1.
Enantiomers
These are stereoisomers that are non-superimposable mirror images of each other. They have
identical physical properties (M.P., B.P., solubility) in an achiral environment but rotate plane-
polarized light in opposite directions.
2. Chiral or Asymmetric Carbon Atom
A tetrahedral carbon atom that is bonded to four different atoms or groups is called a chiral or
asymmetric carbon. Its presence is the primary requirement for a molecule to show optical activity.
3. Specific Rotation, Optical Rotation, and Centre of Symmetry
• Optical Rotation: The angle by which the plane of polarized light is rotated when passed
through an optically active substance.
• Specific Rotation: The rotation produced by a solution of $1\text{ g/mL}$ concentration in a
$1\text{ dm}$ tube at a specific temperature and wavelength.
• Centre of Symmetry: An imaginary point in a molecule such that any line drawn through it
meets identical groups at equal distances on opposite sides.
4. Plane of Symmetry and Chirality
• Plane of Symmetry: An imaginary plane that bisects a molecule into two equal halves that
are mirror images of each other.
• Chirality: The property of non-superimposability of a molecule on its mirror image. A
molecule is chiral only if it lacks a plane or center of symmetry.
5. Racemic Mixture and Meso Compounds
• Racemic Mixture: An equimolar mixture of a pair of enantiomers. It is optically inactive due
to external compensation (one isomer cancels the other).
• Meso Compound: A molecule containing two or more chiral centers but possessing an
internal plane of symmetry. It is optically inactive due to internal compensation.
6. Diastereomers
Stereoisomers that are not mirror images of each other. Unlike enantiomers, they have different
physical properties (like melting points and solubility) and can be separated by physical methods.
7. Resolution
The process of separating a racemic mixture into its individual $d$ and $l$ enantiomers is known as
resolution. This is usually done by converting enantiomers into diastereomers.
8. Identification of Optically Active Molecule
Answer: (iii) Butan-2-ol
Reason: In Butan-2-ol ($CH_3-CH(OH)-C_2H_5$), the second carbon is bonded to four different
groups ($-H, -OH, -CH_3, -C_2H_5$), making it chiral and thus optically active.
9. Identification of Chirality Centre
Answer: (i) Sec-butyl chloride and (iii) 3-Bromohexane.
Reason: In both molecules, at least one carbon atom is attached to four distinct groups, satisfying
the condition for a chirality center.
10. Meso Examples
Answer: Meso-tartaric acid and Meso-2,3-dichlorobutane.
Reason: These contain chiral centers but are achiral overall because they possess an internal plane of
symmetry.
11. Highest Dipole Moment
Answer: (i) $CH_2Cl_2$
Reason: In $CCl_4$, the dipoles cancel to zero due to symmetry. In $CH_2Cl_2$, the bond dipoles
reinforce each other more effectively than in $CHCl_3$, leading to the highest net dipole moment.
12. Use of $H_2SO_4$ with Alcohol and KI
Answer: $H_2SO_4$ is a strong oxidizing agent. It oxidizes the $HI$ (produced in situ) into $I_2$,
which prevents the $HI$ from reacting with the alcohol. Phosphoric acid ($H_3PO_4$) is used as a
non-oxidizing alternative.
13. Rate of Hydrolysis
Answer: $C_6H_5CHClC_6H_5$ (Benzhydryl chloride).
Reason: This compound forms a secondary carbocation stabilized by resonance from two benzene
rings, making it more stable and reactive toward hydrolysis than the primary benzyl carbocation.
14. Properties of p-Dichlorobenzene
Answer: Due to its high symmetry, the para-isomer fits more closely into the crystal lattice
compared to ortho or meta isomers. This results in stronger intermolecular forces, leading to a
higher melting point and lower solubility.
15. Faster $S_N1$ Reaction
• (a) 2-Chloro-2-methylpropane: It forms a tertiary ($3^\circ$) carbocation, which is more
stable than a secondary carbocation due to +I effect and hyperconjugation.
• (b) Benzyl Chloride: The benzyl carbocation is highly stabilized by resonance with the
benzene ring, whereas the cyclohexyl carbocation has no such stabilization.
16. Identification of Hydrocarbon $C_5H_{10}$
Answer: The hydrocarbon is Cyclopentane.
Reasoning:
• The molecular formula $C_5H_{10}$ corresponds to either an alkene or a cycloalkane.
• Since it does not react with chlorine in the dark, it cannot be an alkene (which would
undergo addition).
• In bright sunlight, it gives a single monochloro compound ($C_5H_9Cl$). This implies that all
10 hydrogen atoms in the molecule are equivalent. This is only possible in a symmetrical
cyclic structure like cyclopentane.
