CBSE 2024 Compartment Chemistry Set-3 (56/S/3)

Solutions

SECTION A

Questions no. 1 to 16 are Multiple Choice type Questions, carrying 1

mark each.

Q.1. The standard electrode potential for Ni2+/Ni couple is 0.25 V and
for Ag+/Ag couple is 0.80 V. These two couples are connected to make
an electrochemical cell. The redox reaction is spontaneous. The cell
potential will be :
(A) + 1.05 V
(B) - 1.05 V
(C) + 0.55 V
(D) -0.55 V

Solution. (C) + 0.55 V

Q.2. Out of Fe2+, Fe2+, Co2+, Cr3+, Ni2+, the one which shows lowest
magnetic moment is:
(A) Fe2+
(B) Co2+
(C) Cr3+
(D) Ni2+
[Atomic number: Fe = 26, Co = 27, Ni = 28, Cr = 24]

Solution. (D) Ni2+ , To determine which ion has the lowest magnetic
moment, we need to analyse the electronic configurations and the number
of unpaired electrons in each ion. The magnetic moment of a transition
metal ion is related to the number of unpaired electrons in its d-orbital. The
formula to calculate the magnetic moment is:
μ = √η(η + 2)
where n is the number of unpaired electrons.

Let's go through each ion:

1. Fe2+ (Iron (II)):

Atomic number of Fe = 26

Electron configuration of Fe: [Ar] 3d 4s²

Fe2+ loses 2 electrons: [Ar] 3d6

In 3D, the configuration is t₂g¹ e_g² (octahedral complex). Number of

unpaired electrons = 4
Magnetic moment: μ = √4(4 + 2) = √24 ≈ 4.89 BM

2. Fe3+ (Iron (III)):

Fe³+ loses 3 electrons: [Ar] 3d5

In 3D, the configuration is t₂g³ e_g² (octahedral complex). Number of

unpaired electrons = 5

Magnetic moment: μ = 5(5+2) = √35 ≈ 5.92 BM

3. Co2+ (Cobalt (II)):

Atomic number of Co = 27

Electron configuration of Co: [Ar] 3d 4s²

Co²+ loses 2 electrons: [Ar] 3d²

In 3d', the configuration is t₂g e_g¹ (octahedral complex). Number of
unpaired electrons = 3

Magnetic moment: μ = 3(3+2)=√15 ≈ 3.87 BM

4. Cr³+ (Chromium (III)):

Atomic number of Cr = 24
Electron configuration of Cr: [Ar] 3d 4s¹
Cr³+ loses 3 electrons: [Ar] 3d³
In 3d³, the configuration is t₂g³ (octahedral complex). Number of unpaired
electrons = 3
Magnetic moment: μ = 3(3+2) = √15 ≈ 3.87 BM
5. Ni2+ (Nickel (II)):
Atomic number of Ni = 28
Electron configuration of Ni: [Ar] 3d 4s²
Ni2+ loses 2 electrons: [Ar] 3d®
In 3d, the configuration is t₂g e_g² (octahedral complex). Number of
unpaired electrons = 2
Magnetic moment: μ = 2(2+2) = √8 ~ 2.83 BM

Among the given ions, Ni²+ has the fewest number of unpaired electrons
(2), which results in the lowest magnetic moment.
Thus, the correct answer is:
(D) Ni²+

Q.3. The geometry of paramagnetic nickel complex [NiCl4]2-is:

(A) tetrahedral
(B) octahedral
(C) square planar
(D) distorted octahedral

Solution. (A) tetrahedral , To determine the geometry of the paramagnetic

nickel complex \([NiCl_4]^{2-}\), follow these steps:

1.Oxidation State and Electron Configuration:

In \([NiCl_4]^{2-}\), Nickel (Ni) is in the +2 oxidation state.
The electron configuration of Ni in its +2 state is \([Ar] 3d^8\) (after losing 2
electrons from the 4s orbital).

2. Hybridization:
The \([NiCl_4]^{2-}\) complex has four chloride ions as ligands. The
geometry of the complex is determined by the hybridization of the central
nickel ion.
For four ligands, the hybridization is sp³, which typically leads to a
tetrahedral geometry.

3. Geometry Determination:
Nickel(II) chloride complex \([NiCl_4]^{2-}\) is a tetrahedral complex. The
tetrahedral geometry arises from sp³ hybridization and is common for such
complexes.

4.Paramagnetism:
The presence of unpaired electrons in the d-orbital of Ni²⁺ makes the
complex paramagnetic. However, this paramagnetism does not affect the
tetrahedral geometry resulting from sp³ hybridization.

Thus, the geometry of the paramagnetic nickel complex \([NiCl_4]^{2-}\) is:

(A) tetrahedral

Q.4. Which of the following does not undergo Aldol condensation?

(A) HCHO
(B) CH3CH2CHO
(C) CH3COCH3
(D) CH3CHO

Solution.(A) HCHO, To determine which compound does not undergo

Aldol condensation, let’s understand the criteria for Aldol condensation:

Aldol Condensation Overview:

Aldol condensation is a reaction between two aldehydes or ketones, or one
of each, in the presence of a base (or acid), resulting in the formation of
β-hydroxyaldehydes or β-hydroxyketones, which can further dehydrate to
form α,β-unsaturated carbonyl compounds.
The key requirement is that the molecule must have at least one
α-hydrogen (hydrogen atom on the carbon adjacent to the carbonyl group)
for the reaction to occur.

Analysis of Each Compound:

1.Formaldehyde (HCHO):
Formaldehyde does not have an α-hydrogen because its carbonyl group is
attached directly to two hydrogens (making it a CH₂O). Therefore, it cannot
undergo Aldol condensation.

2.Ethanal (CH₃CHO):
- Ethanal has one α-hydrogen (the hydrogen on the carbon adjacent to
the carbonyl group). It can undergo Aldol condensation.
3. Acetone (CH₃COCH₃):
Acetone has two α-hydrogens (the hydrogens on the two carbons adjacent
to the carbonyl group). It can undergo Aldol condensation.

4. Propionaldehyde (CH₃CH₂CHO):
Propionaldehyde has two α-hydrogens (the hydrogens on the carbon
adjacent to the carbonyl group). It can undergo Aldol condensation.

Conclusion:
Based on the requirement of having α-hydrogens for Aldol condensation,
the compound that does not undergo Aldol condensation is:
(A) HCHO (Formaldehyde)

Q.5 The IUPAC name of the complex [Co(NH3)5(ONO)]Cl2 is:

(A) Pentaamminenitrito-O-cobalt(III) chloride
(B) Pentaamminenitrito-N-cobalt(III) chloride
(C) Pentaamminenitro-cobalt(III) chloride
(D) Pentaamminenitrito-cobalt(II) chloride

Solution. To determine the IUPAC name of the complex [Co(NH3)5(ONO)]

Cl2, let's break it down step by step:

1. Identify the Ligands:

NH3: This is the ammine ligand.
ONO: This is the nitro ligand. It can be either nitrito-O or nitrito-N
depending on how it binds to the metal.

