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Answer & Solutions
Chemistry

Section-A
1. Which one of the following has lowest 𝑝𝐾𝑎 value?
A. 𝐶𝐻3 − 𝐶𝑂𝑂𝐻
B. 𝑂2 𝑁 − 𝐶𝐻2 − 𝐶𝑂𝑂𝐻
C. 𝐶𝑙 − 𝐶𝐻2 − 𝐶𝑂𝑂𝐻
D. 𝐻𝐶𝑂𝑂𝐻

Answer (B)
Sol.
As, 𝑝𝐾𝑎 = − log 𝐾𝑎
1 1
So, as 𝑝𝐾𝑎 decreases, acidity will increase, i.e. 𝑝𝐾𝑎 𝛼 𝛼
𝑎𝑐𝑖𝑑𝑖𝑐 𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ −𝐼 𝑐ℎ𝑎𝑟𝑎𝑐𝑡𝑒𝑟
Among the given options, −𝑁𝑂2 has highest −𝐼 character i.e., 𝑂2 𝑁 − 𝐶𝐻2 − 𝐶𝑂𝑂𝐻 has highest acidic character i.e.
it will have lowest 𝑝𝐾𝑎 value.
Hence, option (b) is correct answer.

2. Which one of the following cell was used in Apollo space program?
A. Mercury cell
B. MRI
C. 𝐻2 − 𝑂2 Fuel cell
D. Dry cell

Answer (C)

Sol.
One of the most successful fuel cell uses the reaction of hydrogen with oxygen to form water. This fuel cell was
used for providing electric power in Apollo space program.

3. Consider the following standard electrode potential values:

3+
𝐹𝑒𝑎𝑞 + 𝑒 − → 𝐹𝑒𝑎𝑞2+
; 𝐸° = +0.77 𝑉
𝑀𝑛𝑂4 𝑎𝑞 + 8𝐻 + 5𝑒 − → 𝑀𝑛𝑎𝑞
− + 2+
+ 4𝐻2 𝑂𝑙 ; 𝐸° = +1.51 𝑉
What is the cell potential for the redox reaction?
A. −2.28 𝑉
B. −0.74 𝑉
C. +0.74 𝑉
D. +2.28 𝑉

Answer (C)

Sol.
3+
𝐹𝑒𝑎𝑞 + 𝑒 − → 𝐹𝑒𝑎𝑞
2+
; 𝐸° = +0.77 𝑉
𝑀𝑛𝑂4 𝑎𝑞 + 8𝐻 + 5𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂 ; 𝐸° = +1.51 𝑉
− +
 Overall redox reaction will be:
𝑀𝑛𝑂4− + 5𝐹𝑒 2+ + 8𝐻 + → 𝑀𝑛2+ + 5𝐹𝑒 3+ + 4𝐻2 𝑂
Cell potential for redox reaction = 𝐸°𝐹𝑒 2+ /𝐹𝑒 3+ + 𝐸°𝑀𝑛𝑂4− /𝑀𝑛2+
𝐸°𝑐𝑒𝑙𝑙 = −0.77 + 1.51 𝑉
⇒ 𝐸°𝑐𝑒𝑙𝑙 = +0.74𝑉
Hence, option (c) is correct answer.

4. The following experimental rate data were obtained for a reaction carried out at 25° 𝐶:
𝐴(𝑔) + 𝐵(𝑔) → 𝐶(𝑔) + 𝐷(𝑔)
Initial [𝐴(𝑔) ]/𝑚𝑜𝑙 𝑑𝑚−3 Initial [𝐵(𝑔) ]/𝑚𝑜𝑙 𝑑𝑚−3 Initial rate / 𝑚𝑜𝑙 𝑑𝑚−3 𝑠 −1
3.0 × 10−2 2.0 × 10−2 1.89 × 10−4
3.0 × 10 −2
4.0 × 10 −2
1.89 × 10−4
6.0 × 10 −2
4.0 × 10 −2
7.56 × 10−4
What are the orders with respect to 𝐴(𝑔) and 𝐵(𝑔) ?
Order with respect to 𝐴(𝑔) Order with respect to 𝐵(𝑔)
(a) Zero Second
(b) First Zero
(c) Second Zero
(d) Second First

Answer (C)

Sol.
Given reaction,
𝐴(𝑔) + 𝐵(𝑔) → 𝐶(𝑔) + 𝐷(𝑔)
Rare of reaction ∝ [𝐴]𝑥 [𝐵] 𝑦
Here, 𝑥 → order with respect to A
𝑦 → order with respect to B
From given data,
If we double the concentration of [A] at constant [B], then the rate becomes four times, i.e.,
rate of reaction is of second order with respect to A.
If we double the concentration of [B] at constant [A], then the rate remains same, i.e., rate of
reaction is of zero order with respect to B.
i.e., Rate of reaction ∝ [𝐴]2 [𝐵]°
Hence, option (C) is correct answer.

