ENGG.

CHEMISTRY UNIT -1 (SOLVED QUESTION BANK)

Short Question Answers

Q1. Why helium molecule does not exist in nature OR Why helium does not exist in diatomic form but hydrogen exists as H2?
OR On the basis of MOT explain why hydrogen forms diatomic molecule but helium remains monoatomic? (2014-15)
Ans. Helium molecule does not exist in nature.
H 2 →  1S 2 B.O = (N b − N a ) = (2 − 0) = 1
1 1
2 2
He2 =  1S  1S B.O = ( N b − N a ) = (2 − 2 ) = 0
2  2 1 1
2 2
As the bond order of He2 is zero, the molecule (diatomic) cannot be formed and it remains monoatomic. B.O of H 2 is 1, so it is a
stable molecule.

Q2. Define bond order. What is its significance?

Ans. B.O. – Bond order is equal to one half of the difference between the number of electrons in bonding M.O & the no. of e- is
antibonding M.O.

B.O. =1/2 (Nb-Na)

Nb = electrons is B.M.O.
Na = electrons is anti B.M.O.
1
B.O.  Stability  Bond Energy  Bond Dissociati on Energy
B.L.

Significance of bond order:

• Negative or Zero B.O.: Molecule is unstable does not exist.
• Positive value of B.O.: Molecule exists & is stable.
• Bond order of +1, +2, +3 indicates the molecule has single, double or triple bond respectively.
1
• B.O.  Bond Energy  Bond angle  Stability 
B.L.
Q3.Define nanomaterials. Give the approaches to synthesize nanomaterials. (2018-19)
Ans. Nanomaterials: Materials having at-least one of its dimensions in the nanometre scale (1 nm= 10-9 m).
Nanomaterials synthesis approach:
1. Top down approach: Breaking of bulk material
2. Bottom up approach: Buildup of material: Atom→molecule→cluster

Q4. Give five applications of nanomaterials. OR Write two applications of nanotechnology. OR Give applications of
nanomaterials in electronics and medicines. (2018-19, 2017-18)
Ans. Applications of nanomaterials:
In major view nanomaterials has found their applications in many major areas:
• Electronics: Used to prepare nano chips.
• Medicine: Used for centralized drug delivery.
• Engineering and technology
• Industries
• Environment
• Sensors
• Catalysis

Q5. Why graphite is used as a lubricant? (2018-19)

Ans. Because it is soft and slippery. Its layers can slide over one another due to presence of weak vanderwaals forces between
them.

Q6. Arrange following in order of their increasing bond length: N 2 , N 2− and N 2−2
(2018-19)
Ans. B.O. of N 2 = 1 (N b − N a ) = 1 (10 − 4) = 3
2 2
B.O. of N 2 = (N b − N a ) = (10 − 5) = 2.5
− 1 1
2 2
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B.O. of N 2− 2 =
1
(Nb − N a ) = 1 (10 − 6) = 2
2 2

1
Bond order 
Bond Length

So, acc. to increasing bond length: N 2  N 2−N 2−2

Q7. Calculate the bond order of N2+. (2017-18)

Ans. B.O. of N2 +
 1S 2   1S 2   2S 2    2S 2   2 p 2 x  n2 p 2 y =  2 p 1 x
B.O. =
1
(N b − N a ) = 1 2 (9 − 4) = 1 2  5 = 2.5
2

Q8. Graphite is a good conductor of electricity. Why? (2017-18)

Ans. Because in graphite all the carbon atoms are sp2 hybridised and each carbon has one free electron to conduct the
electricity.

Q9. Arrange the following in the increasing order of their bond energy O 2, O22+, O22-. (2017-18)
Ans. B.O. of O2 B.O. = 1 ( N − N ) = 1 (10 − 6) = 1  4 = 2
2
b a 2 2
B.O. of O22+ = ½(Nb-Na) = ½(10-4) = 3
B.O. of O2-2 = ½(Nb-Na) = ½(8-6) = 1

Since, B.O. α Bond energy. So, the order will be = O22+˃ O2 ˃ O2-2

Q10. Calculate the bond order of N2 (2016-17)

Ans. N2 (14 electrons):  1S 2   1S 2   2S 2    2S 2  n2 p 2 y =  2 p 2 x   2 p 2 z

B.O. of N 2 =
1
(N b − N a ) = 1 (10 − 4) = 3
2 2

Q11. Define the term pitch. (2016-17)

Ans. Pitch: Pitch is the property of Cholesteric liquid crystals. It is defined as distance travelled by the director when it gets
turned by 3600. It is affected+ by temperature, pressure and electric & magnetic fields. It is inversely proportional to the
temperature.

Q12. Explain why bond energy of N2 is greater than that of O2. (2015-16)

Ans. B.O. of O2 = B.O. = 1 ( N b − N a ) = 1 (10 − 6) = 1  4 = 2

2 2 2

B.O. of N 2 =
1
(N b − N a ) = 1 (10 − 4) = 3
2 2
Since, B.O. α Bond energy.