2. Determine the Type of Nitrito Ligand:

Nitrito-O (or O-nitrito): When the oxygen atom of the nitrite group is the
donor atom.
Nitrito-N (or N-nitrito): When the nitrogen atom of the nitrite group is the
donor atom.
In the complex [Co(NH3)5(ONO)] Cl2, the nitro group is bonded through
the oxygen atom, making it nitrito-O.
3. Determine the Oxidation State of the Metal:
The complex is neutral overall, and each chloride ion is -1.
Let's denote the oxidation state of cobalt as x. Since the ammonia (NH3)
and nitrito-O (ONO) ligands are neutral, the overall charge of the complex
must be zero to balance the two chloride ions.

The oxidation state of cobalt is therefore +3 (since the overall charge of the
complex must counterbalance the two negative charges from the chloride
ions).
4. Name the Complex:
The name is constructed in the following order: Ligands (alphabetically),
metal with its oxidation state, and counterions.
The ligands are "pentaammine" (since there are five NH3 groups) and
"nitrito-O" (since the nitrito ligand binds through oxygen).
The metal is cobalt with an oxidation state of +3.
Combining all these parts, the IUPAC name of the complex [Co(NH3)5
(ONO)] Cl2 is:
(A) Pentaammine Nitrito-O-cobalt(III) chloride

Q.6. The most stable complex among the following is:

(A) [Pt(NH3)2C12]
(B) [Ag(NH3)2]Cl
(C) [Pt(en)2Cl2]2+
(D) K4 [Fe(CN)6]

Solution. (D) K4 [Fe(CN)6] ,To determine which complex among the given
options is the most stable, let’s analyse each one based on its stability:

1. [Pt(NH₃)₂Cl₂]:
Type: Square planar complex.
Ligands: Two ammonia (NH₃) and two chloride (Cl⁻) ligands.
Stability: While square planar complexes of platinum (II) are generally
stable, this particular complex is not as stable as some other options due to
less steric and electronic stabilisation compared to others.
2.[Ag(NH₃)₂]Cl:
Type: Linear complex (diamine silver(I)).
Ligands: Two ammonia (NH₃) ligands and one chloride (Cl⁻) as a
counterion.
Stability: This complex is relatively stable due to the involvement of silver (I)
in a linear geometry, which is quite stable in aqueous solution.

3.[Pt(en)₂Cl₂]²⁺:
Type: Octahedral complex.
Ligands: Two ethylenediamine (en) ligands and two chloride (Cl⁻) ligands.
Stability: The ethylenediamine (en) ligands are bidentate and form chelate
rings, which increase the stability of the complex. This complex is generally
more stable due to chelation effects.

4. K₄[Fe(CN)₆]:
Type: Octahedral complex.
Ligands: Six cyanide (CN⁻) ligands.
Stability: This complex is known for its high stability. The cyanide ligands
are strong field ligands and form very stable complexes with iron.
Additionally, the iron in this complex is in the +2 oxidation state (ferrous),
which further contributes to its stability.
Given the above analysis, the most stable complex among the options is:
(D) K₄[Fe(CN)₆]

The high stability of this complex is due to the strong field effect of the
cyanide ligands and the overall stability of the iron (II) centre in the
octahedral arrangement.

Q.8. The chemical test which can be used to distinguish between

ethylamine and aniline is:
(A) Haloform test
(B) Tollens' test
(C) Azo dye test
(D) Hinsberg test
Solution.(D) Hinsberg test, To distinguish between ethylamine and
aniline, we need to use a chemical test that differentiates between a
primary aliphatic amine and a primary aromatic amine. Here’s a breakdown
of the options:

1. Haloform Test:
This test is used to detect methyl ketones or compounds that can be
oxidised to methyl ketones. It’s not suitable for distinguishing between
ethylamine and aniline.

2.Tollens' Test:
Tollens' test is used to detect aldehydes. It’s not applicable for
differentiating between amines.

3.Azo Dye Test:

The Azo dye test is used for aromatic amines, where the amine is
diazotized and then coupled with a suitable coupling component. This test
can differentiate between aromatic amines, like aniline, and other types of
amines.

4. Hinsberg Test:
The Hinsberg test is specifically used to differentiate between primary,
secondary, and tertiary amines. Ethylamine (a primary aliphatic amine) and
aniline (a primary aromatic amine) react differently in this test. Ethylamine
reacts with benzene sulfonyl chloride to form a sulfonamide that is soluble
in alkali, while aniline does not react similarly.

Thus, the chemical test that can be used to distinguish between ethylamine
and aniline is (D) Hinsberg test.

Q.9. The correct IUPAC name of (CH3)3 C - CH2Br is:

(A) 2,2-Methyl-2-bromopropane
(B) 1-Bromo-2,2,2-trimethylethane
(C) 2-Bromo-1,1,1-trimethylethane
(D) 1-Bromo-2,2-dimethylpropane

Solution. (D) 1-Bromo-2,2-dimethylpropane, To determine the correct

IUPAC name for the compound \((CH_3)_3C - CH_2Br\), let's break it
down:

1. Identify the Longest Carbon Chain:

The longest carbon chain here has 2 carbon atoms, making it part of the
propane group. The main chain is a propane chain.

2. Identify the Substituents and Their Positions:

The substituent is a bromine atom attached to a carbon that is connected to
a tert-butyl group \((CH_3)_3C-\), which is attached to the second carbon of
the propane chain.

3.Determine the Correct Naming:

The compound is a 1-bromo derivative of 2,2,2-trimethylpropane. However,
the correct structure must be evaluated based on its longest carbon chain
and substituent positions.

Putting this together:

The main chain is a propane chain with a bromine attached to the first
carbon of this propane chain.
The tert-butyl group is attached to the second carbon of the propane chain.
Thus, the correct IUPAC name is (D) 1-Bromo-2,2-dimethylpropane

Q.10. Considering the strength of the ligand, the highest excitation

energy will be observed in:
(A) [Co(H2O)6]3+
(B) [Co(NH3)6]3+
(C) [Co(CN)6]3-
(D) [CoC16]3-

Solution. (C) [Co(CN)6]3-, To determine which complex will have the

highest excitation energy, we need to consider the strength of the ligand
and its effect on the splitting of the d-orbitals in the metal center. Higher
ligand field strength leads to greater splitting of the d-orbitals and thus
higher excitation energy.

Here’s a brief overview of the ligand strengths and their corresponding field
strengths:
Water (H₂O): A weak field ligand.
Ammonia (NH₃): A weak to moderate field ligand.
Cyanide (CN⁻): A strong field ligand.
Chloride (Cl⁻): A weak field ligand.

