Chemistry 1st Semester

Important Questions

1.Fazan’s Rule:
The variation of non-polar character in ionic compounds can be explained using Fajan's rule interms
of polarization effects. Fajan proposed the rule to determine the extent of covalent character
induced in an ionic compound. The important points of Fajan's rule are,is in your C Boll
(1) Increased charge on a cation or decreased size of a cation, increases the covalent character
induced in an ionic compound.
(ii) due to its polarization, increases the covalent nature induced in an ionic compound.
Increased charge and increased size of an anion
(iii) Cations possessing pseudo noble gas configuration exhibit higher polarizing power than the
cations with actual noble gas configuration.
Examples When comparing Ferric chloride (FeCl,) and Ferrous chloride (FeCL), FeCl, has more
covalent nature than FeCl due to the high charge of Fe"
2. Give an account of VSEPR Theory and its applications:
VSEPR (Valence shell electron pair repulsion) theory was proposed by Sidgwick and Powell and
further extended by Nyholm and Gillspie. It is based on the repulsive interactions of the electron
pairs in the valence shell of atoms
The salient features of VSEPR theory are,
The geometry (shape) of a molecule depends on the repulsions and attractions of lone pair and bond
pait present in valence shell around the central atom
The electron pairs repel with each other as the electron clouds are negatively charged. (on) The
electron pairs try to occupy the positions around the central atom such that the repulsion is less
(minimum)
and distance of separation is large (iv) A valence shell is considered as a sphere with pair of electrons
restricted on the spherical surface at larger distance from each other
The magnitude of the repulsion of electrons in bond are paired depending upon the difference in the
electronegative value between the central atom and the bonded stom. there are two or three
electron pairs in a multiple
A multiple bond is considered as a single pair of electron. If
bond, then it is considered as a single super pair of electrons
If more than one resonance structure can represent a molecule, then this theory is applicable to any
one
resonance structure of that molecule
(vi) The order of repulsive interaction of electron pairs can be given as Lone pair (Lp)-Lone pair (Lp)
Lone pair (Lp) - Bond pair (Bp) Bond pair (Bp)-Bond pair (Bp)
3. Write the salient features of Molecular Orbital Theory:
Ans: Molecular orbital theory was proposed by Hund and Mulliken. Its salient features are as follows,
Electrons of molecules are present in the molecular orbitals and electrons of atoms are present in
atomic orbitals.
Atomic orbitals of same energy and same symmetry with respect to inter nuclear axes combine to
form molecular orbitals.
3. The number of molecular orbitals is equal to the number of combining atomic orbitals.
4. The atomic orbitala are monocentric whereas the molecular orbitals are polycentric. That is, the
electron in an atomic orbital is influenced hy one nucleus whereas electron in a molecular orbital is
influenced by more than one nucleus.
5. The molecular orbital with energy greater than atomic orbital forms bonding molecular orbital
(BMO). It can be represented by s and p bonds.
6. The molecular orbital with energy less than atomic orbital forms antibonding molecular orbital
(ABMO). It
can be represented by s and p bonds.
7.Stability of bonding molecular orbital is greater than antibonding molecular orbital.
8. The order of energies of molecular orbitals is as follows.
Bonding orbital non-bonding orbitals antibonding orbitals.
ZnCl mell of
9. The shape of molecular orbitals depends on the shape of the atomsc orbital
10. The molecular orbitals are filled according to the Aulhau principle, Pauli's exclusion principle and
the Hund's
rule.
11.Molecular orbital gives the probability distribution of electron in a molecule
The formation of bonding (o) and anti bonding (*) molecular orbitals by the linear combination of
atomic orbitals p, and p, ceatred on two atoms A and B respectively are shown in figure

4. Write about molecular orbital and give its types Answer:

An orbital formed due to the overlap of one orbital of an atom with the orbital of another atom is
known as molecular orbital (MO).
Thus, a molecular orbital represents a covalent bond and contains only two electrons. Molecular
orbitals are formed by the addition or subtraction of atomic orbitals that overlap with each other.
Figure (i) gives the basic idea of formation of a molecular orbital
(Antibonding MO)
Energy
(Bonding MO)
Figure: Formation of MO
There are three major types of molecular orbitals, namely, Bonding Molecular Orbital (BMO)
Antibonding Molecular Orbital (ABMO)
(ii) Non-bonding Molecular Orbital (NBMO).
5. Discuss in brief about Molecular Orbital Energy-level Diagram (MOED).
Ans: A molecular orbital diagram, or MO diagram, is a qualitative descriptive tool explaining
chemical bonding in molecules in terms of molecular orbital theory in general and the linear
combination of atomic orbitals (LCAO) method in particular.
Atomic orbitals with equal energies are placed at same level in the energy level diagram. Depending
on the
extent of overlapping of atomic orbitals, they possess different energies. Larger the overlapping of
atomic orbital, greater is the lowering of bonding MO and corresponding raise of antibonding MO.
Therefore, large overlapping of orbitals gives stronger bonds. The sequence of energy levels that are
filled first in the energy level diagram is given by,
<<<<σα < πο= πα<πα = πόσα The diagrammatic representation of Molecular Orbital Energy-Level
Diagram with increasing energy of atomic orbital
6.Structure of Di-borane and Higher Boranes:
Ans:The structure of the diborane molecule consists of four hydrogen atoms and of two boron
atoms coming on the same plane. In between these planes, there are said to be two dividing atoms
of hydrogen. The boron atom is known to be sp3 hybridised and has four hybrid orbitals. From these
four hybrid orbitals, three of the orbitals have one electron each, out of which one is an empty
orbital. The two electrons of the hybrid orbitals in each of the boron atoms form 2 bonds with the 1s
hydrogen atoms. The two atoms of boron left with that of each unpaired electron orbital and empty
orbital form the two bridgings (B–H–B) bonds with that of the two 1s hydrogen atoms, which is also
called the banana bond.
Reactions
– Pure diborane does not react with air or oxygen at room temperature, but it gives B2O3 together
with large amounts of energy in impure form.
B2H6 + 3O2 → B2O3 + 3H2O
ΔH = -2165 KJ mol-1
– Diborane reacts with methyl alcohol to give trimethyl borate.
B2H6 + 6CH3OH → 2B(OCH3)3 + 6H2
– Reaction with ionic hydrides
It forms metal borohydrides when treated with metal hydrides
– Reaction with ammonia
Diborane is given when treated with excess ammonia at low temperatures. It gives borazole when
heated at higher temperatures.
– Hydroboration
The ether solvent, diborane, adds alkenes and alkynes at room temperature. This reaction is called
hydroboration and is commonly used in synthetic organic chemistry, especially for the addition of
anti-Markovnikov.
B2H6 + 6RCH=CHR → 2B(RCH-CH2R)3
7.Lewis Acid Nature of BX3:
Ans: Electron pair acceptor and donor: This concept was given by Lewis. According to Lewis: Lewis
acids are those substances or solutions which can accept electron pairs and Lewis bases are those
substances or solutions which can donate electron pairs.
The order of acidity of BX3
is defined on the basis of p−p
back bonding. It is defined as when one atom has vacant p-orbitals and the atom to which it reacts
has a lone pair then it donates its lone pair to the vacant p-orbitals of the atom, this process is
known as pπ−pπ
back bonding. Now the boron and fluorine belong to the same period hence the size of these
elements are not too much different i.e. their size are almost similar so here the greater amount if
back bonding takes place. So now this compound will not have space to accept electron pairs from
other compounds and hence it will be the least acidic. Now as we move down from chlorine to
iodine then size increases so back bonding decreases (less back bonding will create more space so
that they can accept electron pairs from the other compound) hence it will show high acidic
character according to the Lewis concept.
Hence the order of Lewis acidity is as: BF3<BCl3<BBr3<BI3

8. carbides – classification

Carbide is a chemical compound formed by the combination of carbon and a metallic or semi-
metallic element. Carbides are used in various industrial, technical, and home applications. Calcium
carbide is a significant contributor to acetylene and other chemicals. Steel, silicon, tungsten, and
other element carbides are desired for their mechanical toughness, durability, and resistance to
chemical degradation, even at extremely high temperatures. Iron carbide (cementite) is a key
component of steel and cast iron.