17. Centre of Chirality and Stereoisomers
(i) 1,2-Dichloropropane:
• Chiral Centre: The second carbon ($C_2$) is chiral because it is attached to four different
groups: $-H, -Cl, -CH_3,$ and $-CH_2Cl$.
• Stereoisomers: Since there is 1 chiral center, $2^n = 2^1 = \mathbf{2}$ stereoisomers (a pair
of enantiomers) are possible.
(ii) 3-Bromo-pent-1-ene:
• Chiral Centre: The third carbon ($C_3$) is chiral. It is attached to $-H, -Br, -CH=CH_2$ (vinyl
group), and $-CH_2CH_3$ (ethyl group).
• Stereoisomers: With 1 chiral center, $\mathbf{2}$ stereoisomers are possible.
18. Difference between Enantiomers and Diastereomers
Property Enantiomers Diastereomers
Non-superimposable mirror Stereoisomers that are not mirror
Relationship
images. images.
Physical
Identical (B.P., M.P., solubility). Different physical properties.
Properties
Rotate light in equal but May rotate light differently or not
Optical Rotation
opposite directions. at all (if meso).
$d$-Tartaric acid and Meso-tartaric
Example $d$ and $l$ lactic acid.
acid.
19. Storage and Uses of Chloroform ($CHCl_3$)
Storage: Chloroform is stored in closed, dark-coloured bottles filled up to the brim to prevent its
oxidation by air in the presence of light into a poisonous gas called Phosgene ($COCl_2$).
$$2CHCl_3 + O_2 \xrightarrow{light} 2COCl_2 + 2HCl$$
Four Uses:
1. As an industrial solvent for fats, waxes, and resins.
2. In the production of Freon refrigerant (R-22).
3. As a laboratory reagent (e.g., in the Reimer-Tiemann reaction).
4. Historically used as an anesthetic (though now replaced by safer alternatives).
20. Optical Activity Identification
Answer: (i) and (iii) will show optical activity.
Justification:
• (i) Tartaric acid: Contains chiral carbons and lacks a plane of symmetry (in its $d/l$ forms).
• (ii) Isopropyl alcohol ($CH_3-CH(OH)-CH_3$): Inactive. The central carbon is attached to two
identical methyl groups, so it is achiral.
• (iii) 2,3-Dichlorobutane (non-meso): The structure shown has chiral centers. As long as it
isn't the meso form, it is optically active.
21. Boiling Point and Nucleophilic Substitution
[a] Higher Boiling Point:
• Answer: 1-Chloropentane has a higher B.P. than 2-methyl-2-chlorobutane.
• Reason: 1-chloropentane is a straight-chain isomer with a larger surface area, leading to
stronger van der Waals forces. Branching (in 2-methyl-2-chlorobutane) makes the molecule
spherical, decreasing surface area and lowering the B.P.
[b] p-Nitrochlorobenzene vs. Chlorobenzene:
• Answer: p-Nitrochlorobenzene reacts faster.
• Reason: The $-NO_2$ group is a strong electron-withdrawing group (-I and -R effect). It
stabilizes the intermediate carbanion (Meisenheimer complex) by withdrawing electron
density from the benzene ring, especially when located at the para position. Chlorobenzene
lacks this activation, making it less reactive toward nucleophiles.
22. Dipole Moment: Chlorobenzene vs. Cyclohexyl Chloride
• Answer: Chlorobenzene has a lower dipole moment.
• Reason: In Chlorobenzene, the carbon is $sp^2$ hybridized (more electronegative), which
reduces the electron-withdrawing power of Chlorine. In Cyclohexyl Chloride, the carbon is
$sp^3$ hybridized. Additionally, the resonance in chlorobenzene causes a $C—Cl$ bond with
partial double-bond character, shortening the bond length ($d$). Since Dipole Moment $\mu
= q \times d$, the smaller bond length and $sp^2$ hybridization result in a lower $\mu$.
23. Immiscibility of Alkyl Halides in Water
• Answer: Alkyl halides are polar but cannot form Hydrogen bonds with water.
• Reason: For a substance to dissolve in water, the energy released during new bond
formation must exceed the energy required to break existing $H$-bonds in water. Alkyl
halides cannot break the strong $H$-bonds between water molecules.
24. Grignard Reagents Preparation
• Answer: They must be prepared under anhydrous (dry) conditions.
• Reason: Grignard reagents ($R—MgX$) are highly reactive. Even traces of moisture will
decompose them into hydrocarbons:
$$RMgX + H_2O \rightarrow R—H + Mg(OH)X$$
25. p-Dichlorobenzene Properties
• Reason: Due to its symmetrical structure, the para-isomer fits more closely into the crystal
lattice than the ortho or meta isomers. This symmetry leads to stronger intermolecular
attractions, resulting in higher Melting Point and lower solubility.