5. The magnetic moment of [𝑁𝑖𝐶𝑙4 ]2−

A. 1.82 𝐵𝑀
B. 2.82 𝐵𝑀
C. 4.42 𝐵𝑀
D. 5.46 𝐵𝑀
[Atomic number: 𝑁𝑖 = 28]

Answer (D)

Sol.
[𝑁𝑖𝐶𝑙4 ]2−
Oxidation state of Ni:
𝑥 − 4 = −2
𝑥 = −2 + 4 = +2
i.e., 𝑁𝑖 2+
Electronic configuration of 𝑁𝑖 ∶ [𝐴𝑟]3𝑑 8 4𝑠 2
Electronic configuration of 𝑁𝑖 2+ : [𝐴𝑟] 3𝑑 8
For 3𝑑 8 : (As Cl is a weak field ligand)

i.e., No. of unpaired electron = 2

 thus, 𝜇 = √𝑛(𝑛 + 2) = √8 𝐵𝑀 = 2.82 𝐵𝑀
Hence, option (b) is correct answer.

6. Which of the following ions has the electronic configuration 3𝑑 6 ? (Atomic number: 𝑀𝑛 = 25, 𝐶𝑜 = 27, 𝑁𝑖 = 28)
A. 𝑁𝑖 3+
B. 𝐶𝑜 3+
C. 𝑀𝑛2+
D. 𝑀𝑛3+

Answer (B)

Sol.
Electronic configuration of 𝑁𝑖 3+ : [𝐴𝑟]3𝑑 7 4𝑠°
Electronic configuration of 𝐶𝑜 3+ : [𝐴𝑟]3𝑑 6 4𝑠°
Electronic configuration of 𝑀𝑛2+ : [𝐴𝑟]3𝑑 5 4𝑠°
Electronic configuration of 𝑀𝑛3+ : [𝐴𝑟]3𝑑 4 4𝑠°
Hence, option (b) is the correct answer.

7. Which of the following aqueous solution will have highest boiling point?
A. 1.0 𝑀 𝐾𝐶𝑙
B. 1.0 𝐾2 𝑆𝑂4
C. 2.0 𝑀 𝐾𝐶𝑙
D. 2.0 𝑀 𝐾2 𝑆𝑂4

Answer (D)

Sol.
As we know, Δ𝑇𝑏 = 𝑖 𝐾𝑏 𝑚
At high dilution, 𝑚 ≈ 𝑀 (i.e., molality ≈ molarity)
So, Δ𝑇𝑏 = 𝑖 𝐾𝑏 𝑀
For 1.0 𝑀 𝐾𝐶𝑙, 𝑖 = 𝑛 = 2
Δ𝑇𝑏 = 2 × 𝐾𝑏 × 1 = 2𝐾𝑏
For 1.0 𝑀 𝐾2 𝑆𝑂4 , 𝑖 = 𝑛 = 3
Δ𝑇𝑏 = 3 × 𝐾𝑏 × 1 = 3𝐾𝑏
For 2.0 𝑀 𝐾𝐶𝑙, 𝑖 = 𝑛 = 2
Δ𝑇𝑏 = 2 × 𝐾𝑏 × 2 = 4𝐾𝑏
For 2.0 𝑀 𝐾2 𝑆𝑂4 , 𝑖 = 𝑛 = 3
Δ𝑇𝑏 = 3 × 𝐾𝑏 × 2 = 6𝐾𝑏
Thus, 2.0 𝑀𝐾2 𝑆𝑂4 has highest elevation in boiling point. So, it has highest boiling point.
Hence, option (d) is correct answer.

8. A voltaic cell is made by connecting two half cells represented by half equations below:
2+
𝑆𝑛(𝑎𝑞) + 2𝑒 − → 𝑆𝑛(𝑠) ; 𝐸° = −0.14 𝑉
3+ 2+
𝐹𝑒(𝑎𝑞) + 𝑒 − → 𝐹𝑒(𝑎𝑞) ; 𝐸° = +0.77 𝑉
Which statement is correct about this voltaic cell?
A. 𝐹𝑒 2+ is oxidized and the voltage of the cell is -0.91V
B. 𝑆𝑛 is oxidized and the voltage of the cell is 0.91 V
C. 𝐹𝑒 2+ is oxidized and the voltage of the cell is 0.91 V
D. 𝑆𝑛 is oxidized and the voltage of the cell is 0.63 V
Answer (B)

Sol.
2 𝐹𝑒 3+ + 2𝑒 − → 2 𝐹𝑒 2+ ; 𝐸° = 0.77 𝑉
𝑆𝑛 → 𝑆𝑛2+ + 2𝑒 − ; 𝐸° = 0.14 𝑉
-----------------------------------------------
2 𝐹𝑒 3+ + 𝑆𝑛 → 2 𝐹𝑒 2+ + 𝑆𝑛2+ ; 𝐸°𝑐𝑒𝑙𝑙 = 𝐸°𝐹𝑒 3+/𝐹𝑒 2+ + 𝐸°𝑆𝑛/𝑆𝑛2+ = 0.77 + 0.14 = 0.91 𝑉
Hence, option (b) is correct answer.
9. Amides can be converted into amines by the reaction named
A. Hoffmann degradation
B. Ammonolysis
C. Carbylamine
D. Diazotisation

Answer (A)

Sol.
Hoffman degradation reaction used to convert an amide into an amine (primary).

10. Which of the following statements is not true about glucose?

A. It is an aldohexose.
B. On heating with HI, it forms n-hexane.
C. It is present in pyranose form.
D. It gives 2, 4-DNP test.

Answer (D)

Sol.
Glucose is an aldohexose which on heating with HI, forms n-hexane. It is found in cyclic pyranose form. Glucose
does not react with 2, 4-DNP reagent despite having aldehyde group because there is no free aldehyde group
present in cyclic form as it forms hemiacetal. Thus, it does not give 2, 4-DNP test.