A carbide is a chemical compound made up of carbon and metallic or semi-metallic components. It

can be found in ionic form. The ionic or covalent link connects the carbide group to the metal or
semi-metallic element. The symbol C2-2 denotes carbide. It denotes that carbide ions are composed
of two carbon atoms. The carbide formula indicates that the carbide occurs in dianionic form. Based
on the carbide ion formula, we can tell what lone pairs and hybridisation are.

Structure of a carbide
Two carbon atoms are joined together by three covalent bonds in a carbide formation. Two of such
covalent bonds are pi-bonds. This lateral overlaying of the p-orbitals results in the formation of such
pi-bonds. Another type of bond is the sigma bond, created by the s-orbitals overlapping head-on.
The carbon in the carbide structure exhibits sp hybridisation. Each carbon has a single lone pair on it.

Basic characteristics of carbides

Carbides usually have a fairly high melting point.

Carbides are excellent electrical conductors.
Carbides are good thermal conductors.
Carbides have a lustrous appearance in general.

Classification of carbides

Carbides are classed broadly based on the sort of chemical linkages they contain, as follows:

(i) salt-like (ionic) compounds

(ii) covalent compounds

(iii) interstitial compounds, and

(iv) transition metal carbides classified as “intermediate.”

1) Salt-like or saline carbides are made of highly electropositive atoms combined with carbon, such
as alkali, alkali earth, and group-III metals.

2) Covalent carbides are present in silicon and boron carbides. Because of their close
electronegativity and size to carbon, these two elements produce “covalent” carbides. As a result,
their bond is covalent. Silicon carbide exists in two crystalline forms connected to diamond
structures.

3) Interstitial carbides are transition metal carbides of groups IV, V, and VI. These carbides have
metallic and refractory properties.

4) The transition-metal ion in intermediate transition metal carbides is smaller than the crucial 135
pm, and the configurations are not interstitial but rather complicated. Several stoichiometries are
quite common. These carbides are more reactive than interstitial carbides; for example, the carbides
of Cr, Mn, Fe, Co, and Ni are all hydrolysed by dilute acids, and occasionally by water, to produce a
combination of hydrogen and hydrocarbons. These compounds have properties in common with
both inert interstitials and much more reactive salt-like carbides.
9. silicones – classification
Silicones are polymers, also known as polysiloxanes, which are inert, synthetic compounds made up
of repeating units of siloxanes. They are typically colorless oils or rubber-like substances and can be
used in a variety of applications such as sealants, lubricants, insulation, and medical devices.

Silicones can be classified as either Room Temperature Vulcanized (RTV), Liquid Silicone (LSR),
Fluorosilicone, and Standard Liquid Silicone Rubber (SLR). RTV silicones are used for forming gaskets,
sealing and coating, and creating special effects. LSR silicones are used for injection molding and for
creating custom liquid silicone rubber molds. Fluorosilicone is typically used for applications where
extreme temperatures and high chemical resistance are needed. SLR silicones are used for a variety
of applications, including medical, automotive, and consumer products.

10. nitrides - classification

Nitride is a compound of nitrogen in which nitrogen is present in the oxidation state of -3.
Nitride has an ionic radius of approximately 140 pm.
Most of the metal nitrides are unstable.
In most cases, when nitrides react with water, they form ammonia. But there are some exceptions
also.
Nitrides of some elements, such as boron, vanadium, silicon, titanium are very hard and resistant to
chemicals.
Classification of Nitrides
Nitrides are classified into four different groups on the basis of their nature of bonding character.
The four groups are:- Ionic or saline nitrides, covalent nitrides, Transition metal nitrides, and
Molecule forming nitrides.

(i) Ionic or Saline nitrides:-

These nitrides form when nitrogen is combined with alkali metals, alkaline earth metals, and the
metals of Group 3. They form ammonium ions after reacting with hydrogen.

Among all alkali metals, only Lithium is able to form nitride. But in the case of alkaline earth metal,
all the elements form nitride in the formula of M3N2. When these compounds (which consist of
metal cations and N3- ions) undergo the hydrolysis process, Ammonia and metal hydroxide are the
final results obtained.
Ionic nitrides show a wide range of variability in their stability.
(ii) Covalent nitrides:-
When nitrogen combines with the elements of groups 13-15, it forms covalent nitrides. Some
examples of covalent nitrides are BN, Si3N4, etc.

These nitrides are very hard.

Most of them are nonconductors.
These nitrides show a wide range of properties on the basis of that element to which nitrogen is
bonded. Some of the important covalent nitrides are following:-
Boron nitride (BN)
Boron nitride is a colorless crystal with a molar mass of 24.82 g/mol. It is insoluble in water. Boron
nitride is said to be isoelectronic. This is because both boron and nitrogen share the same number of
valence electrons with two bonded carbon atoms.

11. Inductive effect

The inductive effect refers to the phenomenon wherein a permanent dipole arises in a given
molecule due to the unequal sharing of the bonding electrons in the molecule. This effect can arise
in sigma bonds, whereas the electromeric effect can only arise in pi bonds. When an electron-
releasing or an electron-withdrawing species is introduced to a chain of atoms (generally a carbon
chain), the corresponding negative or positive charge is relayed through the carbon chain by the
atoms belonging to it. This causes a permanent dipole to arise in the molecule and is referred to as
the inductive effect.

Inductive effect image 1

An illustration describing the inductive effect that arises in a chloroethane molecule due to the more
electronegative chlorine atom is provided.