26. Aqueous vs. Alcoholic KOH
• Aqueous KOH: Contains $OH^-$ ions which act as a strong Nucleophile, leading to
Substitution to form Alcohols.
• Alcoholic KOH: Contains Alkoxide ions ($RO^-$) which act as a strong Base. This leads to
$\beta$-Elimination (Dehydrohalogenation) to form Alkenes as the major product.
27. Ease of Hydrolysis
• Answer: $C_6H_5CHClC_6H_5$ is hydrolysed more easily.
• Reason: It forms a secondary carbocation stabilized by resonance from two benzene rings,
whereas $C_6H_5CH_2Cl$ forms a primary benzyl carbocation stabilized by only one ring.
28. KCN vs. AgCN Reaction
• KCN: It is ionic. Both $C$ and $N$ can donate electrons, but $C—C$ bonds are stronger than
$C—N$ bonds, so Alkyl Cyanides ($RCN$) are formed.
• AgCN: It is predominantly covalent. Only the Nitrogen atom has a lone pair available for
bonding, resulting in Alkyl Isocyanides ($RNC$).
29. Addition of KI to RCl Hydrolysis
• Reason: $I^-$ is a better nucleophile than $OH^-$ and also a better leaving group than $Cl^-
$. It first replaces $Cl$ to form $RI$, which is then much more rapidly hydrolysed by $OH^-$
than the original $RCl$.
30. $S_N2$ Reactivity Order (Increasing)
• Order: $(CH_3)_2CHCl < CH_3CH_2Cl < CH_3Cl < CH_3Br$
• Reason: $S_N2$ reactivity decreases with increasing steric hindrance ($1^\circ > 2^\circ >
3^\circ$). $CH_3Br$ is faster than $CH_3Cl$ because $Br^-$ is a better leaving group.
31. $S_N1$ Reactivity Order (Decreasing)
• Order: $CH_2=CHCH(Cl)CH_3 > CH_3CH_2CH(Cl)CH_3 > CH_3CH_2CH_2Cl$
• Reason: $S_N1$ depends on carbocation stability. Allylic carbocations (from the first
molecule) are resonance-stabilized. Secondary carbocations ($2^\circ$) are more stable than
primary ($1^\circ$).
32. Hydrolysis Comparisons
1. Allyl Chloride vs n-Propyl Chloride: Allyl chloride forms a resonance-stabilized carbocation,
making it more reactive in $S_N1$.
2. Vinyl Chloride vs Ethyl Chloride: Vinyl chloride is extremely slow due to the resonance
between Chlorine and the double bond, giving the $C—Cl$ bond partial double-bond
character which is harder to break.
33. Substitution Types
• Haloalkanes: Undergo Nucleophilic Substitution because the polar $C—X$ bond creates an
electron-deficient carbon.
• Haloarenes: Undergo Electrophilic Substitution because the electron-rich $\pi$-cloud of the
benzene ring attracts electrophiles.
34. Chlorine: Withdrawing yet Ortho-Para Directing
• Reason: Chlorine has two opposing effects:
1. -I effect (Inductive): Withdraws electrons, deactivating the ring.
2. +R effect (Resonance): Donates a lone pair to the ring, increasing electron density
specifically at ortho and para positions. The resonance effect determines the
direction, while the inductive effect determines the reactivity.
35. Faster $S_N2$ Reaction
1. $C_6H_{11}CH_2Cl$ (Cyclohexylmethyl chloride): It is a $1^\circ$ halide, while the other is a
$2^\circ$ halide. $S_N2$ prefers $1^\circ$ due to less steric hindrance.
2. $CH_3CH_2CH_2CH_2I$: $I^-$ is a better leaving group than $Cl^-$.
36. Reactivity Prediction
• (a) $S_N1$: $3^\circ > 2^\circ > 1^\circ$ | $S_N2$: $1^\circ > 2^\circ > 3^\circ$.
• (b) $S_N1$: Reactivity increases with the number of phenyl groups because the resulting
carbocations are stabilized by more resonance.
37. $S_N2$ Arrangement (Increasing Order)
1. 2-Bromo-2-methylbutane ($3^\circ$) < 2-Bromopentane ($2^\circ$) < 1-Bromopentane
($1^\circ$).
2. 2-Bromo-2-methylbutane ($3^\circ$) < 2-Bromo-3-methylbutane ($2^\circ$) < 1-Bromo-3-
methylbutane ($1^\circ$).
3. 1-Bromo-2,2-dimethylpropane < 1-Bromo-2-methylbutane < 1-Bromo-3-methylbutane < 1-
Bromobutane.
(Note: For $1^\circ$ halides, reactivity decreases as branching near the chiral center increases).