So, Bond energy of N2 ˃ O2

Q13. What are micelles? Give two examples of micellar systems. (2012-13)
Ans. Micelles formation is done by substances like soaps and detergents when dissolved in water. The Molecules of such
substances contain a hydrophobic and a hydrophilic part. When present in water, these substances arrange themselves in

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spherical structure in such a manner that their hydrophobic parts are present towards the centre, while the hydrophilic parts are
pointing towards outside. This is known as micelles formation. E.g. Soap and detergent forms micelles.

Q14. F2 is diamagnetic while O2 is paramagnetic. Why?

Ans. MO electronic configuration of F2 (18e-)
 1S 2   1S 2   2S 2    2S 2   2 p 2 z   2 p 2 x =  2 p 2 y    2 p 2 x =   2 p 2 y
All the electrons in molecular orbitals are paired so, it is diamagnetic.
MO electronic configuration of O2 (16e-)
 1S 2   1S 2   2S 2    2S 2   2 p 2   2 px 2 =  2 p 2 y    2 px1 =   2 p y1
z

There are two unpaired elections in *2px & *2py; So, O2 is paramagnetic

Q15.Which of the following is not an allotrope of carbon: Graphite, Diamond, Fullerene, Bakelite. (2009-10)
Ans. Bakelite.

Q16. Which of the following is diamagnetic in nature: H2+, H2-, H2? (2009-10)
Ans. H 2 →  1S 2
H2+ = σ1S1
H2- = σ1S2    1S 1
Only H2 is diamagnetic as only it contains all paired electrons.

Q17. Differentiate between bonding and antibonding molecular orbitals. (2013-14, 2009-10)
Ans.
BONDING MOLECULAR ORBITALS ANTIBONDING MOLECULAR ORBITALS
1. They are formed by additive overlapping of atomic orbitals. They are formed by subtractive overlapping of atomic
orbitals.
2. b = A + B a = A - B
3. Leads to the stability of molecule. Leads to instability of molecule

4. They have low energy and high stability. They have high energy and low stability.
5. They are shown as σ , π etc. They are shown as σ*, π* etc.
6. Maximum electrons are located in between the two nuclei. Electrons are scattered.

Q18. Graphite is an allotrope of carbon. (2009-10)

Q19. What is meant by LCAO? Explain

Ans. LCAO- Linear Combination of Atomic Orbitals. It says that atomic orbitals combine linearly to form molecular orbitals.
If A & B are wave functions of atoms A & B then according to LCAO:
b = A +B and a = A-B
Where, b= Bonding molecular orbital and a= Antibonding molecular orbital
M.O = A ± B

Q20. Why metals are malleable and ductile?

Metals are malleable (can be beaten into sheets) and ductile (can be drawn into wires) due its non-directional nature of metallic
bond. The layers of atoms can slide over each other easily when force is applied. Hence, only the shape of metal (crystal)
changes, the crystal structure does not change.

Q21. How is bond order related to bond length?

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Ans. B.O.  1
B.L.

Q22. CO+ molecular ion is less stable than CO molecule. (2009-2010)

Q23. Which of the following is diamagnetic in nature? (2009-10)

(i) H2+ (ii) H2 (iii) H2-(iv) None of these

Ans. H2 is diamagnetic in nature.

Q24. Explain impurity defects? (2020-21)

Ans. Impurity defects arises when foreign atoms i.e. atoms different from host atoms, are present in the crystal lattice.
Germanium is common impurity in silicon. There are two types of impurity defects-
Substitutional defects: when the host atom is substituted by some other atom.
Interstitial defects: When the atoms different from host atoms are present in the interstitial spaces.

Q25. Why oxygen is paramagnetic and nitrogen is diamagnetic? (2020-21)

Ans.
MO electronic configuration of O2 (16e-)
 1S 2   1S 2   2S 2    2S 2   2 p 2   2 px 2 =  2 p 2 y    2 px1 =   2 p y1
z

Since, in oxygen molecule there are two unpaired electrons in antibonding 2p orbitals, it is paramagnetic in nature.
N2 (14 electrons):  1S 2   1S 2   2S 2    2S 2  n2 p 2 y =  2 p 2 x   2 p 2 z
In nitrogen all the electrons are paired so it is diamagnetic in nature.