Hence, option (d) is correct answer.

11. Which of the following alcohols will not undergo oxidation?

A. Butanol
B. Butan-2-ol
C. 2-Methylbutan-2-ol
D. 3-Methybutan-2-ol

Answer (C)

Sol.
Generally, tertiary alcohol does not undergo oxidation. So, 2-methylbutan-2-ol does not undergo oxidation;
whereas 1° alcohol oxidises to aldehyde and 2° alcohol oxidises to ketone.
 Hence, option (c) is correct answer.

12. Four half reactions I to IV are shown below:

𝐼. 2𝐶𝑙 − → 𝐶𝑙2 + 2𝑒 −
𝐼𝐼. 4𝑂𝐻 − → 𝑂2 + 2𝐻2 𝑂 + 2𝑒 −
𝐼𝐼𝐼. 𝑁𝑎+ + 𝑒 − → 𝑁𝑎
𝐼𝑉. 2𝐻 + + 2𝑒 − → 𝐻2
Which two of these reactions are most likely to occur when concentrated brine is electrolysed?
A. I and III
B. I and IV
C. II and III
D. II and IV

Answer (A)

Sol.
When concentrated brine is electrolysed, 𝐶𝑙 − will undergo oxidation at anode to form 𝐶𝑙2 and 𝑁𝑎 + will undergo
reduction at cathode to form Na.

13. Which property of transition metals enables them to behave as catalysts?

A. High melting point
B. High ionization enthalpy
C. Alloy formation
D. Variable oxidation states

Answer (D)

Sol.
Transition metals can act as catalysts because of their variable oxidation states.

14. Which of the following would not be a good choice for reducing nitrobenzene to aniline?

A. 𝐿𝑖𝐴𝑙𝐻4
B. 𝐻2 /𝑁𝑖
C. 𝐹𝑒 𝑎𝑛𝑑 𝐻𝐶𝑙
D. 𝑆𝑛 𝑎𝑛𝑑 𝐻𝐶𝑙

Answer (A)

Sol.
𝐿𝑖𝐴𝑙𝐻4 is not a good choice for reducing nitrobenzene to aniline.

For questions number 15 to 18, 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.

15. Assertion (A): Vitamin C cannot be stored in our body.

Reason (R): Vitamin C is fat soluble and is excreted from the body in urine.

Answer (C)
Sol.
Vitamin C is a water soluble vitamin. Water soluble vitamins must be supplied regularly in diet because they are
readily excreted in urine and cannot be stored in our body.
Hence, assertion (A) is true, but reason (R) is false.

16. Assertion (A): The half life of a reaction is the time in which the concentration of the reactant is reduced to one half
of its initial concentration.
Reason (R): In first order kinetics when concentration of reactant is doubled, its half life is doubled.

Answer (C)

Sol.
Half life of a reaction is the time in which the concentration of reactant is reduced to one half of its initial reaction.
As we know:
1
𝑡1/2 ∝ [𝐴 ]𝑛−1
0
For 1st order, 𝑡1/2 is independent upon initial concentration of reactant.
Hence, assertion (𝐴) is correct but reason (R) is false.

17. Assertion (A): Bromination of benzoic acid gives m–bromobenzoic acid.

Reason (R): Carboxyl group increases the electron density at the meta position.

Answer (C)

Sol.

Carboxyl group (-COOH) is an electron withdrawing group (-I, -R) which decreases the electron density on benzene
ring.

Here, via (-R – effect) decreases the electron density at ortho and para position. So, bromination of benzoic acid
gives meta product. But –I effect is observed at meta position as well, so reason is false.

18. Assertion (A): EDTA is a hexadentate ligand.

Reason (R): EDTA has 2 nitrogen and 4 oxygen donor atoms.

Answer (A)

Sol.
EDTA (Ethylenediaminetetraacetic acid)
 EDTA has 2 nitrogen and 4 oxygen donor atoms. Hence, EDTA is a hexadentate ligand.

Section-B
19. (a) Which of the following species cannot act as a ligand? Give reason.
𝑂𝐻 − , 𝑁𝐻4+ , 𝐶𝐻3 𝑁𝐻2 , 𝐻2 𝑂
(b) The complex [𝐶𝑜(𝑁𝐻3 )5 (𝑁𝑂2 )]𝐶𝑙2 is red in colour. Give IUPAC name of its linkage isomer.

Sol.

(a) Usually, species having lone pairs can acts as a ligand. Here, 𝑁𝐻4⊕ ion cannot act as ligand
because it does not possess any lone pairs of electrons which it can donate to central metal ion,
whereas 𝑂𝐻 − , 𝐶𝐻3 𝑁𝐻2 & 𝐻2 𝑂 can act as ligands as they have lone pairs of electron.

(b) [𝐶𝑜(𝑁𝐻3 )5 (𝑁𝑂2 )]𝐶𝑙2

Its linkage isomer: [𝐶𝑜(𝑁𝐻3 )5 (𝑂𝑁𝑂)]𝐶𝑙2
IUPAC name of linkage isomer: Pentaamminenitrito-O-cobalt (III) chloride

20. For the pair phenol and cyclohexanol, answer the following:
(a) Why is phenol more acidic than cyclohexanol?
(b) Give one chemical test to distinguish between the two.