In the complexes given:

1.[Co(H₂O)₆]³⁺: Water is a weak field ligand, leading to a smaller crystal field
splitting.
2.[Co(NH₃)₆]³⁺: Ammonia is a weak to moderate field ligand, leading to
moderate crystal field splitting.
3.[Co(CN)₆]³⁻: Cyanide is a strong field ligand, causing significant crystal
field splitting.
4.[CoCl₆]³⁻: Chloride is a weak field ligand, leading to minimal crystal field
splitting.
Conclusion:
The strongest field ligand among the given options is cyanide (CN⁻), which
results in the largest crystal field splitting and therefore the highest
excitation energy.
So, the correct answer is: (C) [Co(CN)₆]³⁻

Q.11. For a chemical reaction, A B, it was observed that the rate of

reaction doubles when the concentration of A is increased four times.
The order of the reaction is :
(A) 2
(B) 1
(C) 1/2
(D) Zero
Solution. (C) ½, To determine the order of the reaction, we can use the
relationship between the rate of reaction and the concentration of reactant.
For a reaction where the rate r depends on the concentration of a single
reactant A, the rate law can be written as: r = k[A]
where k is the rate constant and n is the order of the reaction.
Given the information:
When the concentration of A is increased by a factor of 4, the rate of
reaction doubles.
We can set up the equation based on the rate law:

1. Initial rate: r₁ = k[A] n

2. New concentration: [A] new = 4[A] New rate: r2 = k(4[A])" 4" k[A]
According to the problem, the new rate 12 is twice the initial rate 71:
r2 = 2r1
4k [A] 2k[A] 22
Divide both sides by k[A]":
72 2
To solve for n, take the logarithm base 2:
4=2
(22) = 2
22n = 21
2n = 1
n= 12
Therefore, the order of the reaction is:
(C) 1/2

Q.12. Williamson's synthesis of preparing dimethyl ether is a/an:

(A) electrophilic substitution
(B) SN1 reaction
(C) electrophilic addition
(D) SN2 reaction

Solution.(D) SN2 reaction, Williamson's synthesis involves the

preparation of ethers by reacting an alkyl halide with an alkoxide. This
reaction is typically characterised as an **SN2** (bimolecular nucleophilic
substitution) reaction.

1. Reaction Mechanism: Williamson's synthesis involves a nucleophilic

attack by an alkoxide ion (the nucleophile) on the carbon of the alkyl halide
(the electrophile). This process happens in a single step where the
nucleophile displaces the leaving group (halide) from the alkyl halide,
leading to the formation of an ether.

2. Characteristics of SN2 Reaction: In SN2 reactions, the nucleophile

attacks the electrophile from the opposite side of the leaving group, leading
to a simultaneous bond formation and bond breaking process. This is
consistent with the mechanism of Williamson's synthesis.

Thus, Williamson's synthesis of dimethyl ether (or any ether) is a classic

example of an SN2 reaction.

For Questions number 13 to 16, two statements are given one labelled
as Assertion (A) and the other labelled as Reason (R). Select the
correct answer to these questions from the codes (A), (B), (C) and (D)
as given below.

(A) Both Assertion (A) and Reason (R) are true and Reason (R) is the
correct explanation of the Assertion (A).
(B) Both Assertion (A) and Reason (R) are true, but Reason (R) is not
the correct explanation of the Assertion (A).
(C) Assertion (A) is true, but Reason (R) is false.
(D) Assertion (A) is false, but Reason (R) is true.

Q.13. Assertion (A): Rate constant increases with increase in

temperature.
Reason (R): Increasing the temperature of the substance increases
the fraction of molecules, which collide with energies greater than
activation energy.
Solution. Assertion (A):** Rate constant increases with increase in
temperature.
Reason (R): Increasing the temperature of the substance increases the
fraction of molecules, which collide with energies greater than activation
energy.
Explanation:
Assertion (A) is true because, according to the Arrhenius equation, the rate
constant \( k \) of a reaction increases with an increase in temperature.
Reason (R) is also true because raising the temperature increases the
number of molecules with energy equal to or greater than the activation
energy, which in turn increases the rate constant.
Answer: (A) Both Assertion (A) and Reason (R) are true and Reason (R) is
the correct explanation of the Assertion (A).

Q.14. Assertion (A): Cu2+ iodide is known.

Reason (R): Cu2+ has a strong tendency to oxidise I to Iodine.

Solution. Assertion (A): Cu²⁺ iodide is known.

Reason (R): Cu²⁺ has a strong tendency to oxidise I to Iodine.
Explanation:
Assertion (A) is false because Cu²⁺ iodide (CuI₂) is not a stable or known
compound. Copper typically forms CuI (copper(I) iodide) rather than CuI₂.
Reason (R) is true in the context of chemistry; Cu²⁺ can indeed oxidise
iodide ions to iodine, but this does not validate the existence of Cu²⁺ iodide.
Answer:(D) Assertion (A) is false, but Reason (R) is true.

Q.15. Assertion (A): Maltose is a non-reducing sugar.

Reason (R): Maltose is composed of two glucose units in which C-1 of
one glucose unit is linked to C-4 of another glucose unit.
NHCOCH3

Solution. Assertion (A): Maltose is a non-reducing sugar.

Reason (R): Maltose is composed of two glucose units in which C-1 of one
glucose unit is linked to C-4 of another glucose unit.
Explanation:
Assertion (A) is false because maltose is a reducing sugar. It has a free
aldehyde group available in the open-chain form, which makes it a reducing
sugar.
Reason (R) is true as it accurately describes the linkage in maltose
(α-1,4-glycosidic bond).
Answer:(D) Assertion (A) is false, but Reason (R) is true.**

Q.16. Assertion (A): Acetanilide is more basic than aniline.

Reason (R): Acetylation of aniline results in decrease of electron
density on nitrogen.

Solution. Assertion (A): Acetanilide is more basic than aniline.

Reason (R): Acetylation of aniline results in decrease of electron density on
nitrogen.

Explanation:
Assertion (A) is false. Acetanilide is actually less basic than aniline. The
acetylation of aniline decreases the electron density on the nitrogen atom
due to the electron-withdrawing effect of the acetyl group.
Reason (R) is true because acetylation does decrease the electron density
on the nitrogen atom.
Answer:(D) Assertion (A) is false, but Reason (R) is true.

SECTION B

Q.17. (a) Account for the following:

(i) CH3CHO is more reactive than CH3COCH3 towards reaction with

HCN.

(ii) Carboxylic acids are higher boiling liquids than aldehydes and
ketones.
OR
Solution. (a) Account for the following:

(i) CH₃CHO is more reactive than CH₃COCH₃ towards reaction with HCN.
Explanation:
CH₃CHO (acetaldehyde) is more reactive than CH₃COCH₃ (acetone)
towards nucleophilic addition reactions like those with hydrogen cyanide
(HCN).
The reason lies in the electronic nature of the carbonyl group. In CH₃CHO
, the carbonyl carbon is more electrophilic compared to CH₃COCH₃. This
increased electrophilicity is due to the greater electron-donating effect of
the two alkyl groups in acetone compared to the one alkyl group in
acetaldehyde.
Specifically, acetaldehyde has only one alkyl group (methyl), which
provides less electron donation to the carbonyl carbon. In contrast, acetone
has two alkyl groups (both methyl groups) that donate electron density
through inductive effects. This donation decreases the positive charge on
the carbonyl carbon in acetone, making it less electrophilic and less
reactive towards nucleophiles like HCN.

(ii) Carboxylic acids are higher boiling liquids than aldehydes and ketones.