12. Resonance –mesomeric effects

Introduction

This topic explains the Resonance effect or Mesomeric effect and its types. In organic chemistry, the
behaviour of electrons differs when elements other than that of the carbon atoms and hydrogen
actively take part in the formation of molecular bonds.
The electronic factors influencing the organic reactions include the electromeric effect, the inductive
effect, resonance effects, hyperconjugation, etc. All these factors relate to the organic molecules, in
a diverse manner. Most of the biological molecules consist of a combination of these six elements:
carbon, nitrogen, hydrogen, oxygen, sulphur, and phosphorus. Yet, they do not prevent the organic
compounds from taking on the diverse properties of their chemical reactivity and physical
characteristics.
Resonance Effect Organic molecules have a feature known as resonance or mesomerism. The
delocalized electrons within some compounds where one single Lewis structure does not express
the bonds are described by the factor termed resonance or Mesomerism in organic chemistry. The
delocalized electrons in an ion or molecule can be represented by providing multiple structures
known as resonances.
Definition of Resonance Effect – The polarity induced in a molecule by the interaction of a lone pair
of electrons with a pi bond or the interaction of two pi bonds in nearby atoms is known as the
resonance effect.
Mesomeric effect – The mesomeric effect is the polarity that develops in a molecule as a result of
interaction between two -bonds or a -bond and a lone pair of electrons.
The main difference between resonance and the mesomeric effect is that the resonance effect
describes how a molecule’s lone pair of electrons and bond pair of electrons determine its chemical
structure, whereas the mesomeric effect describes how a molecule’s chemical structure is stabilized
by using a functional group.
13.Hyperconjugation and its application to Stability of Carbonium Ions:
Ans: Hyperconjugation is the delocalization of sigma electrons or lone pairs of electrons into nearby
empty or partially filled p- or pi-orbitals. It is caused by the overlapping of a sigma-bonding orbital or
an orbital containing a lone pair with a neighbouring pi-orbital or p-orbital. It is also often referred to
as the “Baker-Nathan effect” or “no bond resonance.”
Electron delocalization may also take place via parallel overlap of p orbitals with hybridized orbitals
involved in sigma bonds during the process of hyperconjugation. Hence, it is also known as no-bond
resonance and a variation of resonance theory. Now, take ethyl carbocation as an example.

In structure 2, the vacant p orbital on C1

 and the sp3
-hybridized orbital on C2
involved in the C2
—H1 bond are almost parallel, permitting parallel overlap. This lowers the electron deficit at C1
but increases the electron deficiency at H1
. The free rotation around theC1—C2
bond cannot be entirely prevented by this overlap. As a result, the vacant p orbital on C1
also shares electrons with the C2—H2
bond and the C2—H3
bond. Therefore, the delocalization of sigma electrons in ethyl carbocation can be depicted as

The overall structure of the carbocation represents the sharing of net +1 charge by all the four atoms
including one carbon atom and three hydrogen atoms.

The given example also explains the stability of carbocations. When there are more alkyl groups
attached to the positively charged carbocation, the effect of hyperconjugation would be more. In
other words, there will be greater delocalization of sigma electrons. As a result, the carbocation with
a greater number of alkyl groups attached to it will be the most stable.
14.Kolbe’s Synthesis:
Ans:The Kolbe Synthesis
The phenolate ion can react with carbon dioxide to form carboxylic acids. This reaction is one of the
steps in the synthesis of acetylsalicylic acid (aspirin). The reaction, which is carried out under 100
atm. pressure of carbon dioxide, is called the Kolbe reaction.
Kolbe’s electrolysis method is a general method of preparation of substituted hydrocarbons from
the substituted carboxylic acids by the use of the electric discharge method where carbon dioxide
gas is released. It is one of the most widely used methods for the preparation of alkanes and
substituted hydrocarbons.
The Kolbe reaction is a radical reaction that is essentially a decarboxylative dimerisation. An aqueous
solution of sodium or potassium salt of carboxylic acid is electrolyzed in this reaction, resulting in the
dissociation of the salt into carboxylate ion and sodium or potassium ions.
For the production of ethane and higher alkanes, this process is used.
Kolbe reaction:
CH3COOH(aq) + * ↔ CH3COO* + (H+ + e- ) (x2) ………….(1)

CH3COO* ↔ TSCH3-COO* ↔ CH3* + CO2(g) (x2) ………..(2)

2CH3* ↔ TSCH3-CH3* ↔ C2H6(g) + 2*……… (3)

Oxygen evolution reaction (OER):

H2O(aq) + * ↔ H2O* …………..(4)

H2O* ↔ OH* + (H+ + e- ) ……………(5)

OH* ↔ O* + (H+ + e- ) ………….(6)

O* + H2O(aq) ↔ OOH* + (H+ + e- )……….. (7)

OOH* ↔ O2(g) + (H+ + e- ) + * ……….. (8)
Where * denotes the surface sites for adsorption. In addition to the thermodynamics of the
elementary steps, we have computed explicitly TSCH3-COO* and TSCH3-CH3*, the transition states
corresponding to the decarboxylation of CH3COO* and dimerization of CH3* respectively, which
interact significantly with the interfacial electric field and are decisive in the reaction energetics, as
we discuss below. We have, for simplicity, neglected non-Kolbe processes in this analysis.
Conclusion
Kolbe electrolysis has been presented as a useful electrooxidation method for producing
(un)symmetrical dimers from biomass-derived carboxylic acids. The reaction mechanism of Kolbe
electrolysis, however, is still debated. We use a DFT-based microkinetic model to investigate the
reaction mechanism of Kolbe electrolysis of acetic acid (CH3COOH) on pristine and partially oxidised
anodes in this paper. We show that the shift in the rate-determining phase of the oxygen evolution
process (OER) on the surface from OH* production to H2O adsorption causes the enormous Tafel
slopes, or inflection zones, observed in tests on Pt anodes at high anodic potentials. In the presence
of Kolbe species (i.e., CH3COO* and CH3*), activity passivation as a result of the inflection zone is
worsened.
The activity of the Kolbe reaction during the inflection zone is determined by the CH3COO*
decarboxylation and CH3* dimerization stages, according to our simulations. has no activity towards
Kolbe products, in contrast to the surface, since the CH3COO* The decarboxylation step is limited
throughout the potential range. The origin of the inflection zone and the identity of the rate limiting
step are two main disputes in mechanistic investigations of Kolbe electrolysis on Pt anodes.

15.Preparation Of Alkenes:
Ans: From alkyl halides: Alkenes are obtained by heating alkyl halides with alcoholic potash.
Alcoholic potash is obtained by dissolving potassium hydroxide in alcohol. In this reaction,
dehydrohalogenation takes place i.e. a single molecule of halogen acid is removed
Alkynes undergo partial reduction with a particular quantity of dihydrogen to produce alkenes. The
reaction takes place in the presence of palladised charcoal that has been deactivated with poisonous
compounds such as quinolone or sulfur compounds, also known as Lindlar’s catalyst.

The reaction leads to the formation of compounds having cis-geometric conformation. However, if
the same alkynes reduction takes placed with sodium present in liquid ammonia, the resultant
product will be trans alkenes.

Preparation of Alkenes from Alkyl Halides

R-X or Alkyl Halides undergo heating with alcoholic potash to form alkenes. Dissolving potassium
hydroxide in an alcohol such as ethanol leads to the formation of alcoholic potash. In this reaction,
the heating of alkyl halides with alcoholic potash will remove one molecule from halogen acid
leading to the formation of alkenes. Thus, it is a β-elimination reaction example because removal of
hydrogen atom takes place from the β carbon atom.
alkenes
The rate of reaction is dependent on the alkyl group and nature of halogen atom. The order, in this
case, is iodine > bromine > chlorine. The rate of reaction according to the alkyl group is tertiary >
secondary > primary.

16. Zaitsev's Rule : states that when there is more than one possible beta carbon that can be
deprotonated while performing an elimination reaction, the more substituted one (the one with
fewer hydrogen atoms attached) is preferred. Deprotonating the more substituted beta carbon will
lead to a more substituted alkene.
It states that in an elimination reaction the major product is the more stable alkene with the more
highly substituted double bond. This situation is illustrated by the 2-bromobutane and 2-bromo-2,3-
dimethylbutane elimination examples given below.
It's due to the fact that conjugation lowers the energy of an alkene. Zaitsev's Rule regarding forming
the more substituted alkene is based on the fact the more substituted alkene is typically the more
stable alkene.
Zaitsev's Rule states that when there is more than one possible beta carbon that can be
deprotonated while performing an elimination reaction, the more substituted one (the one with
fewer hydrogen atoms attached) is preferred. Deprotonating the more substituted beta carbon will
lead to a more substituted alkene.