Sol.
(a) Phenol is more acidic than cyclohexanol because conjugate base of phenol i.e., phenoxide ion is more stable
due to resonance.
 (b) Bromine water test can be used to distinguish between phenol and cyclohexanol. Phenol decolorizes bromine
water and gives white precipitate of 2, 4, 6 – tribromophenol. But cyclohexanol does not give this test.

21. (a) (i) Draw the zwitter ion structure for sulphanilic acid.
(ii) How can the activating effect of − 𝑁𝐻2 group in aniline be controlled?
OR
(b) (i) Complete the reaction with the main product formed:

(ii) Convert Bromoethane to Propanamine.

Sol.
(a) (i) Zwitter ion structure of sulphanilic acid:

(ii) The activating effect of −𝑁𝐻2 group can be controlled by acetylation of −𝑁𝐻2 group.

In acetanilide lone pairs of nitrogen are involved in resonance with adjacent -C=O group as well, so it
decreases the activating effect of − 𝑁𝐻2 group.

(b) (i) Benzene diazonium chloride reacts with ethyl alcohol to give acetaldehyde and benzene.
 (ii) Convert bromoethane to propanamine: Reaction of bromoethane with KCN followed by reduction gives
propanamine.

22. Write equations for the following:

(a) Oxidation of chloroform by air and light
(b) Reaction of chlorobenzene with 𝐶𝐻3 𝐶𝑙/ anhyd. AlCl3

Sol.
(a) Chloroform is slowly oxidized by air in the presence of light to an extremely poisonous gas, carbonyl chloride,
also known as phosgene.
1 𝑙𝑖𝑔ℎ𝑡
𝐶𝐻𝐶𝑙3 + 𝑂2 → 𝐶𝑂𝐶𝑙2 + 𝐻𝐶𝑙
2

(b) Reaction of chlorobenzene with 𝐶𝐻3 𝐶𝑙/ 𝑎𝑛ℎ𝑦𝑑. 𝐴𝑙𝐶𝑙3 gives ortho and para substituted methylbenzene as
products, this reaction is known as Friedel Crafts reaction.

23. What happens to the rate constant k and activation energy 𝐸𝑎 as the temperature of a chemical reaction is
increased? Justify.

Sol.
As the temperature of chemical reaction is increased, the rate constant k increases, whereas,
activation energy 𝐸𝑎 decreases.
According to Arrhenius equation:
𝑘 = 𝐴𝑒 − 𝐸𝑎 / 𝑅𝑇
So, rate constant k increases exponentially with increase in temperature.
Ea decreases with increase in temperature as shown in following graph:
 Here, 𝐸𝑎1 > 𝐸𝑎 2 i.e., with increase in temperature activation energy decreases because energy of
reactant increases at higher temperature.
0
24. (a) (i) What should be the signs (positive /negative) for 𝐸𝐶𝑒𝑙𝑙 and Δ 𝐺 0 for a spontaneous redox reaction occurring
under standard conditions ?
(ii) State Faraday’s first law of electrolysis.

OR

(b) Calculate the emf of the following cell at 298 K:

+
𝐹𝑒(𝑠) | 𝐹𝑒 2+ (0.01𝑀)||𝐻(1𝑀) |𝐻2(𝑔) (1 𝑏𝑎𝑟 ), 𝑃𝑡(𝑠)
0
Given 𝐸𝑐𝑒𝑙𝑙 = 0.44 𝑉.

Sol.
(a) (i) Δ𝐺 0 for a redox reaction should to negative for a reaction to occur spontaneously.
As , Δ 𝐺 0 = −𝑛𝐹𝐸 0
So, 𝐸 0 should be positive for spontaneous redox reaction.
(ii) Faraday’s first law of electrolysis states that the amount of chemical change being produced
by a current at an electrode-electrolyte interface is proportional to the quantity of electricity used.

OR

(b)
Cell : 𝐹𝑒(𝑠) |𝐹𝑒 2+ (0.01 𝑀 ||𝐻 + (1 𝑀)|𝐻2 (𝑔)(1 𝑏𝑎𝑟 ), 𝑝𝑡 (𝑠)
0
𝐸𝑐𝑒𝑙𝑙 = 0.44 𝑉
2+
Reaction at anode : 𝐹𝑒(𝑠) → 𝐹𝑒(𝑎𝑞) + 2𝑒 −
+
2𝐻(𝑎𝑞) +2𝑒 − →𝐻2 (𝑔)
Reaction at cathode : + →𝐹𝑒 2+ +𝐻 (𝑔) …….(1)
𝐹𝑒(𝑠)+2𝐻(𝑎𝑞) (𝑎𝑞) 2
According to Nernst equation at 298 K:
0.0591 [𝐹𝑒 2+ ]𝑃𝐻2
𝐸 = 𝐸0 − 𝑙𝑜𝑔 [𝐻 + ]2
𝑛
As n = 2 from reactions,
0.0591 0.01
𝐸 = 0.44 − 𝑙𝑜𝑔
2 1
0.0591
𝐸 = 0.44 + 2 ×
2
E = 0.44 + 0.0591 = 0.4991 V

25. Give the reaction of glucose with acetic anhydride. Presence of which group is confirmed by this reaction ?

Sol.
Reaction of glucose with acetic anhydride :
 Acetylation of glucose with acetic anhydride gives glucose pentaacetate which confirms the presence of five – OH
groups. Since, it exists as a stable compound, five – OH groups should be attached to different carbon atoms.