Explanation:
Carboxylic acids have significantly higher boiling points compared to
aldehydes and ketones. This is due to the presence of strong hydrogen
bonding in carboxylic acids.
Carboxylic acids can form dimers through hydrogen bonding, which means
two molecules of the acid interact with each other through two hydrogen
bonds. This dimerization leads to a significant increase in boiling point due
to the stronger intermolecular forces.
Aldehydes and ketones, on the other hand, do not have the ability to form
such extensive hydrogen bonds. They primarily have dipole-dipole
interactions, which are weaker than the hydrogen bonding in carboxylic
acids. As a result, carboxylic acids have higher boiling points compared to
aldehydes and ketones.
(b) Give chemical tests to distinguish between the following pair of
compounds:

(i) Propanal and Propanone

(ii) Benzaldehyde and Benzoic acid

Solution. To distinguish between the given pairs of compounds, you can

use specific chemical tests. Here's how you can differentiate between each
pair:
(i) Propanal and Propanone
1. Tollens' Test:
Propanal: It will give a positive result with Tollens' reagent. This is because
propanal is an aldehyde, and aldehydes generally reduce Tollens' reagent
(a solution of silver nitrate in ammonia) to metallic silver, resulting in a silver
mirror on the inner surface of the test tube.
Propanone: It will not react with Tollens' reagent. Propanone is a ketone,
and ketones generally do not reduce Tollens' reagent.

2. 2,4-Dinitrophenylhydrazine (2,4-DNPH) Test:

Propanal: When treated with 2,4-DNPH, propanal will form a yellow or
orange precipitate of 2,4-dinitrophenylhydrazone. This is because propanal
reacts with 2,4-DNPH to form a hydrazone derivative.
Propanone: Similarly, propanone will also form a yellow or orange
precipitate with 2,4-DNPH. However, this test is not specific to
differentiating aldehydes from ketones but confirms the presence of
carbonyl groups.
3. Iodoform Test:
Propanal: It does not give a positive iodoform test.
Propanone: It will give a positive iodoform test, which is a characteristic test
for ketones with a methyl group adjacent to the carbonyl group. A yellow
precipitate of iodoform (CHI₃) will be observed.

(ii) Benzaldehyde and Benzoic Acid

1.Tollens' Test:
Benzaldehyde: It will give a positive Tollens' test. Benzaldehyde, being an
aldehyde, reduces Tollens' reagent, producing a silver mirror.
Benzoic Acid: It will not react with Tollens' reagent. Benzoic acid is a
carboxylic acid and does not reduce Tollens' reagent.

2. Sodium Bicarbonate Test:

Benzaldehyde: It does not react with sodium bicarbonate solution.
Benzoic Acid: It will react with sodium bicarbonate to produce carbon
dioxide gas. This reaction occurs because benzoic acid is a carboxylic acid
and reacts with the bicarbonate to release CO₂.

3.2,4-Dinitrophenylhydrazine (2,4-DNPH) Test:

Benzaldehyde: It will give a positive 2,4-DNPH test, forming a yellow or

orange precipitate, similar to propanal.
Benzoic Acid: It will not give a positive result with 2,4-DNPH, as carboxylic
acids do not react with this reagent to form a hydrazone.

These tests help to specifically identify and differentiate between the

compounds in each pair based on their chemical reactivity.

Q.18. Write the reaction involved in the following:

(a) Reimer-Tiemann reaction

(b) Kolbe's reaction

Solution.(a) Reimer-Tiemann Reaction

The Reimer-Tiemann reaction is used to introduce a formyl group (-CHO)
into the ortho position of phenols, typically resulting in the formation of
ortho-hydroxybenzaldehyde (salicylaldehyde).
Reaction:
C6H5OH + CHCl3 + NaOH → C6H4(OH)(CHO) + 2HCl + NaCl
In this reaction:
Phenol (C6H5OH) reacts with chloroform (CHCl3) in the presence of a
strong base (sodium hydroxide, NaOH).
The result is ortho-hydroxybenzaldehyde (salicylaldehyde).

(b) Kolbe's Reaction

Kolbe's reaction is an electrochemical reaction used to produce alkanes
from the corresponding carboxylate salts by decarboxylation.
Reaction:
2RCOONa electrolysis R-R+ 2NaOH + 2CO2
In this reaction:
Sodium carboxylate salts (RCOONa) are electrolyzed.
The result is the formation of the corresponding alkane (R-R), along with
sodium hydroxide ( NaOH) and carbon dioxide (CO2).
In summary:
Reimer-Tiemann Reaction: Phenol + Chloroform + NaOH products
Ortho-Hydroxybenzaldehyde + By-
Kolbe's Reaction: Sodium Carboxylate Salts → Alkane + NaOH + CO2

Q.19. Write the reaction of glucose with:

(a) HI
(b) Br2 water

Solution. (a) Glucose with HI

When glucose reacts with hydriodic acid (HI), it undergoes a cleavage
reaction where the sugar is broken down into simpler compounds.
Specifically, glucose is converted into n-hexane (an alkane) and iodoform.
Reaction:
C6H12O6 + 6HI C6H14+612+ 6H2O
In this reaction:
Glucose (C6H12O6) reacts with hydriodic acid (HI).
The result is n-hexane (C6H14), iodine (I2), and water (H2O).
(b) Glucose with Br2 Water
When glucose reacts with bromine water (Br₂ water), it undergoes an
oxidation reaction, where the aldehyde group of glucose is oxidized to a
carboxyl group, converting glucose to gluconic acid.
Reaction:
C6H12O6 + Br2 + H2O C6H12O7 + HBr
In this reaction:
Glucose (C6H12O6) reacts with bromine water (Br₂) and water (H2O).
The result is gluconic acid (C6H12O7) and hydrobromic acid (HBr).
To summarise:
Glucose + HI: Converts to n-hexane and iodine.
Glucose + Br2 water: Oxidises to gluconic acid.

Q.20. The thermal decomposition of an acid is a first order reaction

with a rate constant of 2.3×10-3 s-1 at a certain temperature. Calculate
how long it will take for three-fourths of the initial quantity of acid to
decompose. (log 40.6021, log 2 = 0.301)

Solution.
 SECTION C

Q.22. Give plausible explanation for the following:

(a) Diazonium salts of aromatic amines are stable.
(b) Aniline does not undergo Friedel-Crafts reaction.
(c) Aniline on nitration gives a substantial amount of meta product.

Solution. (a) Diazonium salts of aromatic amines are stable.

Explanation:
Diazonium salts of aromatic amines are generally stable due to the
following reasons:
1. Resonance Stabilisation: The diazonium ion (R-N₂) can delocalize its
positive charge through resonance with the aromatic ring. This resonance
stabilisation of the diazonium ion contributes to its stability.

2. Strong ionic Bonding: In the diazonium salt, the diazonium ion is

stabilised by ionic interactions with the counterion (usually a halide or
sulphate). This ionic bonding helps in stabilising the diazonium salt.

3. Substitution Effects: The stability of the diazonium salt can be enhanced

by substituents on the aromatic ring that stabilise the positive charge
through inductive or resonance effects.

(b) Aniline does not undergo Friedel-Crafts reaction.

Explanation:
Aniline does not undergo Friedel-Crafts reactions (either acylation or
alkylation) because:

1. Strongly Activating Amino Group: The amino group (-NH2) is a strongly

activating group for electrophilic aromatic substitution, making the ring
highly reactive. However, in Friedel-Crafts reactions, the electrophiles (such
as alkyl or acyl cations) are often too reactive and can lead to side
reactions or rearrangements.

2. Formation of Complexes: The amino group can coordinate with the

Lewis acid catalysts used in Friedel-Crafts reactions (like AlCl3), forming
complexes that deactivate the catalyst or prevent it from effectively reacting
with the aromatic ring. This complex formation reduces the effectiveness of
the Friedel-Crafts catalyst.