17. markovnikov's rule mechanism

When a protic acid (HX) is added to an asymmetric alkene, the acidic hydrogen attaches itself to the
carbon having a greater number of hydrogen substituents whereas the halide group attaches itself
to the carbon atom which has a greater number of alkyl substituents.
When a protic acid (HX) is added to an asymmetric alkene, the acidic hydrogen attaches itself to the
carbon having a greater number of hydrogen substituents whereas the halide group attaches itself
to the carbon atom which has a greater number of alkyl substituents. To simplify the rule, it can also
be stated as – “Hydrogen is added to the carbon with the most hydrogens and the halide is added to
the carbon with the least hydrogens”. An example of a reaction that observes Markovnikov’s rule is
the addition of hydrobromic acid (HBr) to propene

It can be observed from the reaction illustrated above that the majority of the products formed obey
Markovnikov’s rule, whereas the minority of the products do not. Let us consider the addition
reaction wherein an alkene reacts with water to give rise to alcohol. This reaction proceeds via the
formation of a carbocation. It is observed in this reaction that the hydroxyl group attaches itself to
the carbon with more carbon-carbon bonds whereas the hydrogen atom attaches itself to the other
carbon in the double bond, which has more carbon-hydrogen bonds.

18. The Diels–Alder reaction : is an electrocyclic reaction, which involves [4+2]‑cycloaddition of 4

π-electrons of the conjugated diene and 2 π-electrons of the dienophile (an alkene or alkyne). The
reaction involves the formation of new σ-bonds, which are energetically more stable than the π-
bonds.

The Diels–Alder reaction is the reaction between a conjugated diene and an alkene (dienophile) to
form unsaturated six-membered rings. Since the reaction involves the formation of a cyclic product
via a cyclic transition state, it is also referred to as a "cycloaddition". The Diels–Alder reaction is an
electrocyclic reaction, which involves [4+2]‑cycloaddition of 4 π-electrons of the conjugated diene
and 2 π-electrons of the dienophile (an alkene or alkyne). The reaction involves the formation of
new σ-bonds, which are energetically more stable than the π-bonds. This reaction has great
synthetic importance and was discovered by two German chemists, Otto Diels and Kurt Alder in
1928. They were awarded the Nobel Prize in 1950.1

The hetero-Diels–Alder reaction is a variant of this reaction and is useful for the synthesis of six-
membered heterocyclic rings. In this reaction, either the diene or the dienophile contains a
heteroatom, usually nitrogen or oxygen.

19. preparation of alkynes by dehydrohalogenation of vicinal dihalide

Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the

presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with
the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination
reactions.

It is possible to employ dehydrohalogenation of vicinal dihalides as an intermediary step in

the conversion of alkenes and alkynes. For example, chlorination of 1-propene results in the
formation of 1,2-dichloropropane, a vicinal dihalide that, after being dehydrohalogenation
twice, provides 1-propyne.
Dehydrohalogenation of vicinal dihalides is a useful intermediate step in the conversion of
alkenes to alkynes. For example, chlorination of 1-propene gives 1,2-dichloropropane – a
vicinal dihalide, which upon double dehydrohalogenation yields 1-propyne. The first
dehydrohalogenation is the formation of dichlorocarbene: KOH + CHCl3 → KCl + H2O + CCl.
Two successive base-mediated dehydrochlorination steps result in formation of the
isocyanide.

20. chemical reactivity - electrophilic addition of tautomerism

The stability of carbocation decides the rate of electrophilic addition reaction. More the
stability of carbocation more is its reactivity. So the reactivity depends on the stability of
carbocation and the stability of carbocation depends upon the number of electron donation
groups present in the organic compound.

Hence the correct reactivity order toward electrophilic substitution reaction is

phenol>toluene>benene>nitrobenene.

Addition of hydrogen halides such as HBr is an example of electrophilic addition reactions of

alkenes. Electrophilic Addition Reaction: It is an addition reaction in which a substrate is
initially attacked by an electrophile with the formation of a chemical compound containing
two new sigma (σ) bonds and has a broken double or triple pi(π) bond.

21. Mechanism Nitration, sulphonation and halogenations

Nitration : As such, in Organic Chemistry, nitration is a process, in which there is the replacement of
a hydrogen atom (organic compound) with one or more nitro groups (single bond NO2). The reaction
usually occurs at high temperatures, or we can say that the reaction is exothermic.

Nitric acid accepts a proton from sulphuric acid and then dissociates to form nitronium ion. The
nitronium ion acts as an electrophile in the process which further reacts with benzene to form an
arenium ion. The arenium ion then loses its proton to Lewis base forming nitrobenzene.

Sulfonation of Benzene is a process of heating benzene with fuming sulphuric acid (H2SO4 +SO3) to
produce benzenesulfonic acid. The reaction is reversible in nature.

The mechanism for Sulfonation of benzene

Due to higher electronegativity, oxygen present in sulphuric acid pulls an electron towards itself,
generating an electrophile. This attacks the benzene ring, leading to the formation of
benzenesulfonic acid.
Halogenation of Benzene
Benzene reacts with halogens in the presence of Lewis acid like FeCl3, FeBr3 to form aryl halides.
This reaction is termed as halogenation of benzene.
The mechanism for halogenation of benzene:
Being a Lewis acid, FeBr3 helps in the generation of electrophile bromine ion by combining with the
attacking reagent.
The bromine ion acts as an electrophile in the process which further reacts with benzene to form
arenium ion which finally converts to bromobenzene.

22. Friedel-Crafts Reaction

A Friedel-Crafts reaction is an organic coupling reaction involving an electrophilic aromatic

substitution that is used for the attachment of substituents to aromatic rings. The two primary types
of Friedel-Crafts reactions are the alkylation and acylation reactions. These reactions were
developed in the year 1877 by the French chemist Charles Friedel and the American chemist James
Crafts.

Friedel-Crafts Alkylation
Friedel-Crafts Alkylation refers to the replacement of an aromatic proton with an alkyl group. This is
done through an electrophilic attack on the aromatic ring with the help of a carbocation. The Friedel-
Crafts alkylation reaction is a method of generating alkyl benzenes by using alkyl halides as
reactants. The Friedel-Crafts alkylation reaction of benzene
Mechanism
The Friedel-Crafts alkylation
The deprotonation of the intermediate leads to the reformation of the carbon-carbon double bond,
restoring aromaticity to the compound. This proton goes on to form hydrochloric acid, regenerating
the AlCl3 catalyst.

Friedel-Crafts Acylation
The Friedel-Crafts acylation reaction involves the addition of an acyl group to an aromatic ring.
Typically, this is done by employing an acid chloride (R-(C=O)-Cl) and a Lewis acid catalyst such as
AlCl3. In a Friedel-Crafts acylation reaction, the aromatic ring is transformed into a ketone. The
reaction between benzene and an acyl chloride under these conditions

Mechanism
Friedel-Crafts acylations
The intermediate complex is now deprotonated, restoring the aromaticity to the ring. This proton
attaches itself to a chloride ion (from the complexed Lewis acid), forming HCl. The AlCl3 catalyst is
now regenerated.