26. (a) (i) Why is the C – O bond length in phenols less than that in methanol?
(ii) Arrange the following in order of increasing boiling point:
Ethoxyethane, Butanal, Butanol, n – butane
(iii) How can phenol be prepared from anisole? Give reaction.

OR
(b) (i) Give mechanism of the following reaction:
𝐻2 𝑆𝑂4, 413 𝐾
𝐶𝐻3 𝐶𝐻2 𝑂𝐻 → 𝐶𝐻3 𝐶𝐻2 − 𝑂 − 𝐶𝐻2 𝐶𝐻3 + 𝐻2 𝑂

(ii) Illustrate hydroboration-oxidation with an example.

Sol.
(a) (i) C-O bond length in phenol is less than in methanol because in phenol C-O bond has some double bond
character due to resonance.

(ii) Increasing order of boiling point:

n-butane < Ethoxyethane < Butanal < Butanol

(iii)

(b) (i)
 (ii) Hydroboration – Oxidation: Diborane reacts with alkenes to give trialkyl diboranes as addition product. This
is oxidised to alcohol by hydrogen peroxide in the presence of aqueous sodium hydroxide.

27. (a) On the basis of crystal field theory write the electronic configuration for 𝑑 5 ion with a weak ligand for which
Δ0 < 𝑃.
(b) Explain [𝐹𝑒(𝐶𝑁)6 ]3− is an inner orbital complex whereas [𝐹𝑒𝐹6 ]3− is an outer orbital complex.
[Atomic number: 𝐹𝑒 = 26 ]

Sol.
a) For weak field ligand; Δ0 < 𝑃 i.e., pairing will not occur for 𝑑 5 ion.

b). [𝐹𝑒(𝐶𝑁)6 ]3− :

𝐹𝑒 ⇒ +3 oxidation state i.e., E. C. = 3𝑑 5
𝐶𝑁 − ⇒ strong field ligand i.e., Δ0 > 𝑃 ⇒ Pairing will take place
Electronic configuration of 𝐹𝑒 3+ : 3𝑑 5

i.e., Hybridisation will be: 𝑑 2 𝑠𝑝3

i.e., Inner orbital complex

[𝐹𝑒𝐹6 ]3−
𝐹𝑒 ⇒ +3 oxidation state i.e., E.C. ⇒ 3𝑑 5
𝐹 − ⇒ weak field ligand i.e., Δ0 < 𝑃 ⇒ Pairing will not take place
 Electronic configuration of 𝐹𝑒 3+ ∶ 3𝑑 5

i.e., Hybridisation will be: 𝑠𝑝3 𝑑 2

i.e., Outer orbital complex

28. Give reasons for any 3 of the following observations:

a. Penta-acetate of glucose does not react with hydroxylamine.
b. Amino acids behave like salts.
c. Water soluble vitamins must be taken regularly in diet.
d. The two strands in DNA are complimentary to each other.

Sol.
a) When D-glucose is reacted with hydroxylamine, due to the aldehydic group present in it,
oxime formation occurs. However, D-glucose pentacetate does not react with hydroxylamine
because the aldehyde group is absent due to cyclic structure formed due to hemiacetylation.

b) Amino acids behave like salts rather than simple amines or carboxylic acids. This behavior is due
to the presence of both acidic and basic groups in the same molecule. In aqueous solution, amino
acid acts as dipolar or zwitter ion.

c) Water soluble vitamins must be supplied regularly in diet because they are readily excreted
in urine and cannot be stored in our body.

d) The two strands in DNA are complimentary to each other because the hydrogen bonds are
formed between specific pairs of bases. Adenine forms hydrogen bond with thymine whereas
cytosine forms hydrogen bonds with guanine.

29. (a) For the reaction:

2𝑁2 𝑂5(𝑔) → 4𝑁𝑂2 (𝑔) + 𝑂2 (𝑔) at 318 K
Calculate the rate of reaction if rate of disappearance of 𝑁2 𝑂5 (𝑔) is 1.4 × 10−3 𝑀 𝑠 −1 .
(b) For a first order reaction derive the relationship 𝑡99% = 2 𝑡90%

Sol.
(a.) 2 𝑁2 𝑂5 (𝑔) → 4 𝑁𝑂2 (𝑔) + 𝑂2 (𝑔)
𝑑[𝑁2 𝑂5 ]
− 𝑑𝑡
= 1.4 × 10−3 𝑀𝑠 −1 (Given)
1 𝑑[𝑁2 𝑂5 ] 1
Rate of reaction = − 2 𝑑𝑡
= 2 × 1.4 × 10−3 = 0.7 × 10−3 𝑀𝑠 −1
= 7 × 10−4 𝑀𝑠 −1

(b.) Relation for 1st order reaction:

2.303 [𝜃 ]
𝑡= 𝑙𝑜𝑔 0
𝑘 [𝜃]
For 𝑡90% ∶ [𝜃] = 0.1[𝜃0 ]
2.303 [𝜃0 ] 2.303
𝑡90% = 𝑘 𝑙𝑜𝑔 0.1[𝜃 ]
= 𝑘 𝑙𝑜𝑔 10
0
2.303
i.e. 𝑡90% = 𝑙𝑜𝑔 10 -------------------(1)
𝑘

For 𝑡99% : [θ] = 0.01[θ0 ]

 2.303 [𝜃0 ]
𝑡99% = 𝑘
𝑙𝑜𝑔 0.01[𝜃
0]
2.303
i.e., 𝑡99% = 𝑘 log 102
2.303
⇒ 𝑡99% = × 2 log 10--------------------------(2)
𝑘
Comparing eq (2) with (1), we get:
𝑡99% = 2 𝑡90%

30. (a) Illustrate Sandmeyer's reaction with an equation.