3. Formation of by-products: The Friedel-Crafts reaction involves the

generation of carbocation intermediates, which can lead to polymerization
or side reactions when interacting with the highly nucleophilic amino group.

(c) Aniline on nitration gives a substantial amount of meta product.

Explanation:
Aniline on nitration typically yields a substantial amount of meta product
due to the following
reasons:

1. Strong Activating Effect of the Amino Group: The amino group (-NH2) is
a strong electron- donating group through resonance. This increases the
electron density of the ring, making the ring more reactive towards
electrophiles such as the nitronium ion (NO₂).

2. Formation of a Nitrosonium Intermediate: The nitronium ion (NO₂) is a

strong electrophile in the nitration reaction. The amino group can form a
nitrosylated intermediate that results in the formation of the meta product
as well as the ortho and para products.

3. Deactivating Effects: Despite being strongly activating, the amino group

can also exert a deactivating effect under certain conditions, leading to a
preference for meta substitution. This is due to steric hindrance or the
formation of resonance structures that may favor meta positions over ortho
and para positions.
In summary, the amino group in aniline, while being strongly activating, can
influence the distribution of products due to its electronic effects and
interactions with the electrophile in the nitration reaction.

Q.23. Account for the following:

(a) The dipole moment of chlorobenzene is lower than that of
cyclohexyl chloride.
(b) Alkyl halides are immiscible in water.
(c) t-butyl bromide has lower boiling point than n-butyl bromide.

Solution.(a) The dipole moment of chlorobenzene is lower than that of

cyclohexyl chloride.
Explanation:
1. Electron Withdrawing Effects: In chlorobenzene, the chlorine atom is
attached to a benzene ring. The chlorine atom is highly electronegative and
withdraws electron density through the sigma bond. However, the benzene
ring also has resonance structures that can delocalize some of the electron
density, which reduces the overall dipole moment.
2. Resonance Stabilisation: The delocalization of the electron density in the
aromatic ring of chlorobenzene leads to a partial offset of the dipole
moment. This resonance effect causes the dipole moment of
chlorobenzene to be less than that of cyclohexyl chloride.
3. Cyclohexyl Chloride Characteristics: Cyclohexyl chloride, where the
chlorine is attached to a cyclohexane ring, lacks such delocalization.
Therefore, the dipole moment of cyclohexyl chloride is higher because the
entire dipole due to the chlorine is preserved without resonance effects
counteracting it.

Q.24. (a) Draw the geometrical isomers of the complex [Pt(NH3)2Cl2].

(b) Give the electronic configuration of d4 ion when Ao > P.
(c) Solution of [Ni(H2O)6]2+ is green in colour whereas [Ni(CN)4]2- is
colourless. Give a reason. [Atomic number: Ni = 28]

Solution. (a) Geometrical Isomers of [Pt(NH3)2CI2]

The complex [Pt(NH3)2C12] can exhibit geometrical isomerism due to the
different spatial arrangements of the ligands around the platinum ion.
Platinum (II) complexes typically adopt a square planar geometry. For
[Pt(NH3)2C12], the geometrical isomers are:

1. Cis-Isomer:
In the cis-isomer, the two ammonia (NH3) groups are adjacent to each
other, and the two chloride (Cl) ions are also adjacent.

2. Trans-Isomer:
In the trans-isomer, the two ammonia (NH3) groups are opposite each
other, and the two chloride (Cl) ions are also opposite each other.

(b) Electronic Configuration of d² lon when A0 > P

In the context of octahedral complexes, the electronic configuration of a d
ion depends on the magnitude of the crystal field splitting energy (A0)
compared to the pairing energy (P).
When A > P: The crystal field splitting energy is large compared to the
pairing energy. This leads to the low-spin configuration where electrons pair
up in the lower energy t₂g orbitals.
For a d¹ configuration in an octahedral field with A0 > P:
Electronic Configuration: The d-orbitals will be arranged as follows:

t2g: 1111 (paired)

e_g: (empty)

Thus, the electronic configuration will be:

t2g: 4 electrons (all paired)

e_g: 0 electrons

(c) Colour Differences between [Ni(H2O)6]2+ and [Ni(CN)4]2-

1. [Ni(H2O)6]²+:
The complex [Ni(H2O)6]²+ is typically green in color. This is due to the
relatively weak field strength of water as a ligand, which causes partial
splitting of the d-orbitals in the octahedral field. This partial splitting allows
for the absorption of light in the visible region, particularly in the red to
orange part of the spectrum, while the green color is transmitted.

2. [Ni(CN)4]2:
The complex [Ni(CN)4]² is colorless. Cyanide (CN) is a strong field ligand
and causes a large splitting of the d-orbitals in a square planar field (or
tetrahedral for some complexes). This large splitting results in a large
energy gap between the split d-orbitals, and thus, no visible light is
absorbed. The absorption occurs in the ultraviolet region, and the complex
appears colorless to the visible eye.
Summary:
[Ni(H2O)6]2+ is green due to weak field ligands causing partial d-orbital
splitting and visible light absorption.
[Ni(CN)4]2 is colorless due to strong field ligands causing large d-orbital
splitting, absorbing UV light instead of visible light.

Q.25. The electrical resistance of a column of 0.05 M NaOH solution of

cell constant 50 cm-1 is 4.5×103 ohm. Calculate its resistivity,
conductivity and molar conductivity.

Solution.
Q.26. Calculate elevation of the boiling point of the solution when 4 g
of MgSO4 (molar mass = 120 g/mol) was dissolved in 100 g of water,
assuming MgSO4 undergoes complete ionisation. (Kb for water = 0.52
K kg mol-1)

Solution.
Q.27. Hydrolysis of ethyl ethanoate takes place by the chemical
reaction : CH3COOC2H5 + H2O (excess) H+ Based on the above
reaction, write : CH3COOH + C2H5OH
(a) What do you call such reactions?
(b) Rate law equation
(c) What do you call such reactions?
Solution. The hydrolysis of ethyl ethanoate (ethyl acetate) in the presence
of an acid catalyst is known as acid- catalysed hydrolysis or more
specifically, ester hydrolysis. This type of reaction is also referred to as
saponification when it is done under basic conditions, but in the given
scenario with an acid catalyst, it's simply ester hydrolysis.
(b) Rate Law Equation
The rate law for the acid-catalysed hydrolysis of ethyl ethanoate can be
expressed as follows:
Rate = k[CH3COOC2H5] [H2O]
In this reaction:
k is the rate constant.
[CH3COOC2H5] is the concentration of ethyl ethanoate (ester).
[H2O] is the concentration of water.
For ester hydrolysis in an acid-catalysed reaction, the rate typically
depends on the concentration of the ester and the acid catalyst. However,
since water is in excess, its concentration is essentially constant and does
not affect the rate of reaction significantly, thus making the rate law
primarily depend on the concentrations of the ester and the acid.

Q.27. Hydrolysis of ethyl ethanoate takes place by the chemical

reaction: CH3COOC2H5 + H2O (excess) H+ Based on the above
reaction, write: CH3COOH + C2H5OH

(a) What do you call such reactions?