LONG QUESTIONS

Q1. Arrange the species O 2, O2-,O2-2, O 2+ the decreasing order of bond order and stability and also indicate their
magnetic properties. (2013-14, 2010-11)
Ans. The molecular orbital configuration of O2, O2-, O22-, O2+ are as follows:
O2 = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px1 = π*2py1
Bond order = (10-6)/2 = 2, Number of unpaired electrons = 2; Therefore paramagnetic
O2- = σ 1s2, σ *1s2, σ 2s2, σ *2s2, σ 2pz2, π2px2 = π2py2, π*2px2 = π*2py1
Bond order = (10-7)/2 = 1.5, Number of unpaired electrons = 1; Therefore paramagnetic
O22- = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px2 = π*2py2
Bond order = (10-8)/2 = 1, Number of unpaired electrons = 0; Therefore diamagnetic
O2+ = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px1= π*2py0
Bond order = (10-5)/2 = 2.5, Number of unpaired electrons = 1; Therefore paramagnetic
The bond order decreases in the order is: O2+ >O2>O2->O22-
Since B.O.  Stability, so stability order is: O2+ >O2>O2->O22-

Q2. Explain on the basis of M.O.T. why nitrogen is diamagnetic and oxygen is paramagnetic? OR
Draw the molecular orbital diagram of N2 molecule. Calculate its bond order and predict its magnetic behaviour. OR
Which has higher bond order N2 or O2. (2017-18, 2016-17 2013-14)
Ans. N2 is diamagnetic & O2 is paramagnetic

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Molecular Orbital Diagram of O2 Molecular Orbital Diagram of N2

Oxygen is paramagnetic as in molecular orbital diagram of oxygen there are two unpaired electrons in π*2p x and π*2py.
Nitrogen is diamagnetic as all the electrons in its molecular orbital diagram are paired.

Q3. Outline the salient features of molecular orbital theory on the basis of LCAO principle. Draw the molecular orbital
diagram of CO. What is its bond order? Also comment on its magnetic behaviour. (2018-19, 2016-17, 2013-14)
Ans. Salient Features or Postulates of MOT:
1. Atomic orbitals with same energy & symmetry combine to form molecular orbitals by LINEAR COMBINATION OF ATOMIC
ORBINTALS (LCAO)
If A&B are wave functions of atoms A & B then according to LCAO =
M.O = A ± B
2. Two types of molecular orbitals are formed: bonding and antibonding molecular orbitals. Molecular orbitals formed the
additive overlap of two atomic wave functions is known as Bonding Molecular orbital. i.e. b = A + B
Molecular orbitals formed by subtractive overlap of two atomic orbitals wave function is called Anti-bonding molecular orbital
i.e. a = A - B

3. The no. of molecular orbitals formed is always equal to the number of atomic orbitals taking part in bond formation.
4. Energy level of bonding M.O. is less than that of individual atomic orbitals. So, e - present in bonding M.O stabilizes the
molecule.
Energy level of antibonding M.O is more than that of individual atomic orbitals. So e- present in anti-bonding M.O destabilizes
the molecule.
5. Molecular orbitals that do not participate in bonding are called non-bonding M.O & their energy is equal to that of individual
atomic orbitals.
6. Molecular orbitals are polycentric.

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7. The atomic orbitals involved in the formation of M.O. completely lose their identity after the formation of molecular orbitals.
8. Electrons filling in the molecular orbitals follow Aufbau principle, Pauli’s exclusion principle & Hunds rule of maximum
multiplicity.
9. The electrons are filled in the molecular orbitals according to the following order:
From H2 to N2: σ1s, σ*1s, σ2s, σ*2s, π2px = π2py, σ2pz, π*2px= π*2py, σ*2pz
From O2 to Ne2: σ1s, σ*1s, σ2s, σ*2s, σ2pz, π2px = π2py, π*2px= π*2py, σ*2pz
10. Molecules or ions with one or more unpaired e- in molecular orbitals are paramagnetic while those with all paired electrons
in M.O. are called diamagnetic.
11. Stability & strength of a chemical bond is expressed in terms of bond order.
12. B.O. – Bond order is equal to one half of the difference between the number of electrons in bonding M.O & the no. of e - is
antibonding M.O.

Molecular orbital diagram of CO:

It is diamagnetic in nature as all the electrons are paired.

Q4. What are crystal defects? What is meant by point defects, stoichiometric and non-stoichiometric defects? Distinguish
between Schottky and Frenkel defects. (2017-18, 2016-17, 2014-15)

Ans. CRYSTAL DEFECT OR CRYSTAL IMPERFECTION

Any deviation from a perfectly ordered arrangement of constituents (ions or atoms) in a crystal is known as crystal imperfection
or defect.
Crystal defect may occur in three ways: at a point, along a line and over a surface.

Point Defects or Zero dimensional defects: When the deviation exists from the regular or periodic arrangement around an atom
or a group of atom in a crystalline substance, the defects are called point defects.

Point defects

Stoichiometric Defects Non Stoichiometric Defects

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a) Stoichiometric Defects:
The compounds in which the number of +ve & -ve ions are exactly in the ratios indicated by their chemical formulas are called
stoichiometric defects.

