9.

Explain valence bond structure of

Carbon monoxide molecule
The electronic configuration of CC is 1s^22s^22p^2.1s
2
2s
2
2p
2
..
Consider formation of two sp-sp−hybrid orbitals, one
directed toward oxygen and directed 180^o180
o
opposite.
This contains carbon lone pair, leaving empty spsp hybrid
orbitals with a filled oxygen \sigmaσ-orbital.
To complete the octet, C forms a pi bond and a dative bond.
Hence, the valence bond structure of carbon
monoxide is best described as : C \equiv O:C≡O
with a dative bond from oxygen atom to the less
electronegative carbon atom.
OR

The electronic configuration of C is 1s22s22p2..

Consider formation of two sp−hybrid orbitals, one directed toward oxygen and
directed 180o opposite.
This contains carbon lone pair, leaving empty sp hybrid orbitals with a filled
oxygen σ-orbital.
To complete the octet, C forms a pi bond and a dative bond.
Hence, the valence bond structure of carbon monoxide is best described
as :C≡O with a dative bond from oxygen atom to the less electronegative carbon
atom.
 10.Draw the molecular orbitals formed by the S-S
combination of atomic orbitals also illustrate the
electron densities for these orbitals and explain them

When these atomic orbitals

combine, the electron density
increases and the shaped formed is
given below .
Explanation:
Orbital
It is a region where probability of finding the electron is
maximum.
In quantum mechanics, electron configurations of atoms are
described as wave functions.The orbitals can combine in
two ways : Either their region adds up or the regions get
subtracted .

1. The addition of orbitals give rise to bonding orbitals and

subtraction of orbitals give rise to anti-bonding orbitals .
2. The mutual overlap between the half filled "S" orbitals of
two atoms is called s – s overlap and the covalent bond
formed is known as sigma (s) bond.

The mutual overlap of p-p bond occurs in two ways :

If it occurs along the inter-nuclear axis --the bond formed is
Sigma bond .
If it occurs side to side overlapping --the bond formed is pi
bond
 11.

The propertie of some compounds to have same chemical

properties but different structures is called as structural
isomers.
Example of butane is given below:

OR
Structural isomerism refers to the chemical phenomenon
in which two or more compounds have the same molecular
formula but different bonding patterns and atomic
organisations. They are of 3 types :-
1. chain isomers
2. functional group isomers
3. positional isomers
HOPE IT HELPS(:
Explanation: Structural Isomers have the same molecular
formula but different arrangements of atoms. There are
three types of structural isomers: chain isomers, functional
group isomers and positional isomers. Chain isomers have
the same molecular formula but different arrangements or
branches.

12. What are racemic mixtures? Discuss their resolution involving the formation of
diastereomers

In chemistry, a racemic mixture, or racemate (/reɪ

ˈsiːmeɪt, rə-, ˈræsɪmeɪt/), is one that has equal
amounts of left- and right-handed enantiomers of a
chiral molecule. The first known racemic mixture
was racemic acid, which Louis Pasteur found to be
a mixture of the two enantiomeric isomers of
tartaric acid.
A racemic mixture is a 50:50 mixture of two
enantiomers. Separation of racemates into their
component enantiomers is a process called
resolution. Since enantiomers have identical
physical properties, such as solubility and melting
point, resolution is extremely difficult.
OR
13. drawNewman and Sawhorse projection for the eclipsed
and straggered conformations of ethane. Whichof these is
conformations is more stable and Why???
 in staggered form of ethane, the electron
clouds of carbon-hydrogen bonds are as far apart as possible. Thus, there
are minimum repulsive forces, minimum energy and maximum stability of
the molecule. On the other hand, when the staggered form changes into
the eclipsed form, the electron clouds of the carbon-hydrogen bonds come
closer to each other resulting in increase in electron cloud repulsions. To
check the increased repulsive forces, molecule will have to possess more
energy and thus has lesser stability

14. Compare the relative acidities of ethanoic acid,

propanoic acid, fluoroethanoic acid andiodoethanoic
acid. Explain your answer giving appropriate reasons.

+-The relative acidities of ethanoic acid, propanoic acid,

fluoroethanoic acid and iodoethanoic acid is given as :
Fluoroethanoic acid > Iodoethanoic acid > Ethanoic acid >
Propanoic acid.
- With the increase of the carbons in the chain, acidity of
carboxylic acid decreases. Hence, ethanoic acid is more
acidic than propanoic acid.
- The acidity of carboxylic acid increases with the increase
of the electronegativity of adjacent groups. Hence,
iodoethanoic acid is more acidic than ethanoic acid and
fluoroethanoic acid is even more acidic than iodoethanoic
acid.
- So the correct order of acidity is :
Fluoroethanoic acid > Iodoethanoic acid > Ethanoic acid >
Propanoic acid
OR

15. Which is more stable in each pair given below? Give reasons for your answer.

(a)see the question paper

(b)
(c)

In the first pair, the first compound is the most stable, since the carbation is unstable if the
positive charge is at the carbon atom that contains the acceptor group.
In the second pair of particles, the second is the most stable, since the chlorine pulls the
electron density on itself, thereby destabilizing the radical if the unpaired electron is in the b-
position relative to the chlorine.
Answer:
a) - 1
b) - 2
The stability of the radical decreases in the following series:
tertiary>secondary>primary.
 Therefore, the most stable radical in this variant is C (CH3) 3
Answer:
C (CH3) 3

16. (a) Explain the following:

(i) Wurtz reaction, has limited synthetic applications.
(ii) Alkanes are relatively unreactive or do not react with
most of the reagents.
(iii) Physical constants like boiling points, densities, etc. of
alkanes generally increase with
increase in the number of carbon atoms.