(b) Rate law equation
(c) Molecularity and order of reaction

Solution. The reaction you described is an example of ester hydrolysis. In

the presence of an acid catalyst, this reaction is specifically known as
acid-catalysed hydrolysis of an ester or simply acid hydrolysis of ethyl
ethanoate. This process results in the formation of acetic acid and ethanol.

(b) Rate Law Equation

For the hydrolysis of ethyl ethanoate (ethyl acetate) in the presence of
excess water and an acid catalyst, the rate law can be expressed as:
Rate = k[CH3COOC2H5] [H+]
In this rate law:
k is the rate constant.
• [CH3COOC2H5] is the concentration of ethyl ethanoate.
[H^+] is the concentration of the hydrogen ions (acid catalyst).
Since water is present in excess, its concentration remains nearly constant
and is not included in the rate law.

(c) Molecularity and Order of Reaction

Molecularity: The molecularity of a reaction refers to the number of
molecules (or ions) that come together to react in an elementary step. For
this reaction, the rate-determining step typically involves the collision
between one molecule of ethyl ethanoate and one hydrogen ion, so it is
bimolecular in the context of the rate-determining step.
Order of Reaction: The order of reaction with respect to each reactant is
determined by the rate
law. Based on the rate law:
Rate = k[CH3COOC2H5] [H+]
The order of reaction with respect to ethyl ethanoate is 1, and the order
with respect to the acid catalyst (H+) is also 1. Thus, the overall order of the
reaction is:
Overall order = 1+1=2
Therefore, the reaction is second-order overall.

Q.28. What happens when: (any three)

MgBr (a) is treated with CH3CHO followed by hydrolysis.

(b) Phenol is treated with conc. (HNO3 + H2SO4).

(c) Anisole is treated with CH3COCI in the presence of anhydrous

AlCl3.

(d) Propan-2-ol is heated with Cu at 573 K.

Solution. (a) MgBr2 is treated with CH3CHO followed by hydrolysis
Reaction: This is a Grignard reaction followed by hydrolysis.

Step 1: The Grignard reagent (MgBr2, although this is typically denoted as

RMgX) reacts with the aldehyde (CH3CHO, which is acetaldehyde) to form
a tertiary alcohol.
RMgX + CH3CHO RCH(OH)CH3MgX
Step 2: Hydrolysis of the reaction mixture produces the corresponding
alcohol.
RCH(OH)CH3MgX + H2O → RCH(OH)CH3 + Mg(OH)X

Result: If R = CH3, the product is 1-Phenylethanol.

(b) Phenol is treated with concentrated HNO3 and H2SO4

Reaction: Phenol reacts with concentrated nitric acid (HNO3) in the
presence of sulfuric acid (H2SO4) to give nitrophenols.
Product Formation: The reaction typically results in the formation of a
mixture of ortho- and para-nitrophenol due to the activating effect of the
hydroxyl group in phenol.

C6H5OH + HNO3 H2SO4 2,4-Dinitrophenol (major) and 2-Nitrophenol

(minor)

Result: The main products are 2-nitrophenol and 4-nitrophenol.

(c) Anisole is treated with CH3COCI in the presence of anhydrous AlCl3

Reaction: This is a Friedel-Crafts acylation reaction.
Reaction: Anisole (methoxybenzene) reacts with acetyl chloride
(CH3COCI) in the presence of anhydrous aluminum chloride (AlCl3),
resulting in the formation of acetophenone.

C6H5OCH3 + CH3COCI AlCl3 C6H5COCH3 + HCl

Result: The product is acetophenone (C6H5COCH3).

(d) Propan-2-ol is heated with Cu at 573 K
Reaction: This is a dehydrogenation reaction.
Reaction: Propan-2-ol (isopropanol) is heated with copper at high
temperature (573 K), leading to the removal of hydrogen and the formation
of acetone.
Cu, 573 K

CH3CH(OH)CH3 CH3COCH3 + H2

Result: The product is acetone (propan-2-one).

Feel free to ask if you need further details or explanations on these
reactions.

SECTION D

The following questions are case-based questions. Read the case

carefully and answer the questions that follow.

Q.29. The particles in the nucleus of the cell, responsible for heredity,
are called chromosomes which are made up of proteins and another
type of biomolecules called nucleic acids. These are mainly of two
types, DNA and RNA. Nucleic acids on hydrolysis yield a pentose
sugar, phosphoric acid and nitrogen containing heterocyclic
compounds. Nucleic acids have a very diverse set of functions, such
as cell creation, the storage and processing of genetic information,
protein synthesis and the generation of energy cells. Although their
functions may differ, the structure of DNA and RNA are very similar,
with only a few fundamental differences in their molecular make-up.
Based on the above passage, answer the following questions:

(a) Write three types of RNA molecules.

(b) What products will be formed when a nucleotide from DNA

containing thymine is hydrolysed?
(c) (i) Give two differences between DNA and RNA.

OR
(ii) (1) Why are the two strands of DNA complementary ?

(ii) What type of linkage joins two nucleotides?

Solution.Certainly! Let's tackle the questions based on the provided

passage about nucleic acids:
(a) Three Types of RNA Molecules
The three main types of RNA molecules are:
1. mRNA (messenger RNA) - Carries genetic information from DNA to the
ribosome, where proteins are synthesized.
2.tRNA (transfer RNA) - Brings amino acids to the ribosome during protein
synthesis, matching the amino acids to the appropriate codons on the
mRNA.
3. rRNA (ribosomal RNA) - Combines with proteins to form ribosomes,
which are the sites of protein synthesis.
(b) Products Formed When a Nucleotide from DNA Containing Thymine is
Hydrolysed
When a nucleotide from DNA containing thymine is hydrolyzed, the
following products are formed:
1. Pentose Sugar- Deoxyribose (in DNA).
2. Phosphoric Acid - Phosphate group.
3. Nitrogen-Containing Heterocyclic Compound** - Thymine (one of the
four nitrogenous bases in DNA).

(c) Differences Between DNA and RNA

(i) Two Differences Between DNA and RNA:**
1. Sugar Component:
DNA: Contains deoxyribose sugar.
RNA: Contains ribose sugar.
2.Nitrogenous Bases:
DNA: Contains adenine (A), cytosine (C), guanine (G), and thymine (T).
RNA: Contains adenine (A), cytosine (C), guanine (G), and uracil (U)
instead of thymine.
OR

(ii) Why Are the Two Strands of DNA Complementary?**

The two strands of DNA are complementary because of the specific base
pairing rules:
Adenine (A) pairs with Thymine (T) via two hydrogen bonds.
Cytosine (C) pairs with Guanine (G) via three hydrogen bonds.
This complementary base pairing ensures that the genetic information is
accurately replicated and transcribed.
Nucleotides are joined together by **phosphodiester bonds**. These bonds
connect the phosphate group of one nucleotide to the hydroxyl group of the
sugar in the next nucleotide, forming the backbone of the nucleic acid
strand.

Q.30 The cause for deviation from Raoult's law in the colligative
properties of non-ideal solutions lie in the nature of interactions at the
molecular level. These properties show deviations from Raoult's law
due to differences in interactions between solute solvent, solute
solute and solvent solvent. Some liquids on mixing, form azeotropes
which are binary mixtures having the same composition in liquid and
vapour phase and boil at a constant temperature. In such cases, it is
not possible to separate the components by fractional distillation.
There are two types of azeotropes called minimum boiling azeotrope
and maximum boiling azeotrope.
Based on the above passage, answer the following questions:

(a) Pure ethanol cannot be prepared by fractional distillation of

ethanol - water mixture. Comment.

