 𝑨+ 𝑩−

 Cation leaves its initial site but not lattice.

Only for cation →

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Size of cation < size of anion shown where cation is smaller than anions.(all cations are
of same size)

 It results when certain cations leave their normal sites and due to which holes are
created in the crystal.

 CONDITION FAVOURING FRENKEL DEFECTS: -

1. It is found in ionic compounds with low coordination no.

2. In which the size of cat ions < size of anions

Example - Silver halides like AgCl, AgBr, AgI where size of Ag+ ion is very less then
halides ion.

Consequences: -

1. The electrical conductivity of the crystal increase.

2. The stability of the crystal decrease.

3. Density remains unaltered since no. of ions/volume is same.

This defect is also known as “Dislocation Defect.”

NON- STOICHIOMETRIC CRYSTAL:-

Points defects in non- stoichiometric crystal.

Metal Excess Defect Metal Deficiency Defect

(+𝒗𝒆 > −𝑣𝑒) (+𝒗𝒆 < −𝑣𝑒)

 Metal Excess Defects: -

1) By anion-vacancies

2) By extra- Cation occupying the interstitial site.

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• By Anion Vacancies: -

𝑨+ 𝐵− 𝑨+ 𝑩−

𝑩− 𝑨+ 𝑩− 𝑨+

𝐴+ 𝒆− 𝑨+ 𝑩−

𝒆− trapped in anion
vacancy (F-centre)
F → 𝑭𝒂𝒓 𝒃𝒆 → 𝒄𝒐𝒍𝒐𝒖𝒓

−𝑒 𝑒 Absorb energy
𝑁𝑎 (𝑔) �� 𝑁𝑎+
Release after
led chip a level
𝑁𝑎 𝐶𝑙 impacts colour
𝐶𝑙 − to crystal.

Here no. of metal ions > no. of halides ions (-ve)

This defect arises when anion is missing from its original site creating an anion vacancy
in which an e-is trapped and is referred to as F-centre.

Example - In NaCl when its crystal is heated in the atm. Of Na vapours, the Na atoms get
deposited on the surface and ionize to from Na+ ion.

The 𝐶𝑙 − ion leaves it original site and combines with Na+ ions and the e- lost by sodium
atoms accommodate in the anion vacancies maintaining the electrical neutrality of the
crystal.

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Consequences:-

1) It imparts color to the crystal.

2) It is paramagnetic due to presence crystal of unpaired electrons.

3) The crystal is able to conduct electricity. (Vibration→stable→imparts colour)

Q. Discuss why the vapors of Li will be imparts pink color to LiCl crystal white K vapors will
impart violet colour to the crystal (KCl).

Ans. =Due to F-Center. (diff.)

When they ionize.

e- lost→ trapped.

= specific color imparted.

• By Extra cations Occurrence: -

𝑨+ 𝐵− 𝑨+ 𝑩−

𝑨+ Extra cation
occupying
𝑩− 𝑨+ 𝑩− 𝑨+
interstitial site

𝒆−
𝐴+ 𝑩− 𝑨+ 𝑩−

𝒆− trapped in interstitial
site

Q. Zn oxide crystal exhibit yellow colour on standing?

1
=𝑍𝑛𝑂 → 𝑍𝑛+2 + 2 𝑂2 + 2𝑒 −

(Electrical neutrality remains)

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Consequences of Metal Excess DEFECTS: -

(For extra cation occurrence)

1. They are generally coloured.

2. Paramagnetic in nature

3. They are conducting due to presence of free e-s.

 Metal Deficiency Defects:-

Created by:-

1. Cation vacancy

2. Extra anion occupying interstitial site

• Cation Vacancy:-
𝑨+ 𝐵− 𝑨+ 𝑩−

𝑩− 𝑩− 𝑨+

Cation acquiring 𝐴2+ 𝑩− 𝑨+ 𝑩−

extra +𝑣𝑒 charge

Shown by elements -

→Variable oxidization state

→due to 1 vacant “I” cation (metal ion) will increaseoxidized state.

• This defect is generally shown by transition metals which have a tendency to show
variable oxidation state.

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For Example - In FeS or iron pyride crystal some 𝐹𝑒 +2 ions may be missing from the
lattice & there the change is balanced by extra +ve charge on neighbouring ions. Ions
acquire +3 oxidation state.

• Extra anion occupying interstitial site:-

𝑨+ 𝐵− 𝑨+ 𝑩−
Anion in interstitial
𝐵−
site
𝑩− 𝑨+ 𝑩− 𝑨+

𝐴+2 𝒆− 𝑨+ 𝑩−

Cation acquiring extra the An extra – 𝒗𝒆 so to

charge compare extra +𝒗𝒆

Consequences of Metal Deficient:-

1. They conduct electricity.(Present of hole)

2. The density increases. in( b),but in (a) it ↓) Density of the crystal change.

IMPURITY DEFECT

In Co-valent solids

(Group 14 doped with group

13 → hole conduction (So p- In Ionic solids
type group 14, group 15)
(extra 𝒆− )

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• In Co-valent solids: - 1) p- Type

2) n-Type

The introduction of defects in a particular crystalline solid by addition of impurities of other

elements is termed as “Doping” and result (gp.13,15) in the formation of 2 types of semi-
Conductors.

P-Type & n- Type.

Such type of semi – Conductor are called extrinsic semi conductor.

• In ionic solids: -

The electrical conductivity of ionic solids can be increased by adding impurities of other
metal ions. For Example ⇒

If we mix a small amount of molten 𝑆𝑟𝐶𝑙2 (strontium chloride) to the crystal of Nacl then some Na+
ions will leave the crystal and are the replaced by 𝑆𝑟 +2 ions.