Schottky Defect Frenkel Defect

1 Equal no. of cations and anions are missing from An ion is missing from the lattice site and
crystal lattice. occupies interstitial position.
2 It is a vacancy defect. It is a hybrid of vacancy defect & interstitial
defect.
3 Occurs in highly ionic compounds, which have Occurs in compounds with low coordination
high coordination number. number.
4 Occurs in crystals having same size of anions & Occurs in crystal where cations & anions are
cations. of difference sizes (cations are smaller)
5 It decreases the density of the crystal. Density of the crystal remains the same as
before.
6 Found in pure alkali metal halides. Not found in pure alkali metal halides as in
them cations are large in size.
7 E.g. - NaCl, AgBr e.g. - ZnS, AgCl, AgI, AgBr

Pair of ions missing from lattice A cation missing from the lattice

Schottky Defect Frenkel Defect

b) Non-Stoichiometric Defects :
The defects which disturb the stoichiometry of the compounds are called Non-stoichiometric defects.
These are either due to the presence of excess metal ions or deficiency of metal ions.

Q5. Explain the band theory in solids OR Explain metallic bond on the basis of M.O.T.
OR
Explain metallic bond on the basis of MOT (2010-11) OR
Explain MOT in case of metals and on its basis differentiate between conductors, semiconductors and insulators. (2017-18)
With the help of molecular orbital theory how metallic bonding in metals can be explained? (2020-21)

Ans. Explanation of Metallic bond on the basis of M.O.T. or band theory of Solids
*According to this theory electron in the metal cover the whole crystal lattice.
*Metallic bond is formed by the delocalization of all the orbitals containing free electrons.
*According to M.O.T. when two atomic orbitals combine two molecule orbitals are formed i.e. bonding and anti-bonding.
*When three atomic orbitals combine, three M.O.'s are formed i.e. bonding, non-bonding & anti-bonding mol. orbitals.
*Similarly when 'n' atomic orbitals combine, 'n' molecular orbitals are formed.
*In case of metals 'n' is of the order of 1023.
*So, 1023 molecular orbitals are formed and these are so closely spaced that they form a continuous energy band. That is why
the theory is known as band theory. F

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For e.g. - Bonding in Sodium Metal

Na = 1S2, 2S2,2p6,3s1
Na2→ Na+ Na
Na3→ Na + Na + Na
Na4→ Na + Na +Na + Na
Nan→ Na+ Na + Na + ………………..Nan

Application of band theory in solids: Formation of conductors, semiconductors and insulators on the basis of band theory of
solids. OR
Classification of solids into conductors, semiconductors and insulators on the basis of molecular orbital theory or band
theory.
With the help of band theory we can classify solids into conductors, semiconductors and insulators. In case of solids there are
three bands:
*The outermost completely filled or partially filled (e.g. Lithium) energy band is known as valence band.
*The band above the valence band that is empty at 0 K is known as conduction band.
*The energy gap between valence & conduction band is known as Energy Gap or band gap or forbidden gap.

Formation of various bands in solids

Conductors: No forbidden gap between valence band and conduction band. The two bands overlap. Hence even at room
temperature, a large number of electrons are available for conduction. E.g. iron
Insulators: Large forbidden gap in between the conduction band and the valence band (about 7 eV).
Electrons can-not jump from the valence band to the conduction band. Hence, such materials cannot conduct electricity.
Example: diamond, glass, wood, mica, paper etc.
Semiconductors: The forbidden gap is in between conductors and insulators (1 eV).
Doping or the energy provided by the heat at room temperature can move the electrons from the valence band to conduction
band.
Therefore at room temperature, semiconductors are capable of conduction.

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Q6. Give the structure, properties and uses of graphite. OR With the help of neat diagram describe the structure of graphite.
Also give at-least five applications of graphite. (2017-18, 2016-17, 2014-15, 2013-14, 2010-11)
Ans. Structure of graphite:
*Graphite is an allotrope of carbon (it is made up of only pure carbon atoms).
*Each carbon atom in graphite is sp2 hybridised.
*6 such carbon atoms join with the covalent bonds to form hexagons.
*In hexagons each carbon atom forms 3 covalent bonds (C-C distance is 1.42 Ǻ) with other carbon atoms.
*Fourth electron of each carbon atom is free to move within the layer.
*Various hexagons join together to form a plane or sheet called graphene.
*Various sheets (graphene) are arranged one above the other.
*Different layers of graphite are attached to each other with weak Vander Waals forces.
*Distance between two successive sheets is 3.41 Ǻ.
*Graphite has planar, two dimensional structure. Hybridisation of C in graphite:

Properties of Graphite:
1. It is greyish black and greasy substance.
2. High Melting point.
3. Slippery nature.
4. Low coefficient of friction.
5. Ineffective in vacuum conditions.
6. Graphite exists in two forms: α and β-graphite.
7. Graphite is a conductor of electricity.

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Structure Of Graphite
Applications of Graphite:
• Used as a lubricant as layers can slide over one another due to weak vanderwaals forces.
• Used in pencil leads due to soft, slippery nature and it leaves a black mark on paper when rubbed against it.
• Used in the preparation of electrodes as it conducts electricity due to presence of free electron on each carbon atom.
• Due to high melting point it is used to prepare crucible for making high grade steel.
• It is used as moderator in nuclear reactors as it absorbs fast moving neutrons.