(b) Explain, why (𝐶𝐻3 )2 𝑁𝐻 is more basic than (𝐶𝐻3 )3 𝑁 in aqueous solution.

Sol.
(a) Sandmeyer's Reaction:

Sandmeyer reaction is a chemical reaction used to synthesize aryl halide from aryl diazonium
chloride using copper salt as reagent or catalyst.
(b) Basic strength of amines ∝ stability of Conjugate Acid

(𝐶𝐻3 )2 𝑁𝐻 is more basic than (𝐶𝐻3 )3 𝑁 in aqueous solution. (𝐶𝐻3 )2 𝑁𝐻2+ is hydrated to a
greater extent than (𝐶𝐻3 )3 𝑁𝐻 ⊕ . As the number of methyl group increases, the extent of hydration
decreases due to steric hindrance. Greater is the extent of hydration, greater is the stability of ion
and greater is the basic strength of amine.

SECTION – D

The following questions are case-based questions. Read the passage carefully and answer the questions that
follow:

31. Rahul set-up an experiment to find resistance of aqueous KCl solution for different
concentrations at 298 K using a conductivity cell connected to a Wheatstone bridge.
He fed the Wheatstone bridge with a.c. power in the audio frequency range of 550 to 5000 cycles per
second. Once the resistance was calculated from null point, he also calculated the conductivity (K)
and molar conductivity (∧𝑚 ) and recorded his reading in tabular form

S.No Conc.(M) k S cm−1 Λ𝑚 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1

1. 1.00 111.3 × 10−3 111.3
2. 0.10 12.9 × 10−3 129.3
3. 0.01 1.41 × 10−3 141.0

Answer the following questions:

(a) Why does conductivity decrease with dilution?

(b) If ∧0𝑚 𝑜𝑓 𝐾𝐶𝑙 𝑖𝑠 150.0 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1 , calculate the degree of dissociation of 0.01 M KCl.
(c) If Rahul had used HCl instead to KCl then would you expect the ∧𝑚 values to be more or less
than those per KCl for a given concentration. Justify.

OR

(c) Amit a classmate of Rahul repeated the same experiment with 𝐶𝐻3 𝐶𝑂𝑂𝐻 solution instead of 𝐾𝐶𝑙
solution. Give one point that would be similar and one that would be different in his observations as
compared to Rahul.
Sol.
(a) The conductivity of solution is the conductance of ions present in a unit volume of the
solution. The number of ions (responsible for carrying current) decreases when the solution is
diluted. As a result, conductivity of solution decreases with dilution.

(b.) Λ0𝑚 (𝐾𝐶𝑙) = 150.0 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1

Λ𝑚 (0.01 𝑀 𝐾𝐶𝑙) = 141 𝑆 𝑐𝑚2 𝑚𝑜𝑙 −1
Λ
As we know: 𝛼 = 𝑚 0Λ𝑚
141
⇒ 𝛼= = 0.94
150

(c) If Rahul had used HCl instead to KCl then the Λ𝑚 value will be higher than that for KCl for a
given concentration.
The reason behind the increase in molar conductivity of 𝐻 ⊕ as compared to 𝐾 ⊕ is that 𝐻 ⊕ has the highest
value of molar conductance in aqueous state because the proton is transferred from one water
molecule to another in hydrogen bonded chain of water molecules.

OR

(c) Amit observed that molar conductivity increases with dilution but specific conductivity
decreases on dilution.

Nucleophilic Substitution

Nucleophilic Substitution reaction of haloalkane can be conducted according to both 𝑆𝑁 1 and 𝑆𝑁 2

mechanisms. 𝑆𝑁 1 is a two-step reaction while 𝑆𝑁 2 is a single step reaction. For any haloalkane
which mechanism is followed depends on factors such as structure of haloalkane, properties of
leaving group, nucleophilic reagent and solvent.
Influences of solvent polarity : In 𝑆𝑁 1 reaction, the polarity of the system increases from the
reactant to the transition state, because a polar solvent has a greater effect on the transition state
than the reactant, thereby reducing activation energy and accelerating the reaction.
In 𝑆𝑁 2 reaction, the polarity of the system generally does not change from the reactant to the transition state
and only charge in dispersion occurs. At this time, polar solvent has a great stabilizing effect on Nu than the
transition state, thereby increasing activation energy and slow down the reaction rate. For example,
the decomposition rate (𝑆𝑁 1) of tertiary chlorobutane at 25∘ 𝐶 in water (dielectric constant 79) is
300000 times faster than in ethanol (dielectric constant 24). The reaction rate (𝑆𝑁 2) of
2-Bromopropane and NaOH in ethanol containing 40 % water is twice slower than in absolute
ethanol. Hence the level of solvent polarity has influence on both 𝑆𝑁 1 and 𝑆𝑁 2 reaction, but with
different results. Generally speaking weak polar solvent is favourable for 𝑆𝑁 2 reaction, while strong
polar solvent is favourable for 𝑆𝑁 1. Generally speaking the substitution reaction of tertiary haloalkane is based
on 𝑆𝑁 1 mechanism in solvents with a strong polarity (for example ethanol containing water).