𝑵𝒂+ 𝐶𝑙 − 𝑵𝒂+ 𝑪𝒍−

𝑪𝒍− 𝑪𝒍− 𝑵𝒂+

Hole (covalent
𝑪𝒍. 𝑪)
𝑆𝑟 +2 𝑪𝒍− 𝑵𝒂+ 𝑪𝒍−

So electrical neutrality is maintained as 𝑆𝑟 +2 16 compensates loss of cation

For the two Na+ ions one𝑆𝑟 +2 is replaced.

Impurities of 𝑆𝑟𝐶𝑙2 is doped.

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B0NDS THEORY FOR METALS

Bands

Valence Conductance

Gap (forbidden zone/ energy)

(In metals)

For: -

→ Conductors

→ Semi – Conductors

→ Insulators

Conduction band

No energy
difference

Valence band (outer most

energy shell exited state)

CONDUCTORS

No energy difference

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C. B.

Forbidden Zone

V. B.
Semi-conductors

C. B.

V. B.
For insulators

No conduction in insulators due to high energy difference

Exited ⟶ do not ablate move

OVERLAP: -

C. B.

Overlap

V. B.

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PROPERTIES OF SOLIDS

Electrical Properties MISSING

(Solids – conductors,
semi-conductors,
insulators)

Electrical Properties: -

In terms of capacity to conduct electricity, solids are of three types:-

1. Conductors

2. Semi-conductors

3. Insulators

→Conduction of electricity in Semi- Conductors:-

SEMI CONDUCTORS

Intrinsic Extrinsic

𝑆𝑖 (P-type & n-type imp.

cond.)

𝑆𝑖 𝑆𝑖 𝑆𝑖 (Doping)

𝑆𝑖

When heated they

become free & conduct
electricity.

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Intrinsic Semi Conductors:-

A semi- conductor when heated to a high temp. acts as intrinsic- semi- conductor. This
happens because certain co-valent bonds are broken due to energy supplied & the e-s are
set free to conduct electricity.

Same For Extrinsic

• Magnetic prop. Of Solids: -

Magnetic properties of the substance because of magnetic moments associated with the e-s
present in third atoms.

The magnetic moment in a e- is from 2 source

1. Orbital motion around the nucleus

2. Spin of the e- around its axis

→ On the basis of the influence of the external magnetic field solids are classified as under:-

1) Paramagnetic Substance:-

⇒ Attracted towards electrical field .

Substance which are attracted by the magnetic fields are said to be paramagnetic in
nature and the atoms of the element present have certain unpaired e-s , but these
substance lose their magnetic character, once the magnetic field is removed i.e, their
magnetic character is temporary. Magnetic moment ≠0.

Example: - Co, Ni, Fe, No (Nitric oxide) n≠0

2) Diamagnetic Substance:-

Those substances which have all paired e-s and are repelled under the influence of
magnetic field.

The resultant magnetic moment aligned in opposite direction cancel each other on
account of pairing.

Example: - 𝑇𝑖𝑂2 , 𝑁2 ,Nacl,etc.

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3) Ferromagnetic Substance:-

Certain paramagnetic substance generally transition elements like Co, Ni, Fe. Become
paramagnetic under the influence of magnetic field i.e they do not lose their magnetic
character even if, they are not in contact with magnet. They have magnetic moment
aligned in the same direction.

Ex. 𝐶𝑟𝑂2 used in magnetic tapes for audio recording.

e- rotate around axis & revolve.

All ferromagnetic→ paramagnetic but not vice versa

↑↑↑↑↑↑↑

4) Anti- Ferromagnetic Substance:-

Certain paramagnetic substances align the magnetic moment in such a way that they
mutually cancel out each other and thus posses ‘O’ magnetic moment.

µ=0

↑↓↑↓↑↓↑↓↑↓↑↓

Opp.dir. equal no.

5) Ferri magnetic Substance:-

Certain paramagnetic substances have the magnetic moment aligned in parallel and anti
parallel direction in unequal numbers. So that they have net magnetic moment but ferri
magnetic Substance are less magnetic than ferromagnetic Substance.

↑↑↓↓↓↑↓↓↓↓↑↑

𝑢 ≠0 Magnetic

Ex..Magnetic oxide of Fe 𝐹𝑒3 𝑂4

Ferri-Ferro oxide → (𝐹𝑒𝑂. 𝐹𝑒2 𝑂3)

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• Dielectric properties of Solids: - Depending upon the alignment of electric dipole the solids
have following character.
1. Piezo Electricity:-

A di- electric crystal which has resultant dipole movement and can product electricity
when external pressure is applied such as crystal is called piezo electric crystal and the
prop. is termed as piero electricity.

Such crystal are used in ultrasonic generators and solar detectors. Ex….

 Lead Zirconate (𝑃𝑏𝑍𝑟𝑂2)

 Ammonium, di- hydrogen phosphate (𝑁𝐻4 𝐻2 𝑃𝑂4 )

2. Pyro electricity (heat pyro): -

Certain crystals on heating produce electric current this phenomena is called pyro electricity.

3. Ferro Electricity (Sam to ferromagnetic substance): -

In such crystals dipole are permanently polarized even in the absence of electric field.

Example: - (Sodium Potassium Tatarate (Rochelle’s Salt))

2, 3 di-hydroxy

COOH

H C OH

H C OH

COOH

Sodium salt

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12 Chemistry Ch-1 The Solid State

COONa (Rochelle’s alt)

H C — OH

H C OH

𝐶𝑂𝑂𝑁𝑎

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