Q7. Give the structure preparation, properties and uses of fullerene or Give the structure preparation, properties and uses of
an allotrope of carbon with truncated icosahederon geometry. (2020-19, 2018-19, 2016-17, 2015-16, 2014-15, 2011-12, 2009-
10)
Ans. Fullerene (Discovered by Kroto & Smalley)
• It is an allotrope of carbon, also called Buckminster fullerene or Bucky Ball.
Structure: There are 12 pentagons & 20 hexagons of C atoms.
• No two pentagons touch each other
• Diameter of C60 7A°; geometry-geodesic dome.
• There are 30 (C=C) double bonds in C60
• There are 60 vertices, 32 faces.
• C-C single bond length-104.5 A°; C=C double bond length=1.38A°
• It is highly symmetrical molecular & is said as zero dimensional
• Fullerene crystal structure is FCC.
• Its density is 1.65 gm /cc

Preparation of Fullerene: Fullerenes are prepared by Arc Discharge Method:

Graphite rods kept in an inert atmosphere (He gas)(.05 to .1 atm pressure)

Electric current

Rods evaporate to give fullerene soot containing 5 to 15 % fullerenes.

Sublimation

Fullerene mixture

Chromatography
using alumina hexane

C60

Properties
• Mustard coloured solid.
• Basically semiconductors but on doping with alkali metals can be converted into conductor or super conductor.
• Shows poor aromatic nature.
• Strongest known material to man.
• Exists as discrete molecule.
• Can be compressed to lose 30% of its original volume.
Uses
• Have powerful antioxidant properties, so used in health & personal care areas.
• C60 shows catalytic process.

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• Act as drug delivery agent.

• C60 derivatives act as potential inhibitors to HIV.
• Used in preparation of superconductors.
• In Optical devices.
• Used in batteries.

Q8. Differentiate between nematic and Smectic liquid crystals. (2018-19, 2017-18, 2009-10)
Ans.
Nematic Liquid Crystals Smectic Liquid Crystals
1 They are thread like. They are soap like and are clayey or greasy.
2 Molecule have elongated rod like shape. Molecules are cigar shaped.
3 Do not have layered structure. These are arranged in layers i.e. have layered structure.
4 Flow like normal liquids. They do not flow like normal liquids and has limited
mobility.
5 They have low viscosity. They have high viscosity.
6 Formed at relatively higher temperature. Formed at comparatively lower temperature.
7 Can be aligned by the application of electric on Not affected by external electric or magnetic field.
magnetic field.
8. Molecules are free to move in all the Molecules are free to move within the layers but not
directions. from one layer to another.
9. Flow in all directions & not in layers. Flow in layers and difference layers can slide over one
another.
10. Total loss of positional order but they have Have short range orientational as well as positional order.
orientational order.
11. E.g.- p-azoxy anisole E.g. - Ethyl-p-azoxyphenetole.

Q9.What are liquid crystals? What are their essential characteristics? Give their classification and application. (2018-19, 2017-
18, 2016-17, 2014-15, 2011-12, 2010-11)

Ans. Liquid Crystals:

Liquid Crystals are state of matter which has properties between liquids and solid crystals.
The liquid-crystalline state is often called mesomorphic (mezos meaning "intermediate"), and the substance itself is called
mesophase.

Essential requirements for a molecule to be a liquid crystal:

• Shape of the molecule must be rod like or disc like.
• Molecule must be anisotropic in nature.
• Molecule must have some rigidity in its central region and the ends must be flexible.

Properties of liquid crystals:

• The molecules are rod shaped or disc shaped.
• Molecules are anisotropic in nature.
• These molecules possess very strong dipole moment
• The liquid crystal molecules prefer to align parallel to each.

Classification of liquid crystals:

Liquid crystals are basically classified into:
1. Thermotropic liquid crystals
2. Lyotropic liquid crystals

Thermotropic liquid crystals: They are formed by change of temperature. They occur as liquid crystals over a certain
temperature range between the solid and liquid phase. Example – LCD TV’s, alarm clocks.

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These liquid crystals are further classified into:

a) Nematic b) Smectic c) Cholesteric d) Discotic

a) Nematic liquid crystals: Word nematic is derived from the Greek word, ‘Nema’ which means "thread". They show following
properties:
• No positional order, but has orientational order.
• It is only crystal phase with no long transitional order.
• Molecule have rod like shape and are thread like.
• Do not have layered structure.
• Flow like normal liquids.
• They have low viscosity.
• Formed at relatively higher temperature.
• Can be aligned by the application of electric on magnetic field.
• Molecules are free to move in all the directions.
• Flow in all directions & not in layers.
• E.g.- p-azoxy anisole (first synthetic liquid crystal to be produced).

b) Smectic Liquid Crystals:

• They are soap like and are clayey or greasy.
• Molecules are cigar shaped.
• These are arranged in layers.
• They do not flow like normal liquids and has limited mobility.
• They have high viscosity.
• Formed at comparatively lower temperature.
• Not affected by external electric or magnetic field.
• Molecules are free to move within the layers but not from one layer to another.
• Flow in layers and difference layers can slide over one another.
• Have short range orientational as well as positional order.
• Are of two types: Smectic A and Smectic C.
• E.g. - Ethyl-p-azoxyphenetole

c) Cholesteric Liquid Crystals: Cholesteric liquid phase is made of nematic molecule containing a chiral centre .This phase is
usually observed from cholesterol derivatives.
• The molecules are essentially chiral.
• The molecules are arranged in layers like Smectic liquid crystals.
• The structure of layers is similar to nematic phase and so it is also known as chiral nematic.
• Each layer in Cholesteric liquid crystal is tilted with respect to the other one, and hence the molecules take a one
complete turn of 360 degrees to make a helix.
• The distance covered by the director in making a one complete turn is known as pitch.
• Pitch is inversely proportional to the temperature. It is affected by temperature, pressure and electric & magnetic
fields.
• Example: Cholesteryl benzoate (it was the first liquid crystal to be identified).

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Discotic Liquid Crystals:

Molecules are essentially disc shaped.
Are of two types:
Discotic nematic: Disc shape, have orientational order but no positional order.
Discotic columnar or Discotic Smectic: Disc shape, have orientational order as well as positional order.

Discotic nematic Discotic smectic

Lyotropic Liquid Crystals:

• These are made on change in the concentration of solvent and/or change in temperature.
• LLC are made by adding solvent to the solid until critical micelle concentration (CMC) is reached. On further addition of
solvent LLC changes into liquid phase.

• These are made up of two parts: Hydrophilic polar ‘head’ and hydrophobic ‘tail’, so they are amphiphillic in nature.
• Examples: molecules of soaps, phospholipids (present in cell membranes)

Applications of liquid crystals:

• Liquid crystals are used in cosmetics.
• Due to their colour effect Cholesteric liquid crystals are used in nail paints, eye shadows etc.
• Liquid crystals are used for displays in LCD's, Calculator, wrist watches etc.
• Cholesteric liquid crystals are used in coloured thermometers.
• Used in research work.
• Used in electronic industries.
• Used for localized drug delivery.

Q10. Define nanomaterials. Give the approaches to synthesize nanomaterials. What are the applicatons of nanomaterials?
Ans. Nanomaterials: are materials having at-least one of its dimensions in the nanometre scale (1 nm= 10-9 m).
Nanomaterials synthesis approach:
1. Top down approach: Breaking of bulk material
2. Bottom approach: Buildup of material: Atom→molecule→cluster

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Applications of nanomaterials:
In major view nanomaterials has found their applications in many major areas:
• Electronics
• Medicine
• Engineering and technology
• Industries
• Environment
• Sensors
• Catalysis

Q11. Differentiate between BMO and ABMO. Draw molecular orbital diagram of NO and CO. Calculate bond order, and tell about
its magnetic behaviour. (2015-16, 2014-15, 2009-10)

BONDING MOLECULAR ORBITALS ANTIBONDING MOLECULAR ORBITALS

1. Formed by additive overlapping of atomic orbitals. Formed by subtractive overlapping of atomic orbitals.

2. b = A + B a = A - B
3. Leads to the stability of molecule. Leads to instability of molecule
4. They have low energy and high stability. They have high energy and low stability.
5. They are shown as σ ,π etc. They are shown as σ*, π* etc.
6. Electrons are located in between the two nuclei. Electrons are scattered.

M.O. diagram of NO M.O. diagram of CO

B.O. of CO = (N b − N a ) = (10 − 4) = 3
1 1
B.O. of NO =
1
(N b − N a ) = 1 (7 − 3) = 2
2 2 2 2
It is paramagnetic (unpaired electron) It is diamagnetic (paired electron)

Q11. Differentiate between BMO and ABMO. Draw molecular orbital diagram of NO+. Calculate bond order, and tell about its
magnetic behaviour. (2018-19)
Ans.
B.O. =
1
(N b − N a ) = 1 (7 − 2) = 3
2 2
It is diamagnetic in nature as all the electrons are paired.

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Q13. What do you mean by mesomorphic state and illustrate it with the help of vapour pressure-temperature curve? Discuss its
classification on basis of temperature and give their important applications. (2018-19)
Ans. Liquid Crystals are state of matter which has properties between liquids and solids
The liquid-crystalline state is also called mesomorphic state, and the liquid crystals are called mesophase.
Essential requirements for a molecule to be a liquid crystal:
• Shape of the molecule must be rod like or disc like.
• Molecule must be anisotropic in nature.
• Molecule must have some rigidity in its central region and the ends must be flexible.

Classification of liquid crystals:

Liquid crystals are basically classified into:
1. Thermotropic liquid crystals
2. Lyotropic liquid crystals
Thermotropic liquid crystals: They are formed by change of temperature. Example – LCD TV’s, alarm clocks.