23. planck's radiation law

Planck showed that the actual energy distribution per volume per unit frequency was E = 8πhν3/c3 ×
1/(ehν/kT-1), where c is the speed of light, k is the Boltzmann constant, T is the absolute
temperature, and v is the frequency. This equation is called Planck's radiation law.
The phenomenon in which light travels in the form of small discrete particles called quanta is known
as Planck's radiation law. The energy is not radiated or emitted continuously. It is emitted in small
proportions in the form of energy packets called quanta. 2. Radiation when in the form of light, each
particle is known as a photon. Planck's equation describes the quantity of spectral radiance at a
particular wavelength radiated by a black body in equilibrium. The equation is E=hv.
It states that electromagnetic radiation from heated bodies is not emitted as a continuous flow but
is made up of discrete units or quanta of energy, the size of which involves a fundamental physical
constant (Planck’s constant).

24. Compton effect

The Compton effect is defined as the effect that is observed when x-rays or gamma rays are
scattered on a material with an increase in wavelength. Arthur Compton studied this effect in the
year 1922. During the study, Compton found that wavelength is not dependent on the intensity of
incident radiation.
physicist Arthur H. Compton
The effect was discovered in 1922 by the american physicist Arthur H. Compton. Compton received
the Nobel Prize in Physics in 1927
The Compton effect is a phenomenon in which an electron in an atom absorbs some of the photon's
energy and then deflects it at an angle Φ. In contrast, the pounded electrons are thrown at an angle
θ off the trajectory.

25. de broglie's hypothesis

In 1924, Louis de Broglie hypothesised that all matter is wave-like. It means that particles (like atoms
and electrons) have both a particle and wave nature and that the wave nature of particles can only
be observed when they are being followed. The wavelength of a particle is inversely proportional to
its momentum.
De Broglie's Hypothesis says that Matter consists of both the particle nature as well as wave nature.
De Broglie wavelength is given as λ = h p , where represents the particle momentum and can be
written as: λ = h m v. Where, is the Planck's constant, is the mass of the particle, and is the velocity
of the particle.
The de Broglie equation is one of the equations that is commonly used to define the wave properties
of matter.
Electromagnetic radiation exhibits the dual nature of a particle (having a momentum) and wave
(expressed in frequency, and wavelength).
26. heisenberg uncertainty principle
Heisenberg's Uncertainty Principle states that there is inherent uncertainty in the act of measuring a
variable of a particle. Commonly applied to the position and momentum of a particle, the principle
states that the more precisely the position is known the more uncertain the momentum is and vice
versa. In short: the uncertainty principle describes a trade-off between two complementary
properties, such as speed and position. The fundamental law comes into play in the quantum world
because subatomic particles can behave like waves.
According to Heisenberg's uncertainty principle, “it is impossible to calculate the position and
momentum of a small moving object like an electron simultaneously and accurately.”

27. The Vander Waals equation

The van der Waals equation is written like this: (P + an2 /V2 )(V-nb) = nRT. It looks very similar to the
ideal gas law (PV = nRT), except now we account for the attraction between the gas molecules with
a, and the volume of those molecules with b.
More significantly, the Van der Waals equation takes into consideration the molecular size and
molecular interaction forces (attractive and repulsive forces). Sometimes, it is also referred to as the
Van der Waals equation of state.
The Van der Waals equation was derived by Johannes Diderik van der Waals in the year 1873. The
equation is basically a modified version of the Ideal Gas Law which states that gases consist of point
masses that undergo perfectly elastic collisions. However, this law fails to explain the behaviour of
real gases. Therefore, the Van der Waals equation was devised, and it helps us define the physical
state of a real gas.
Critical State of a Gas
The point at which the difference between liquid state and vapour state of the gas disappears is
known as critical point and the gas at such point is known as critical state of gas.
Relationship between Vander Waal's Constants and Critical Constants
The relationship between Vander Waal’s constants and critical constants is given as,
Critical volume (V) = 3b
a Critical pressure (P) = 2762
8a Critical temperature (T) = 200 27bR
Where,
a, b – Vander Waal’s constant

30. Linde’s method

Linde's Process : The Linde method liquefies air by compressing, cooling, and expanding it
repeatedly, each expansion resulting in a significant fall in temperature. Because the molecules
travel more slowly and take up less space at lower temperatures, the air changes phase to liquid.
Air is liquefied by the Linde process, in which air is alternately compressed, cooled, and expanded,
each expansion results in a considerable reduction in temperature. With the lower temperature the
molecules move more slowly and occupy less space, so the air changes phase to become liquid.
Linde's Method- The Joule-Thomson effect is used in this procedure. Pure, dry air is fed into a
compressor, which compresses it to around 200 atmospheres. The heat of compression is then
removed by passing it through a conduit cooled by a refrigerating liquid such as liquid ammonia
31. What is Claude's method
A process for liquefying air on a commercial basis. Air under pressure is used as the working
substance in a piston engine, where it does external work and cools adiabatically. This cool air is fed
to a counter-current heat exchanger, where it reduces the temperature of the next intake of high-
pressure air. The main difference between both is only in the manner that you obtain the cryogenic
cold and subsequent liquefaction. A Claude expansion engine still requires a certain amount of by-
passed high pressure air to go through an expansion valve for free adiabatic expansion.

32. SURFACE TENSION – DETERMINATION OF THE SURFACE TENSION WITH THE STALAGMOMETER
The process of determining surface tension using stalagmometer is based on drop weight method. In
this method, weight and surface tension of the liquid dropping out from capillary are proportional to
each other. Figure below represents the structure of stalagmometer.
Experimental procedure
1.The top portion of the stalagmometer is attached with a rubber tube using pinch cock. This set up
is fixed in a clamp stand.
2. Now the apparatus is filled with distilled water till the level is little above the mark 'M'. The
pressure is adjusted in such a way that the rate of water drop fall is 15-20 drops/min.
3. 10 drops of water is taken into a clean bottle whose weight is already measured when it is empty.
4. Now, the apparatus is cleaned with acetone and same procedure is repeated with a liquid.
5. If surface tension of the water is \gamma_{w}, , the surface tension of a liquid (\gamma_{l}) is
obtained as, \gamma_{1}=\frac{w_{3}-w_{1}}{w_{2}-w_{1}}\times\gamma_{w}

Where,
w_{1} - Weight of the empty bottle
w_{2} - Weight of the bottle + 10 drops of water
w_{3} - Weight of bottle + 10 drops of liquid
(w_{2}-w_{1}) - Weight of 10 drops of water (w_{3}-w_{1}) - Weight of 10 drops of liquid

33. Determination of coefficient of viscosity using Ostwald viscometer

The determination of viscosity using Ostwald's viscometer [2,7] is based on the Hagen-
Poiseuille law, which states that rate of flow of a liquid through a capillary depends upon the
constant vertical pressure head for maintaining the uniform volume flow (P), the radius of the
capillary (r), the length of the capillary ...
The Units of coefficient of viscosity are, C.G.S: 1 Poise = 1dyne/sec/cm², M.K.S (or) SI: Pas (Pascal
second) or Nm's (Newton meter second).
It can be determined using Ostwald viscometer. The Ostwald structure of viscometer is shown in
figure below. It includes a tube in the top portion, bulb in the middle and capillary in bottom portion.
The bottom portion of the capillary is attached with larger bulb 'C" and wider tube CD.
Procedure
1. First clean the apparatus using chromic acid and then with water. After cleaning attach the rubber
tube to the end 'A' and clamp this set up vertically to the stand.
2. Fill the bulb 'C' and 'B' with distilled water through the ends 'D' and 'A' respectively
3. Make the water to flow reverse and note down the time taken by water to flow from etched
marks Mand M.
4.Now, clean and dry the apparatus. Repeat the above process with a liquid.
5. The coefficient of viscosity can be calculated by the following formula.