32. Answer the following questions:

(a) Why racemisation occurs in 𝑆𝑁 1?
(b) Why is ethanol less polar than water?
(c) Which one of the following in each pair is more reactive towards 𝑆𝑁 2 reaction?
(i) 𝐶𝐻3 − 𝐶𝐻2 − 𝐼 or 𝐶𝐻3 𝐶𝐻2 − 𝐶𝑙
(ii)

OR

(c) Arrange the following in the increasing order of their reactivity towards 𝑆𝑁 1 reactions:
(i) 2-Bromo-2-methylbutane, 1-Bromopentane, 2-Bromopentane
(ii) 1-Bromo-3-methylbutane, 2-Bromo-2-methylbutane, 2-Bromo-3-methylbutane

Sol.
a) In 𝑆𝑁 1, intermediate formed is carbocation which is planar. So, nucleophile can attack from same or back side
 leading to racemization

b) Ethanol is less polar than water because the bond between carbon and hydrogen is not very polar unlike the
oxygen-hydrogen bond in a water molecule. Thus, the net dipole moment of ethanol is less than 𝐻2 𝑂 molecule
leading to its less polarity.
(c) (i) 𝐶𝐻3 − 𝐶𝐻2 − 𝐼 is more reactive than 𝐶𝐻3 𝐶𝐻2 − 𝐶𝑙 towards 𝑆𝑁 2 reaction because 𝐼 ⊖ is a better leaving
group than 𝐶𝑙 ⊖
(ii)

is more reactive than towards 𝑆𝑁 2 reaction due to less steric

hindrance.

OR

c) (i) Increasing order of reactivity toward 𝑆𝑁 1 reaction:

2- Bromo -2 –methylbutane > 2- Bromopentane > 1- Bromopentane
3∘ 2∘ 1∘
(ii) Increasing order of reactivity toward 𝑆𝑁 1 reaction:
2-Bromo-2-methylbutane > 2-Bromo-3- methylbutane >1-Bromo-3-methylbutane
3∘ 2∘ 1∘

SECTION – E

33. (a) (i) Write the reaction involved in Cannizaro’s reaction.

(ii) Why are the boiling points of aldehydes and ketones lower than that of corresponding carboxylic acids ?
(iii) An organic compound ‘A’ with molecular formula 𝐶5 𝐻8 𝑂2 is reduced to n-pentane with hydrazine followed by
heating with NaOH and Glycol. ‘A’ forms a dioxime with hydroxylamine and gives a positive Iodoform and Tollen’s
test. Identify ‘A’ and give its reaction for Iodoform and Tollen’s test.

Sol.
a). i) Cannizaro’s reaction:

ii) Boiling point of aldehyde and ketones are lower than that of corresponding carboxylic acids due to the
presence of intermolecular hydrogen bonding in carboxylic acids.
 iii)

OR

(b) (i) Give a chemical test to distinguish between ethanal and ethanoic acid.
(ii) Why a r e the 𝛼-hydrogens of aldehy des and ketones acidic i n nature?
( i i i ) A n organic compound 'A' with molecular formula 𝐶4 𝐻8 𝑂2 undergoes acid hydrolysis to form two
compounds 'B' and'C’. Oxidation of ·’C’ with acidified potassium permanganate also produces 'B'.
Sodium salt of 'B ' on heating with soda lime gives methane .
(1) Identify 'A', 'B’ and 'C'.
(2) Out of 'B' and 'C', which will have higher boiling point?
Give reason .
Sol.
(c) (i) Sodium bicarbonate test is used to distinguish between ethanal and ethanoic acid.
( i i ) 𝛼 −h y d r o g e n s o f a l d e h y d e a n d k e t o n e a r e a c i d i c i n n a t u r e b e c a u s e t h e c o r r e s p o n d i n g
conjugate base is stable due to resonance.

iii)
1)
 (2) From above reaction, its clear that B is ethanoic acid.

Ethanoic acid has higher boiling point than ethanol i.e., B has higher boiling point than C
due to more hydrogen bonding in ethanoic acid than ethanol.

34. (i) Why is boiling point of 1 M NaCl solution more than that of 1 M glucose solution?
(ii) A non-volatile solute ‘X’ (molar mass = 50 g 𝑚𝑜𝑙 −1 ) when dissolved in 78 g of benzene
reduced its vapour pressure to 90%. Calculate the mass of X dissolved in the solution.
(iii) Calculate the boiling point elevation for a solution prepared by adding 10 g of 𝑀𝑔𝐶𝑙2 to
200 g of water assuming 𝑀𝑔𝐶𝑙2 is completely dissociated.
(𝐾𝑏 for water = 0.512 𝐾 𝑘𝑔 𝑚𝑜𝑙 −1 , Molar mass 𝑀𝑔𝐶𝑙2 = 95 𝑔 𝑚𝑜𝑙 −1 )