These liquid crystals are further classified into:

a) Nematic b) Smectic c) Cholesteric
a) Nematic liquid crystals: (Nema= "thread")
• No positional order, but has orientational order.
• Molecule have rod like shape and are thread like.
• Do not have layered structure.
• Flow like normal liquids.
• They have low viscosity.
• Formed at relatively higher temperature.
• Can be aligned by the application of electric on magnetic field.
• Molecules are free to move in all the directions.
• Flow in all directions & not in layers.
• E.g.- p-azoxy anisole (first synthetic liquid crystal to be produced).

b) Smectic Liquid Crystals:

• They are soap like and are clayey or greasy.
• Molecules are cigar shaped.
• These are arranged in layers.
• They do not flow like normal liquids.
• They have high viscosity.

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• Formed at comparatively lower temperature.

• Not affected by external electric or magnetic field.
• Molecules are free to move within the layers but not from one layer to another.
• Flow in layers and different layers can slide over one another.
• Have short range orientational as well as positional order.
• Are of two types: Smectic A and Smectic C.
• E.g. - Ethyl-p-azoxyphenetole.

c) Cholesteric or Chiral nematic Liquid Crystals: Made of nematic molecule containing a chiral centre. The molecules are essentially
chiral.
• The molecules are arranged in layers like Smectic liquid crystals.
• Each layer in Cholesteric liquid crystal is tilted with respect to the other one, and hence the molecules take a one
complete turn of 360 degrees to make a helix.
• The distance covered by the director in Cholesteric liquid crystals making a one complete turn is known as pitch.
• Pitch is inversely proportional to the temperature. It is affected by temperature, pressure and electric & magnetic fields.
• Example: Cholesteryl benzoate (it was the first liquid crystal to be identified).

Discotic Liquid Crystals:

Molecules are essentially disc shaped. Are of two types:
Discotic nematic: Disc shape, have orientational order but no positional order.
Discotic columnar or Discotic Smectic: Disc shape, have orientational order as well as positional order.

Discotic nematic Discotic smectic

Applications of liquid crystals:

• Liquid crystals are used in cosmetics.
• Due to their colour effect Cholesteric liquid crystals are used in nail paints, eye shadows etc.
• Liquid crystals are used for displays in LCD's, Calculator, wrist watches etc.
• Cholesteric liquid crystals are used in coloured thermometers.
• Used in research work.
• Used in electronic industries.
• Used for localized drug delivery.

Q14. Calculate the bond order of N2-, CO, NO, andO2+ . (2015-16)
Ans. .N2- (14 electrons):  1S 2   1S 2   2S 2    2S 2   2 p 2 x   2 p 2 y =  2 p1 x

B.O. of N 2− =
1
(N b − N a ) = 1 (10 − 5) = 2.5
2 2

Molecular configuration of CO:  1S 2   1S 2   2S 2   2 p 2 x   2 p 2 y =  2 p 2 x    2S 2

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B.O. of CO =
1
(N b − N a ) = 1 (10 − 4) = 3
2 2
Molecular configuration of NO: σ 1s2, σ *1s2, σ 2s2, σ *2s2, π2px2 = π2py2, σ 2pz2, π*2px1

B.O. of NO =
1
(N b − N a ) = 1 (7 − 3) = 2
2 2
Molecular configuration of O2+ = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2, π*2px1= π*2py0
Bond order = (10-5)/2 = 2.5
Q15. Draw the Molecular Orbital Diagram of HF and comment on the stability and polarity of the covalent bond between H and F.
(2012-13)
Ans.
B.O. =
1
(N b − N a ) = 1 2 (2 − 0) = 1 2  2 = 1
2
HF is diamagnetic in nature.
HF is a polar molecule as fluorine is highly polar in comparision to Hydrogen. This is why the Molecular Orbital Diagram of HF is
distorted and 1s of hydrogen gets paired with 2p of fluorine.
HF is a stable molecule as the bond order of HF is a positive and non-zero value.

Molecular Orbital diagram of HF:

Q16. F2 is diamagnetic while O2 is paramagnetic. Why? (2011-12)

Ans. F2 is diamagnetic while O2 is paramagnetic.
MO electronic configuration of F2 (18e-)  1S 2   1S 2   2S 2    2S 2   2 p 2 z   2 p 2 x =  2 p 2 y    2 p 2 x =   2 p 2 y
All the electrons in molecular orbitals are paired so, it is diamagnetic.
MO electronic configuration of O2 (16e-)  1S 2   1S 2   2S 2    2S 2   2 p 2   2 p x 2 =  2 p 2 y    2 p x1 =   2 p y1
z

There are two unpaired elections in *2px&*2py; So, O2 is paramagnetic

Molecular Orbital Diagram of Fluorine Molecule

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Q17. Write electronic configuration of N2, N2+, N2-, N2-2. Establish their stability order based on calculation of bond order. Also write
their magnetic behaviour. (2009-10)