Where,
η - Coefficient of viscosity of liquid
NH₂O - Coefficient of viscosity of water
d, - Density of liquid
dH₂O - Density of water
1- Time taken by liquid to flow from M to M'
2- H₂O - Time taken by water to flow from M to M

34. Explain Henry’s law

According to Henry's law, at a constant temperature the amount of gas dissolved in a definite
volume of the solvent is proportional to the pressure of the gas which is in equilibrium with the
solution.
i.e., m a P:
m = k.P
Where,
m-Mass of gas dissolved in unit volume of solvent
P - Equilibrium pressure of the gas
k - Proportionality constant
Gases are soluble (absorbed) in liquid to some extent. The solubility of a gas in liquid depends on
nature of gas, temperature of gas-liquid system and on pressure of the gas.
Following conditions are to be satisfied to apply Henry's law,
1. The pressure of the gas should not be too high.
2. Temperature of the system should not be two low.
3. Gas should not undergo either association or dissociation and it should not be much soluble in
solvent.
4. If liquid obeys Raoult's law over a range of composition, then gas should obey Henry's law over
the same range of composition of liquid.

35. Explain about non-ideal system.

Answer: Most of the liquid solutions deviate from Raoult's law and do not behave ideally. These type
of solutions are known as non-ideal solutions. The deviations may be due to either non - ideality of
either vapour phase or solution.
Real or Non Ideal Solutions
Solutions that deviate from Raoult's law are termed real solutions. In other words, real solutions do
not obey Raoult's law and the deviation from the law may be either positive or negative. Such
deviations arise due to unequal forces of interaction between solute-solute, solute-solvent and
solvent-solvent. Final volume of the real or non-ideal solutions is not equal to the sum of individual
components. Heat is either evolved or absorbed during the mixing process.
When the adhesive force between different components is more than the cohesive force between
the same components, vapour pressure of the solution is less than the sum of the partial pressures
of individual components resulting in a negative deviation from the Raoult's law. This is observed
during salt formation, hydration or hydrogen bonding between the components of the solution.

36. Explain about azeotropes.

Answer: Azeotropes
Azeotropes are the mixtures of liquids which boil at constant temperature like a pure liquid such
that the distillate has the same composition as that of the liquid mixture. Azeotropes are also called
as constant boiling mixture or azeotropic mixtures.
Azeotropes are classified into two types
(i) Minimum boiling azeotropes
(ii) Maximum boiling azeotropes
(i) Minimum Boiling (Point) Azeotropes
Liquid pairs which show positive deviations from ideal behaviour form maximum boiling azeotropes.
These azeotrope correspond to an intermediate composition where the total vapour pressure is the
highest and the boiling point is the lowest. These azeotropes have low boiling points than either of
the pure components.
Example: Ethyl alcohol - water system
(ii) Maximum Boiling (Point) Azeotropes
Liquid pairs which show negative deviations from ideal behaviour form maximum boiling azeotropes.
These azeotrope correspond to an intermediate composition where the total vapour pressure is
lowest and the boiling point is highest. These azeotropes have high boiling points than either of the
pure components.

37. Theory of Sodium Carbonate Extract, Classification and Reactions of Anions 2- CO, Cl, Br, SO,
PO, BO, CH, COO, NO. Interfering lons
Sodium carbonate is a resulting solution obtained when a salt is boiled for a long tin with a strong
solution of Na, CO,. During this, double decomposition takes place and insolub salt gets converted
into the soluble sodium salt. The carbonates thus formed are of heavy metall radicals while sodium
salts of acid radicals.
The excess unreacted Na, CO, must be neutralised or destroyed by a suitable acid before testing. The
selection of acid depends on the radical to be identified.
In a given salt solution, cation is removed or precipitated as carbonate and anion remains as sodium
salt in the solution. Only alkali metal carbonates are insoluble irrespective of any condition.
BaSO, + Na₂CO, Na₂SO₄ + BaCO,
(Salt) (Aqueous (Aqueous (Salt)
solution) solution)
BaSO, cannot be used for testing sulphate radical. When BaSO, salt (which is insoluble) reacts with
Na,CO, aqueous solution, it gets converted into a soluble form as Na₂SO₄. The presence of sulphate
radical can be tested from extract.
2Na₃PO₄ + 3CaCO3 Ca3 (PO4)2+3Na2CO3
(Salt) (Aqueous (Aqueous (Salt)
solution) solution)
Ca3 (PO4)2 cannot be used for testing phosphate. In this, insoluble calcium phosphate forms soluble
sodium phosphate on preparation of sodium carbonate extract. Hence, presence of phosphate can
be tested from the extract.

38. An organic compound contains Hg2+, Ad^{+} , Pb^{+} ions. How will you identify them?
Explain with chemical equations.
Answer :
The separation and identification of all the cations depend on solubility product, common ion effect
and other chemical reactions like precipitation, complexation and redox reaction.
Separation and Identification of Group I Individual Cations
The cations of group I include Ag+, Hg_{2}^{2+} and Pb2+ which precipitate as chlorides on reacting
with diluted HCl.
Separation and Identification of Pb^{2+} ion Separation of PbCl, from Hg_{2}Cl_{2} and AgCl
The PbCl, can be separated by boiling the 7. precipitate which contains PbCl₂, AgCl and Hg_{2}Cl_{2}
followed by filtering hot.
As a result, PbCl, dissolves in hot water but can be separated as needles once the solution gets
cooled. Identification of Pb^{2+} Ion
When K_{2}CrO_{4} is added to the hot PbCl, solution, it precipitates yellow PbCrO4. This confirms
the presence of Pb^{2+} ion.
PbCl2 + K2CrO,
PbCrO4 + 2KCI
(Yellow precipitate)
Separation and Identification of Ag+ and Hg_{2}^{2+} Ions Separation of AgCl from Hg Cl_{2}
To separate AgCl, the left over precipitate containing (AgCl+Hg_{2}Cl_{2}) is combined with diluted
NH_{4}OH solution.