Sol
(a). i) As ∆𝑇𝑏 = 𝑖 𝐾𝑏 𝑚
At higher dilution, 𝑚 ≈ 𝑀
For : 1 𝑀 𝑁𝑎𝐶𝑙 ∶ 𝑖 = 𝑛 = 2 (∵ 𝑁𝑎𝐶𝑙 is strong electrolyte)
i.e., ∆𝑇𝑏 = 2 𝑘𝑏
For : 1 𝑀 𝑔𝑙𝑢𝑐𝑜𝑠𝑒: 𝑖 = 𝑛 = 1
i.e., ∆𝑇𝑏 = 𝑘𝑏
So, elevation in boiling point is higher for NaCl, that’s why NaCl solution has higher boiling point than glucose.

ii) Relative lowering of vapour pressure,

𝑝0 −𝑃𝑆 𝑛𝐵
=
𝑃𝑆 𝑛𝐴
𝑝0 −0.9𝑝0 𝑊 78
= 𝐵×
0.9𝑝0 50 78
0.1 50
⇒ 𝑊𝐵 = × 50 = = 5.5 𝑔
0.9 9

(iii) Boiling point elevation:

∆𝑇𝑏 = 𝑖 𝐾𝑏 𝑚
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
For 𝑀𝑔𝐶𝑙 2 : 𝑖 = 𝑛 = 3 and 𝑚 =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔
10
And 𝑚 =
95 × 0.2
10
So, ∆𝑇𝑏 = 3 × 0.512 ×
95×0.2
∆𝑇𝑏 = 0.80 𝐾

OR

(b) (i) Why is the value of van’t Hoff factor for ethanoic acid in benzene close to 0.5 ?
(ii) Determine the osmotic pressure of a solution prepared by dissolving 2.32 × 10−2 𝑔 𝑜𝑓 𝐾2 𝑆𝑂4
in 2 L of solution at 25 ℃, assuming that 𝐾2 𝑆𝑂4 is completely dissociated.
(R=0.082 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 , Molar mass of 𝐾2 𝑆𝑂4 = 174 𝑔𝑚𝑜𝑙 −1 )
(iii) When 25.6 g of Sulphur was dissolved in 1000 g of benzene, the freezing point lowered by
0.512 K. Calculate the formula of Sulphur (𝑆𝑥 ).
(𝐾𝑓 for benzene = 5.12 𝐾 𝑘𝑔 𝑚𝑜𝑙 −1 , Atomic mass of Sulphur = 32 𝑔 𝑚𝑜𝑙 −1 )

Sol.

(b) (i) As ethanoic acid undergo dimerization in benzene that’s why the value of van’t Hoff factor
for ethanoic acid is close to 0.5.
(ii) Osmotic Pressure :
𝜋 = 𝑖 𝐶𝑅𝑇
𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝐶=
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑆𝑜𝑙𝑢𝑡𝑖𝑜𝑛 (𝑖𝑛 𝐿)
2.32 ×10−2
⟹𝐶= and 𝑇 = 25℃ = 298 𝐾
174 ×2
⟹ 𝑖 (𝐾2 𝑆𝑂4 ) = 3
 2.32 ×10−2
So, 𝜋 = × 0.082 × 298 × 3
174 ×2
−3
𝜋 = 4.89 × 10 𝑎𝑡𝑚
(iii) Depression in freezing point,
∆𝑇𝑓 = 𝑖 𝐾𝑓 𝑚
For sulphur, i = 1
𝑁𝑜. 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 25.6
And 𝑚 = =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑘𝑔 𝑀 ×1
25.6
So, ∆𝑇𝑓 = 1 × 5.12 ×
𝑀×1
25.6
⟹ 0.512 = 5.12 ×
𝑀×1
5.12 × 25.6
⟹𝑀= = 256 𝑔/𝑚𝑜𝑙
0.512
As, Molar mass of sulphur atom is 32 g/mol
Molar mass of Sulphur molecule (𝑆𝑥 ) = 256 𝑔/𝑚𝑜𝑙
i.e., formula of Sulphur ⟹ 𝑆8

35. (a) A transition element X has electronic configuration [𝐴𝑟]4𝑠 2 3𝑑 3 . Predict its likely oxidation states.
(b) Complete the reaction mentioning all the products formed :

(c) Account for the following:

(i) In the 3d transition series, zinc has the lowest enthalpy of atomisation.
(ii) 𝐶𝑢+ ion is unstable in aqueous solution.
(iii) Actinoids show more number of oxidation states than lanthanoids .

Sol.
(a) Electronic configuration of 𝑋 ∶ [𝐴𝑟]4𝑠 2 3𝑑 3
The given element X is Vanadium, a transition element. It will show the following variable
oxidation states: +2 , +3, +4, and +5.
(b)

(c) i) Due to absence of unpaired electrons in ns and (n-1)d shells, the atomic electron bonding
is the weakest in zinc. Consequently, zinc has lowest enthalpy of atomisation in 3d transition series.
(ii) 𝐶𝑢+ is unstable in aqueous solution, this is because although energy is required to remove
one electron from 𝐶𝑢 ⊕ 𝑡𝑜 𝐶𝑢2+ , high hydration energy of 𝐶𝑢2+ compensate for it. Therefore, 𝐶𝑢⊕
ion is unstable in aqueous solution and undergoes disproportionation to give 𝐶𝑢 2+ 𝑎𝑛𝑑 𝐶𝑢.
(iii) Actinides have a greater range of oxidation state, because of very small energy gap between
5f, 6d and 7s subshells. Thus, the outermost electrons get easily excited to higher energy levels
giving variable oxidation states.