(a) Synthesize only Symmetric Alkanes

Explanation:
Wurtz reaction chemical reaction is as follows -
→
Limitations of this reaction are listed below -

 By Wurtz's reaction, we can synthesize only symmetric

alkanes a mixture of alkane products is formed when
dissimilar alkanes are reacted (these mixtures are difficult
to separate).
 Using the Wurtz reaction methane cannot be synthesized
because the product formed must have at least two carbon
atoms
 When tertiary alkyl halides are used as the reactant then
Wurtz coupling reaction does not occur
 A side reaction exists with which an alkene product is
formed.

(B) Alkanes are generally unreactive. Alkanes contain only

C–H and C–C bonds, which are relatively strong and difficult
to break. The similar electronegativities of carbon and
hydrogen give molecules which are non-polar.

(C) Physical properties

The boiling points of alkanes increase with increasing number of carbons. This
is because the intermolecular attractive forces, although individually weak, become
cumulatively more significant as the number of atoms and electrons in the
molecule increases

16.(B)

International Space Station life support. ... NASA is

(i)
using the Sabatier reaction to recover water from
exhaled carbon dioxide and the hydrogen previously
discarded from electrolysis on the International Space
Station and possibly for future missions. The other
resulting chemical, methane, is released into space.
Explanation:
NASA is using the Sabatier reaction to recover water
from exhaled carbon dioxide and the hydrogen
previously discarded from electrolysis on the
International Space Station and possibly for future
missions. The other resulting chemical, methane, is
released into space

(ii) The reaction

The solid sodium salt of a carboxylic acid is mixed

with solid soda lime, and the mixture is heated.

For example, if you heat sodium ethanoate with soda

lime, you get methane gas formed:

This reaction can be done with certain carboxylic

acids themselves. For example, benzene can be made
by heating soda lime with solid benzoic acid
(benzenecarboxylic acid), C6H5COOH

17.(a)

Saytzeff's rule states that “ more substituted an alkene is, more stable it is and hence,
more easily it is formed.”

Examples :

CH3CH(Cl)CH2CH3 (2-chlorobutane) on treatment with alc.KOH gives two products, 1-

butene (CH3CH2CH=CH2) which is a minor product and 2-butene (CH3CH=CHCH3)as
the major product.

This can be explained based on saytzeff's rule that's 2-butene is more substituted than
1-butene
OR

Answer. According to Saytzeff rule "In dehydrohalogenation reactions, the preferred product
is that alkene which has the greater number of alkyl groups attached to the doubly bonded
carbon atoms." For example: The dehydrohalogenation of 2-bromobutane yields two
products 1-butene and 2-butene

17.(b)

(i) The solvated electrons (the free electrons in the solution of sodium in liquid ammonia which
are responsible for the intense blue colour) add to the aromatic ring, giving a radical anion. This
radical anion is supplied with a proton by the alcohol. The alcohol also supplies another proton to
the penultimate carbanion. Now, with the alcohol present, the products – cyclohexadiene and an
alkoxide ion are formed. The Birch reduction mechanism is illustrated below.

Thus, the required 1,4 cyclohexadiene where two hydrogen atoms are attached on opposite
ends of the molecule is formed. Alternative organic solvents such as tetrahydrofuran can be
employed instead of ammonia since liquid ammonia must be condensed into a flask and left to
evaporate overnight post the completion of the reaction (which is a time-consuming task)

(ii)Wittig Reaction Mechanism

The Wittig reaction mechanism proceeds via three steps. These steps are:
Step 1: The negatively charged carbon belonging to the ylide is nucleophilic. This carbon
proceeds to execute a nucleophilic attack on the carbonyl carbon of the aldehyde or ketone. This
leads to the formation of a charge separated (and dipolar) intermediate called a betaine. This
step can be illustrated as follows:

Step 2: The betaine intermediate which is formed in step 1 is now subject to the formation of a
new oxygen phosphorus bond, yielding another intermediate which has a four-membered ring
structure. This step is illustrated below:
Step 3: In the four-membered ring intermediate, the carbon-oxygen bond and the carbon-
phosphorus bonds are cleaved. The oxygen takes both the bonding electrons and forms a new
double bond with the phosphorus which lost the bonding pair of electrons to the carbon atom. A
new carbon-carbon double bond is formed with this electron pair as well, yielding the required
alkene product. This step is illustrated below.