(b) Why does a mixture of chloroform and acetone show deviation

from ideal behaviour ?
(c) (i) The vapour pressure of pure benzene at a certain temperature is
1.25 atm. When 1.2 g of non-volatile, non-electrolyte solute is added
to 60 g of benzene (M = 78 g mol-¹), the vapour pressure of the
solution becomes 1.237 atm. Calculate the molar mass of the non-
volatile solute.
OR

© (ii) The boiling point of benzene is 353.23 K. When 1.80 g of a non-

volatile solute is dissolved in 90 g of benzene, the boiling point is
raised to 354.11 K. Calculate the molar mass of the solute. Ky for
benzene is 2.53 K kg mol-1.

Solution. (a) Pure Ethanol and Fractional Distillation

Pure ethanol cannot be prepared by fractional distillation of an

ethanol-water mixture because ethanol and water form an azeotrope. An
azeotrope is a mixture that has a constant boiling point and composition in
both the liquid and vapour phases. For ethanol-water, this azeotrope boils
at a lower temperature than the boiling points of pure ethanol or pure water.
Therefore, fractional distillation will not completely separate ethanol from
water, as the azeotrope limits the purity of the separated ethanol.

(b) A mixture of chloroform and acetone shows deviation from ideal

behaviour due to strong specific interactions between the molecules of the
two substances. These interactions are different from the interactions in
pure chloroform or pure acetone. In this case, chloroform and acetone form
hydrogen bonds or have other interactions that can alter the vapour
pressure of the mixture compared to what Raoult’s law would predict.
These deviations result in non-ideal behaviour, either as positive or
negative deviations depending on the nature of these interactions.
 SECTION E

Q.31.(a) (i) What type of battery is the lead storage battery? Write the
anode and the cathode reactions and the overall reaction occurring in
a lead storage battery when current is drawn from it.

(ii) Calculate the time to deposit 1.5 g of silver at cathode when a

current of 1.5 A is passed through the solution of AgNO3.
[Molar mass of Ag = 108 g mol-1, 1 F = 96500 C mol-1]

OR
(b) (i) State Kohlrausch's law of independent migration of ions. Molar
conductivity at infinite dilution for NH4Cl, NaOH and NaCl solution at
298 K are 110, 100 and 105 S cm² mol-¹ respectively. Calculate the
molar conductivity of NH4OH solution.

(ii) Calculate AGE° of the following cell at 25°C:

Zn (s) | Zn2+(aq) || Cu2+ (aq) | Cu (s)
Given: E 2+ Zn/Zn = -0.76 V
E 2+ Cu/Cu = + 0.34 V
1 F = 96500 C mol-1

Solution. (i) Lead Storage Battery

Type of Battery:

The lead storage battery is a type of secondary (rechargeable) battery.

Reactions in the Lead Storage Battery:
Anode Reaction (during discharge):

Pb(s) + SO (aq) → PbSO4(s) + 2e 4

Cathode Reaction (during discharge):

PbO2(s) + 3H2SO4(aq) + 2e → PbSO4(s) + 2H2O(1)

Overall Reaction (during discharge):

Pb(s) + PbO2(s) + 2H2SO4(aq) → 2PbSO4(s) + 2H2O(1)

(a) (ii) Calculating Time to Deposit Silver

To deposit 1.5 g of silver, we use the following steps:

Calculate the moles of silver deposited:
Moles of Ag-Mass/molar mass -1.5 g / 0.01389 mol
Moles of Ag Molar Mass 0.01380 g/mol

2. Calculate the total charge required:

The reaction for silver deposition is:
Ag+eAg(s)
For 1 mole of silver, 1 mole of electrons (1 Faraday) is needed. Therefore:
Charge required = Moles of Ag × Faraday Constant = 0.01389 mol × 96500
C/m

3. Calculate the time using the current:

Time/ Charge 1340 C/1.5A =893.33 ≈ 14.89 minutes

OR
(b) (i) Kohlrausch's Law and Molar Conductivity of NH4OH
Kohlrausch's Law:
Kohlrausch's Law states that the molar conductivity at infinite dilution of an
electrolyte is equal to the sum of the molar conductivities of its ions, each
extrapolated to infinite dilution.
Calculate the Molar Conductivity of NH4OH:
Given:
Molar conductivity of NH4Cl = 110 S cm² mol¯¹
Molar conductivity of NaOH = 100 S cm² mol-¹
Molar conductivity of NaCl = 105 S cm² mol-¹
For NH4OH:
Molar conductivity of NH4OH = Molar conductivity of NH4Cl + Molar
conductivity
Molar conductivity of OH = Molar conductivity of NaOH - Molar conductivity
of N Since Na does not contribute to OH's molar conductivity, we directly
use:
Molar conductivity of OH Molar conductivity of NaOH 100
Molar conductivity of NH4OH = 110+100 - 105 105 S cm² mol-1
(ii) Calculating AG for the Cell Reaction
Given:
EZn2+/Zn = -0.76 V
ECu²/Cu = +0.34 V
1. Calculate the cell potential Ecell:
Ecell Ecathode Eanode 0.34 (-0.76) = 1.10 V

2. Calculate AG:
AG°=-nFE cell
For the cell reaction:
Zn(s) → Zn2+ +2e
Cu2+ +2e→ Cu(s)
Number of electrons n = 2:
AG = 2x 96500 C/mol × 1.10 V = -212300 J/mol = -212.3 kJ/mol

Q.32. (a) (i) Explain with the help of chemical reaction when :

(1) Acetone is treated with semicarbazide.

(II) Two molecules of benzaldehyde are treated with conc. NaOH.

(III) Butan-2-one is treated with Zn/Hg and conc. HCl.

(ii) Arrange the following in the increasing order of their acidic

strength:
(I) CH3CH2CH2COOH, BrCH2CH2CH2COOH, CH3CHBrCH2COOH,
CH3CH2CHBrCOOH

(II) Benzoic acid, 4-Methoxybenzoic acid, 4-Nitrobenzoic acid,

3,4-Dinitrobenzoic acid
Solution. (a) (i) Chemical Reactions
(1) Acetone with Semicarbazide:
When acetone reacts with semicarbazide, it forms a semicarbazone. This is
a typical reaction used to detect and identify ketones and aldehydes. The
reaction is:

CH3COCH3 + H2N-NH-C(O)-NH2 → CH3C(=NNHCONH2)CH3 + H2O

(II) Benzaldehyde with Conc. NaOH:

When two molecules of benzaldehyde react with concentrated sodium
hydroxide (NaOH), they undergo benzoin condensation. This reaction
forms benzoin:

2C6H5CHO + NaOH C6H5CH(OH)C(=O)C6H5

(III) Butan-2-one with Zn/Hg and Conc. HCl:

When butan-2-one is treated with zinc amalgam (Zn/Hg) and concentrated
hydrochloric acid (HCI), it undergoes Clemmensen reduction to yield
butane:

CH3COCH2CH3 + Zn/Hg, HCI → CH3CH2CH2CH3

(ii) Acidic Strength

(1) Arrange in Increasing Order of Acidity:
CH3CH2CH2COOH (Butanoic acid) - Base case.
BrCH2CH2CH2COOH (3-Bromobutanoic acid) - The bromine atom is at
the end of the chain, causing a slight electron-withdrawing effect.
CH3CHBrCH2COOH (2-Bromo-butanoic acid) - The bromine atom is
attached to the middle carbon of the chain, causing a stronger
electron-withdrawing effect.
CH3CH2CHBrCOOH (3-Bromo-butanoic acid) - Bromine at the beta
position shows stronger electron-withdrawing effect compared to others.
Thus, the increasing order of acidity is:
CH3CH2CH2COOH < BrCH2CH2CH2COOH < CH3CHBrCH2COOH <
CH3CH2CHBrCH2​COOH<CH3​CH2​CHBrCOOH
(II) Arrange in Increasing Order of Acidity:

● Benzoic acid – Basic carboxyl group with no additional substituents.