As a result, AgCl dissolves into the solution and forms diammine silver(1) [Ag(NH,),]*. In contrast,
Hg,Cl, precipitates as a black mercuric amino chloride [Hg + Hg(NH2)CI].
AgCl + 2NH Oн →[Ag(NH),] CI + 2H₂O
Identification of Ag lon
The reaction of solution obtained in above reaction when treated with diluted HNO,, gives white
precipitate of AgCl. [Ag(NH), CI] + dil HNO,
AgCl + 2NH, NO, (White precipitate)
From the white precipitate, it confirms the presence of Ag ion. Identification of Hg; Ion
The reaction of Hg,Cl, with ammonium hydroxide (NH,OH), gives a black precipitate of mercury and
mercuric amino chloride. Hg,Cl₂ + 2NH Oн →HgNH CI+ Hg + NH4Cl + 2H₂O
From the above reaction, it confirms the presence of Hg ion. Chart for Separation and Identification
of Group I Cations
Flow Solution of Ag, Pb²" and Hg ions
(Reaction with dil HCl)
▼ AgCl + PbCl + Hg,Cl, (Boiling with hot water and filtered)
Residue
(i) Contains (AgCl + Hg,Cl₂)
(ii) PbCl, Solution + K2CrO₄ → PbCrO₄ + 2KCI
(Yellow precipitate confirms presence of Pb2+)
Filtrate
(i) PbCl, solution, crystals on cooling
(ii) AgCl + 2NH OH→[Ag(NH),]Cl + 2H₂O
(iii) [Ag(NH,),] Ci + dil HNO, → AgCl + 2NH NO, of Agion)
NH CL + 2H.O
(White precipitate confirms presence of Ag+ ion)
(iv) HgCl₂ + 2NH4OH → [HgNHCl + Hg] + NH4Cl + 2H₂O
(Black precipitate confirms presence of Hg2+ ion)

39. Explain the theory of flame test.

In analytical chemistry, flame test is used to visually identify the unknown metal ion based on its
colour characteristic when subjected to a Bunsen flame. During the adsorption of the heat from the
flame, electrons in metal ions excite causing the emission of visible light. The emission spectrum of
an element is different from other elements i.e., different salts give different colours to a flame.
Steps to Conduct a Flame Test
Answer :
1. Initially a platinum or nichrome wire must be taken.
2. The wire must be cleaned with acid (HCl or HNO₂) repeatedly.
3. This wire is then rinsed with distilled water or deionizing water.
4. The wire is then placed in the flame to observe no colour. This ensures that the wire is clean.
5. The clean wire is then dipped into a solid or solution of an ionic salt, which is to be tested.
6. The salt present on the wire is placed in the flame and the change in the flame colour is observed.,
while ле mirror
7 . The respective colour determines the unknown salt.

40. Explain in detail about classification of isomers.

Answer: Isomer
The compounds with same molecular formula but different properties are called as isomers.
Classification of Isomers
represents the classification of isomers

1. Constitutional Isomers
: Classification of isomers
The isomers or compounds which have the same molecular formula but differ in connectivity of
atoms in molecules are known as constitutional isomers and the phenomenon is called
constitutional isomerism. Constitutional isomers are classified into the following types,
(1) Chain Isomers
Chain or skeletal isomers are the compounds which have the same molecular formula but differ in
the structure of carbon atoms, and the phenomenon is known as cham or skeletal isomerism.
Butane (C_{4}H_{p}) the simplest alkane exhibiting chain isomerism

In the same manner, pentane (C,H_{1}) also exhibits cham isomerism because the five carbon atoms
can be linked in three different manners. With an increase in the number of carbon atoms, the
number of chain isomers also increase

(B) Functional Isomers

Functional isomers are the compounds which have the same molecular formula but differ in the
functional groups, and the phenomenon exhibited by them is known as functional isomerism
Examples
1. CH3OCH3 2. CH{3}CH{2}COOH 3. C2H5OH 4. CH3COOCH3
Dimethylether Propionic Acid Ethanol Methyl Acetate

(iii) Positional Isomers

Positional isomers are the compounds which have the same molecular formula but differ in the
position of a particular atom or group on the carbon chain, and the phenomenon exhibited by them
is known as positional isomerism.

Examples
1. CH3 CH2 CH2 CI CH3 CH CH3
1-Chloropropane CI
2-Chloropropane

2. CH3-CH2-CH=CH2 CH3-CH=CH-CH3
1-Butane 2-Butane

2. Stereoisomers
The isomers or compounds which have the same structural formula, same connectivity but differ in
special arrangement of atoms or groups in molecules are known as stereoisomerism and the
phenomenon is called stereoisomerism.
Stereoisomers are classified into two types depending on inter convertibility. They are,
(i) Conformational isomers
(ii) Configurational isomers
41. What is conformational analysis? Write the conformational analysis of ethane.
Answer : Conformational Analysis
Conformational analysis is defined as, the study of energy relations between the conformers.
Conformational Analysis of Ethane
The two methyl groups of ethane rotate freely about the single bond to give rise to several spatial
arrangements (conformations) among which the two extreme conformations are staggered and
eclipsed conformations. These can be represented by saw-horse drawings or by Newman projection.

Both the conformations of ethane are interconvertible by rotation around the C C single bond.
Hence, these are known as rotamers or rotational isomers. However, such interconversion requires
thermal energy, (3 kcal/mole) which is easily available at room temperature. Hence, at room
temperature both the forms of ethane exit which cannot be easily separated. Both these rotamers
have similar physical and chemical properties, but have different energies and stabilities.
In eclipsed form, the hydrogen atoms are nearer to each other resulting in greater repulsive force.
This makes this form less stable and of higher energy. The staggered form is more stable and of
lowest energy because the hydrogen atoms in the molecule are far away resulting in lower repulsive
forces. Hence, at any ■ given time, staggered form of ethane molecule is found to be predominant
because it is of lower energy and is more stable. Figure below represents the energy changes
resulting from rotation about carbon-carbon bond of ethane.

42. Explain conformational analysis of n-butane.

Conformation of n-Butane
Butane with a structural formula CH-CH-CH-CH, also exits in staggered and eclipsed conformations.
Staggered Conformation
Each of the two carbon atoms are linked with bulky methyl groups. Due to this, the staggered
conformation is of the following two types, based on the distance between the two methyl groups in
the molecule,
1. Anti conformation: In this conformation, the distance between the two bulky methyl groups
is maximum
2. Gauche conformation: In this conformation the distance between the two bulky methyl
groups is minimum.
Eclipsed Conformation
In butane, apart from eclipsed conformation, a new conformational form of highest energy is also
formed which is called fully eclipsed conformation of butane. In this, the two bulky methyl groups
are very near to each other, resulting in greater steric repulsion and higher energy.
When the energy diagram showing energy differences between different conformations of butane is
referred, it is observed that the anti form is the most stable, followed by the gauche form. The fully
eclipsed conformation is of the highest energy and least stable. Figure below represents the energy
changes resulting from carbon-carbon bond of butane

In higher alkanes, among staggered conformations anti form is more predominant because it than
the gauche form. Since, alkanes are made up of single bonds, the molecules are easily single bond
and hence, the conformations are interconvertible.

43. Explain the conformational analysis of 1, 2 Dichloroethane.

1, 2-Dichloroethane with the structural formula C2H4Cl2 exhibits the staggered conformation.

Each of the two hydrogen atoms are linked with bulky chlorine atoms resulting two types of
staggered configuration i.e., anti and gauche configuration. These conformations are obtained by
measuring dipole moment. The dipole moment in anti conformation is expected to have nearly zero-
dipole while in gauche conformation, it increases with temperature.

1.Anti Conformation: In this conformation, the distance between the two bulky chlorine atoms is
maximum.
2.Gauche conformation: In this conformation, the distance between the two bulky chlorine atoms is
minimum.
Thus, the energy difference between the global maximum and minimum in the 1, 2-dichloroethane
is four times greater than that of ethane molecule and stability of anti conformation is more than
the guache conformation and eclipsed conformation.
In 1, 2-dichloroethane, apart from eclipsed conformation, a new conformation is formed of highest
energy which is known as fully eclipsed conformation of 1, 2-dichloroethane. In this, the two bulky
chlorine groups are very near to each other resulting a great steric repulsion. CI CI CI
When the energy diagram showing energy differences between different conformations of 1, 2-
dichloroethane is referred, it is observed that the anti form is the most stable followed by the
gauche form.