(iii) When an alkyl halide is heated with concentrated solution of KOH, a

molecule of hydrogen halide eliminated and an alkene forms. This reaction is
called dehydrohalogenation

18. what are the difference between markownikoffs and anti

markownikoff's rules

Difference Between Markovnikov Rule And Anti

Markovnikov Rule In Tabular Form
BASIS OF
MARKOVNIKOV RULE
COMPARISON
The Markovnikov rule states
that in addition reactions of
alkenes or alkynes, the proton
Description is added to the carbon atom
that has the greatest number
of hydrogen atoms attached to
it.
The mechanism of
Mechanism Markovnikov rule in chemistry
is an ionic mechanism.
The hydrogen atom is attached
to the carbon atom with the
Hydrogen Atom
highest number of hydrogen
substituent.
No medium is required in
Medium
Markovnikov rule.
The electronegative part of the
alkyl halide usually goes to the
Electronegative
carbon which consists of the
Part Of Alkyl
least number of hydrogen
Halide
atoms attached to a carbon
atom in Markovnikov rule.
The carbocation, which is the
intermediary in this reaction,
Rearrangement
then undergoes a
Reaction
rearrangement which increases
the stability of carbocation.
HBr, HI, HCl and H2O are the
Reactants reactants that are used in
Markovnikov rule.
In Markovnikov rule major
product is given by HBr from
Products
(CH3)2C=CHCH3 will produce
(CH3)2CBrCH2CH3
Attack On The hydrogen ion from the
Carbon-Carbon reactant HX in Markovnikov
Bond rule starts the attack on the
ANTI-MARKOVNIKOV RULE
Anti Markovnikov rule states that
in addition reactions of alkenes
or alkynes, the proton is added
to the carbon atom that has the
least number of hydrogen atoms
attached to it.
The mechanism of anti
Markovnikov rule is a free radical
mechanism.
The hydrogen atom is attached
to the carbon atom with the
least number of hydrogen
substituent
A medium is required for anti
Markovnikov rule. The medium
is generally Peroxide or
ultraviolet.
The electronegative part of alkyl
halide attaches to the carbon
atom that consists of the highest
number of hydrogen atoms
attached to the carbon atom in
anti Markovnikov rule.
The produced intermediary does
not undergo rearrangement.
HBr is the only free reactant that
is used in anti Markovnikov rule
and HCl, or HI are not used in
this kind of addition reaction.
In the presence of peroxide, the
main product of anti
Markovnikov rule will be given as
(CH3)2CHCH(Br)CH3
Halogen-free radical X, which is
formed by the communication
between HX and the radical
 peroxide, usually starts the
carbon-carbon double bond. attack on carbon-carbon double
bond in anti Markovnikov rule.

The Markovnikov addition of

The creation of carbon-free
hydrogen halide to olefin
Reaction radical is generally known as the
usually results in the
Intermediary reaction intermediary in anti
production of carbocation as
Markovnikov rule.
the reaction intermediary.

Examples of Markovnikov and Anti-Marknovnikov Addition

Reactions

The Hydration of Alkenes

When alkenes are treated with certain aqueous acids (usually sulfuric acid), the resulting
electrophilic addition reaction yields an alcohol as the product. The regioselectivity of such
reactions can be predicted by Markownikoff’s rule. Therefore, these reactions can be classified
as Markovnikov reactions. In the hydration of alkenes, the H+ ion acts as an electrophile and
attacks the alkene to generate a carbocation intermediate (the intermediate with greater stability
is protonated). The subsequent nucleophilic attack on the carbocation by water molecules forms
an oxonium ion, which is deprotonated to afford the required alcohol product.

The Hydroboration/Oxidation of Alkenes

When alkenes are treated with borane (BH3) in the presence of hydrogen peroxide or sodium
hydroxide, an alcohol is obtained as the final product. In this electrophilic addition reaction, the
boron atom acts as an electrophile. This reaction does not obey Markovnikov’s rule and can,
therefore, be classified as an anti-Markovnikov reaction.

19.
Vicinal dihalides, compounds that have halogens on adjacent carbons, are prepared by the
reaction between a halogen and an alkene. The simplest example is the reaction between
ethylene and chlorine to give 1,2-dichloroethane (ethylene dichloride)
The geminal dihalides or gem-dihalides are the organic compounds in which two halogen
atoms are attached to same carbon atom
Stereoselective Reaction: A reaction in which there is a choice of pathway, but the product
stereoisomer is formed due to its reaction pathway being more favourable than the others
available
Catalyst poisoning refers to the partial or total deactivation of a catalyst by a chemical
compound. Poisoning refers specifically to chemical deactivation, rather than other
mechanisms of catalyst degradation such as thermal decomposition or physical damage

19.(B) How would you prepare following compounds

from an internal alkyne? Give the mechanism ofthe
reactions.

(i) 3-Hexanone

(ii) Ethanoic acid

3-hexanone
______________________________________
structural formula would be like this- Ch3-ch2-ch2-c--o-ch2-
ch3 (-- this refers to double bond)
Refer to the attachment for 3-Hexanone
______________________________________
Now Ethanoic acid is as follows
Structural formula of Ethanoic acid- Ch3cooh or Ch3c--oh (--
refers to double bond)
Refer to the attachment for Ethanoic acid