● 4-Methoxybenzoic acid – The Methoxy group is an electron-donating
group, which decreases the acidity.
● 4-Nitrobenzoic acid – Nitro group is a strong electron-withdrawing
group, which increases the acidity.
● 3,4-Dinitrobenzoic acid – Two nitro groups strongly withdraw electron
density, making it very acidic.

Thus, the increasing order of acidity is:

Benzoic acid<4-Methoxybenzoic acid<4-Nitrobenzoic

acid<3,4-Dinitrobenzoic acid

OR
(ii) How will you bring about the following conversions?
(I) Propanone to Propene
(II) Benzoic acid to Benzaldehyde
(III) Ethanal to But-2-enal

Solution. (ii) Conversions

(1) Propanone to Propene:
To convert propanone (a ketone) to propene (an alkene), you can use a
reduction reaction followed by dehydrogenation. Specifically:
1. Reduction to Propan-2-ol:
Reduce propanone to propan-2-ol (a secondary alcohol) using a reducing
agent like sodium borohydride (NaBH4) or lithium aluminium hydride
(LiAlH4):
CH3COCH3 + NaBH4 → CH3CH(OH)CH3
2. Dehydration to Propene:
Dehydrate propan-2-ol to propene using an acid catalyst like sulfuric acid
(H2SO4):
heat CH3CH(OH)CH3 → CH3CH=CH2 + H2O H2SO4
(II) Benzoic Acid to Benzaldehyde:
To convert benzoic acid to benzaldehyde, you can use the reduction
reaction known as the "reduction of carboxylic acids to aldehydes":
1. Reduction with Lithium Aluminium Hydride (LiAlH4):
First, reduce benzoic acid to benzyl alcohol:
C6H5COOH + LiAlH4 C6H5CH2OH
2. Oxidation with Pyridinium Chlorochromate (PCC):
Oxidize benzyl alcohol to benzaldehyde using PCC:
C6H5CH2OH + PCC → C6H5CHO

(III) Ethanal to But-2-enal:

To convert ethanal (acetaldehyde) to but-2-enal (an aldehyde with a double
bond in the middle), you can follow these steps:
1. Formation of 1,3-Butadiene:
Perform a Wittig reaction using ethanal and a phosphonium ylide to form
1,3-butadiene. This step is indirect but involves:
CH3CHO Ph₃P-CH2, CH2=CH-CH=CH2
2. Oxidation to But-2-enal:
React 1,3-butadiene with an oxidising agent to introduce an aldehyde
group at the 2-position: CH2=CH-CH=CH2 CH3CH=CH-CHO
This reaction requires specific conditions and reagents to introduce the
aldehyde group at the desired position.

Q.33. Attempt any five of the following: 5×1=5 (a) Cut is not stable in
aqueous solution. Comment. (b) Out of Cr2+ and Fe2+, which one is a
stronger reducing agent and why ? (c) Actinoid contraction is greater
from element to element than lanthanoid contraction. Why? (d)
KMnO4 acts as an oxidising agent in acidic medium. Write the ionic
equation to support this. (e) Name the metal in the first transition
series which exhibits +1 oxidation state most frequently. (f) Transition
metals and their compounds are good catalysts. Justify. (g) Scandium
forms no coloured ions, yet it is regarded as a transition element.
Why?
Solution. Copper(1) ions (Cut) are not stable in aqueous solutions due to
their tendency to disproportionate Into Cu2+ and Cu. This
disproportionation reaction occurs because Cut is thermodynamically
unstable:
2Cu+ → Cu2+ + Cu
The Cut ion is prone to oxidation because the Cut ion has a relatively high
free energy compared 2+ to Cut, and water or oxygen in the environment
can facilitate this oxidation.

Cr2+ is a stronger reducing agent than Fe2+. This is because Cr²+ can be
readily oxidised to Cr³+ , and Cr²+ has a higher tendency to lose electrons
compared to Fe2+, which is oxidised to Fe³+ 2+ The standard reduction
potential (E°) for Cr³+/Cr2+ is more negative than for Fe3+/Fe2+, indicating
that Cr²+ has a greater tendency to lose electrons (be oxidised) compared
to Fe2+.

Actinoid contraction is greater than lanthanoid contraction due to the less

effective shielding of the nuclear charge by the 5f electrons compared to
the 4f electrons. In the lanthanides (lanthanide series), the 4f electrons
shield the nuclear charge fairly effectively, leading to a more gradual
increase in nuclear charge and size reduction. However, in the actinides
(actinide series), the 5f electrons are less effective at shielding, leading to a
greater increase in the effective nuclear charge felt by the electrons. This
results in a more significant contraction in size from element to element in
the actinide series.

In acidic medium, potassium permanganate (KMnO4) acts as a strong

oxidising agent and gets reduced to manganese(II) ion (Mn2+). The
balanced ionic equation for this reaction is:
MnO4 + 8H++5e Mn2+ + 4H2O
In this reaction, MnO (permanganate ion) is reduced to Mn2+, and in the
process, it oxidises 4 other substances.

The metal in the first transition series that exhibits the +1 oxidation state
most frequently is Copper (Cu). Copper commonly shows two oxidation
states: +1 and +2. The +1 oxidation state is particularly notable in
compounds like copper(I) chloride (CuCl) and copper(I) oxide (Cu2O).

Transition metals and their compounds are excellent catalysts due to

several reasons:
1. Variable Oxidation States: Transition metals can exist in multiple
oxidation states, which allows them to participate in various redox reactions
during catalysis.
2. Formation of Complexes: Transition metals can form coordination
complexes with substrates, providing an environment where the reaction
can proceed more efficiently.
3. Ability to Provide Empty d-Orbitals: Transition metals have empty
d-orbitals that can accept electrons from reactants, facilitating the formation
of reaction intermediates.
4. High Surface Area: In heterogeneous catalysis, transition metals often
form solid catalysts with high surface areas, allowing for more effective
interactions with reactants.

Scandium is regarded as a transition element because it has partially filled

d-orbitals in its compounds, which is a characteristic feature of transition
metals. However, Scandium forms only Sc³+ ions in its compounds, which
have no d-electrons (since the 3d orbitals are empty after losing three
electrons). The lack of colour in its ions is due to the absence of d-d
electron transitions in Sc³+. Despite this, Scandium is included in the
transition series because it occupies a position in the periodic table where
transition metals are found and exhibits similar properties, such as variable
oxidation states in its compounds.