44. Explain Bayer-strain theory (BST).

Answer : The stabilities of cycloalkanes was first explained by Adolf von Baeyer and the theory was
called Baeyer's strain theory. According to Baeyer, any deviation of bond angles from normal
tetrahedral value results in an internal strain on the ring. Any strain on the ring decreases the
stability of the molecule, Greater the strain greater is the instability of the ring.

Any upward or downward deviation from the normal tetrahedral angle during the formation of ring
creates a strain in the molecule called angle strain, which determines the stability of the ring.

For example, the four valencies of carbon atoms are usually directed towards the corners of a
regular tetrahedron and hence the angle between any two C C bonds is 109° 28'. The three carbon
atoms of a cyclopropane molecule occupy the three corners of an equilateral triangle. Therefore
each C-C-C bond angle is 60°. Hence, the normal tetrahedral value of 109°28' between adjacent
carbon bonds is reduced to 60°. Therefore angle strain of propane or the deviation through which
each bond bends from normal tetrahedral

Moreover, cyclobutane ring is a square with each C-C bond angles being 90°. To fit the geometry of
the ring, each bond shows an angle strain ½ (109 28’ -90° =9 44’.

Similarly, cyclopentane is a pentagonal ring with five carbon atoms and bond between C-C bonds is
108°. Therefore, each bond deviates from the normal tetrahedral value by ½ (109 28’ -90° =0 44’.
The angle strain for other Cycloalkane can be calculated in a similar manner and is illustrated in table
below.
Cycloalkane Angle strain
1. Cyclopropane +24 44’
2. Cyclobutane +9 44’
3. Cyclopentane +0 44’
4. Cyclohexane -5 16’

Table

From the above table, it is clear that has the greatest angle strain and hence should be the most
unstable. Cyclopropane overcomes the strain in its rings by undergoing ring-opening reactions with
reagents like HBr, Br₂, H, etc. Such reactions help cyclopropane to release the strain within it.
However, the angle strain in cyclobutane is lower than that of cyclopropane, hence it is
comparatively more stable, undergoing ring-opening only under drastic conditions. Cyclopentane
has the least angle strain, is most stable and hence does not take part in ring-opening reactions.
The angle strain of cyclohexane is greater than cyclopentane. In case of other higher cycloalkanes, as
the carbon atoms increase, the ring strain also increases. Hence cyclohexane and other higher
cycloalkanes should be less stable and more reactive. However, it has been found that cyclohexane
and other cycloalkanes are more stable and undergo substitutions reactions like alkanes, rather than
ring- opening reactions exhibited by cyclopropane, butane and pentane.

45. Law of Symmetry

Ans. Law of symmetry states that "All the crystals of the same substances possess the same set of
symmetry elements". The symmetry elements found in crystals are

(i) Plane of symmetry

(ii) Axis of symmetry
(iii) Centre of symmetry
(i) Plane of Symmetry
The imaginary plane bisects the crystal into two equal parts such that the parts are mirror image to
each other. For cubic crystals, there are two types of planes of symmetry.

(a) Rectangular plane of symmetry

(b) Diagonal plane of symmetry

(a) Rectangular plane of symmetry

The plane which passes through the midpoint of the edges and is parallel to opposite crystal faces is
said to be rectangular plane of symmetry. There are three rectangular planes of symmetry.

(b) Diagonal Plane of Symmetry : The plane which passes through the diagonal of opposite faces is
referred as diagonal plane of symmetry. There are three pairs of opposite faces, each pair possesses
two diagonals as shown in figure (iii). Thus, there are six diagonal planes of symmetry in a cubic
crystal.

Therefore, the total number of planes of symmetry in a cubic crystal =(3+6)=9.

(ii)Axis of Symmetry : It is an imaginary line or axis about which the crystal is rotated through 360"
to get identical appearance in one complete rotation. Depending upon the number of times the
identical appearance occurs in one complete rotation of 360°, axes of symmetry are three types,

1. Axis of two fold symmetry

2. Axis of three fold symmetry
3. Axis of four fold symmetry
1. Axis of Two Fold Symmetry : This axis passes through the centres of two diagonally opposite
edges of cube as shown in figure (iv)(a). On rotation about this line gives two identical appearance of
cube after every 180° rotation. Thus, in a cubic crystal there are six such diagonally opposite pairs
present hence six two fold axes are possible.
2. Axis of Three Fold Symmetry : This axis or line passes through the opposite corners of cube along
the body diagonal as shown in figure (iv)(b). On rotation about this line gives three identical
appearance of cube after every 120° rotation. Thus, in a cubic crystal there are four such diagonally
opposite pairs present hence four such fourfold axes are possible.

3. Axis of Four Fold Symmetry : This axis passes through the centres of two opposite faces of a cube
as shown in figure (iv)(c). On rotation about this line gives four identical appearances of cube after
every 90° rotation. Thus in a cubic crystal there are three such opposite pairs present hence three
fourfold axes are possible.

Therefore the total number of axis of symmetry in cubic crystal = (6+4+3)=13.

3. Law of Rotationality of Indices : This law states that for any cubic crystal it is possible to
choose three coordinates axes with unit distance a,b, c (not necessary for same length) such that the
ratio of three intercepts of any plane is given by ma: nb: pc. Where m, n and p are either integral
whole number (or) fractions of whole number (or) may be infinity. The ratio m: n:p is the
characteristic of the plane. These coefficients are known as Weiss indices of planes, and the
intercepts a, b, c on co-ordinate axes are crystal parameters.

(ii) Unit Cell : The unit cell is the smallest block from which the entire crystal is built up by
repetition in three-dimensions. It represents the crystal and it reflects all the properties of a crystal.
With reference to a given crystal, there exists a number of possible unit cells. Consider the space
lattice.
The point, which must be considered as unit cell i.e., a conventional unit cell. In fact, it is a matter of
convenience usually a cell with shortest possible size area (axb) in two dimensions and ā.bxĉ volume
in three-dimensions and the sides are chosen as convenient cell. In this respect, a parallelogram A is
chosen. This cell contains lattice point only at the corners. Since, a lattice point is shared by four unit
cells, 1+n/ 4 of a lattice point is associated with this cell and thus, 4 there is a lattice density of one
point associated with this cell. The cell which contains only single lattice point is called primitive cell.
Hence, the unit cell is the primitive cell with minimum area.

46. Derive Bragg's equation.

Ans . Consider a set of parallel lattice planes of a crystal in which spacing between the successive
planes is d. If a narrow beam of x-rays of wavelength 2 be incident on the planes with a glancing
angle 0, the reflected beam leaves the plane at an angle 0 as shown in figure. Consider the rays
reflected at two consecutive planes AA' and BB'. Thus, the rays XO and X'O' are reflected at O and O'
respectively along OY and O'Y' such that,

If OP and OQ are perpendicular lines drawn from O and X'O' and O' and Y' the path difference
between the beams reflected at two consecutive planes will be,

If this path difference is an integral multiple of the wavelength 2, the reflected beam will interfere
constructively giving maximum intensity, i.e., for constructive diffraction. 2dsin 0 = πλ ... (4)

Where, n is an integer (n=1, 2, 3...) Equation (4) is known as Bragg's law.