Ans. The molecular orbital configuration of N2, N2+, N2-, N2-2 are as follows:
N2 = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py2
Bond order = (10-4)/2 = 3, Number of unpaired electrons = 0; Therefore diamagnetic
N2+ = σ1s2, σ*1s2, σ2s2, σ*2s2, σ2pz2, π2px2 = π2py1
Bond order = (9-4)/2 = 2.5, Number of unpaired electrons = 1; Therefore paramagnetic
N2- = σ 1s2, σ *1s2, σ 2s2, σ *2s2, π2px2 = π2py2, σ 2pz2, π*2px1
Bond order = (10-5)/2 = 2.5, Number of unpaired electrons = 1; Therefore paramagnetic
N22- = σ1s2, σ*1s2, σ2s2, σ*2s2, π2px2 = π2py2, σ2pz2, π*2px2
Bond order = (10-6)/2 = 2, Number of unpaired electrons = 0; Therefore diamagnetic
The bond order decreases in the order is: N2 >N2- >N2+ > N22-
Since B.O.  Stability, so stability order is: N2 >N2- >N2+ > N22-

Q18. What is molecular orbital theory? With the help of MO diagram, calculate the bond order of the following: CO, NO and HF.
(2009-10)
Ans. Explained in answer number 3 (Molecular orbital theory), 11 (NO and CO) and 15 (HF)

Q19. Calculate bond order, magnetic behaviour and order of stability of NO, NO - and NO+. (2020-21)
Ans. NO: According to the molecular orbital theory, its molecular orbital configuration will be:
σ 1s2, σ *1s2, σ 2s2, σ *2s2, π2px2 = π2py2, σ 2pz2, π*2px1
The molecule NO is paramagnetic as it contains one unpaired electron.

B.O. of NO =
1
(N b − N a ) = 1 (10 − 5) = 2.5
2 2
NO-: The molecular orbital configuration of NO- molecule will be-
σ 1s2, σ *1s2, σ 2s2, σ *2s2, π2px2 = π2py2, σ 2pz2, π*2px1, π*2py1
B.O. = 1 ( N − N ) = 1 (10 − 6) = 2
b a
2 2
NO- is paramagnetic in nature since there are two unpaired electrons.

NO+: The molecular orbital configuration of NO+ molecule will be-

σ 1s2, σ *1s2, σ 2s2, σ *2s2, π2px2 = π2py2, σ 2pz2
Bond order: B.O. =1/2 (Nb-Na) = 1 (10 − 4) = 1  4 = 2
2 2
It is diamagnetic as all the electrons in it are paired.
Q20. Explain the types of non-stoichiometric defects with examples. (2020-2021)
Ans.
b) Non-Stoichiometric Defects :
The defects which disturb the stoichiometry of the compounds are called Non-stoichiometric defects.
These are either due to the presence of excess metal ions or deficiency of metal ions.
Compounds with Non-stoichiometric defects are also known as Bertholide compounds.
Electrical neutrality of ionic crystal is maintained due to the presence of either extra positive charge on one of the neighbouring cation
or presence of extra free electron in crystal lattice.
Cations are present in different oxidation states.
Non-Stoichiometric Defects

Metal ion excess defect Metal ion deficiency defect

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Metal ion excess defect: May be due to anionic vacancy or due to extra interstitial cation.

Due to Anionic vacancy Due to extra interstitial cation

Arises when some of the negative ions (anions) are Arises when the voids or interstitial sites are occupied by
missing from the lattice site additional metal ions.
Absence of anion from the crystal lattice leaves a hole Electrical neutrality is maintained by corresponding number of
which is occupied by an electron to maintain electrical electrons present in same interstitial site.
neutrality.
Crystals which are likely to show schottky defects show Crystals which are likely to show Frenkel defects show such
anionic vacancy defects. defects.
F centres or colour centres are created. There are no F centres.
E.g. NaCl E.g. ZnO

Metal ion deficiency defect:

Due to cationic vacancy Due to extra interstitial anion

Arises when a cation is missing from its lattice. Arises due to presence if extra anion at the interstitial site.
Occurs in ionic solids where metal ion can exhibit variable Not practically possible (Anions being large in size cannot
valency. occupy interstitial site).
To maintain electrical neutrality one of the nearest metal ion The extra negative charge is balanced by one extra positive
acquires the positive charge. charge on adjacent metal ion.
E.g. Transition metal compounds like NiO, FeO, FeS etc. No examples known so far.
Consequences of metal excess and metal deficiency defects:
Metal excess defects results in formation of n-type semiconductors whereas metal deficiency defect results in p-type semiconductors.
In metal excess defects flow of current is mainly due to presence of free electrons whereas in metal deficiency defect the current flows
due to movement of positive holes.

IMPURITY DEFECTS:
Impurity defects arises when foreign atoms i.e. atoms different from host atoms, are present in the crystal lattice. Germanium is
common impurity in silicon. There are two types of impurity defects-
Substitutional defects: when the host atom is substituted by some other atom.
Interstitial defects: When the atoms different from host atoms are present in the interstitial spaces.

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