Solution

Section A

1. (a) SOCl2 in presence of pyridine

Explanation: The hydroxyl group of an alcohol is replaced by halogen on reaction with concentrated halogen acids, phosphorus
halides, or thionyl chloride. Thionyl chloride (SOCl 2) is preferred because the other two products SO2 and HCl are escapable
gases. Hence, the reaction gives pure alkyl halides. ROH + SOCl 2 → RCl + SO2 (g) + HCl (g)

2. (a) H2N.CH2.COOH

Explanation: Amino acids contain amino (–NH2) and carboxyl (–COOH) functional groups.

3.
(d) All of these Explanation:
The addition of water to an alkene in the presence of a catalytic amount of strong acid leads to the formation of alcohols
(hydroxy‐alkanes).
H+

CH2 = CH2 + H2O −−→ CH3CH2OH

This reaction proceeds via a standard carbocation mechanism and follows the Markovnikov rule.
The mechanism for the addition of water to ethene follows.
1. The hydrogen ion is attracted to the π bond, which breaks to form a σ bond with one of the double‐bonded carbons. The
second carbon of the original double‐bonded carbons becomes a carbocation.

2. An acid‐base reaction occurs between the water molecule and the carbocation, forming an oxonium ion.

3. The oxonium ion stabilizes by losing a hydrogen ion, with the resulting formation of an alcohol.

4.
(b) (CH3)2C(OC2H5)(OC2H5)
Explanation: Ketones or aldehydes react with alcohols to form acetals. This reaction of alcohol on aldehydes or ketones is
catalyzed in the presence of acid and is a reversible reaction. Firstly a hemiacetal (CH 3)2C(OH)(OC2H5) is formed which
further reacts with alcohol to give acetal.
H+

⇄
(CH3)2C(OC2H5)(OC2H5) CH3COCH3 + 2C2H5OH (CH3)2C(OC2H5)(OC2H5)
5.
(b) Acid catalysed hydrolysis of ethyl acetate
Explanation: In acid catalysed the hydrolysis of ethyl acetate the water is in excess so it is pseudo 1st order reaction, as the does
not change.
6.
(d) (a) ‐ (iv), (b) ‐ (iii), (c) ‐ (ii), (d) ‐ (i)
Explanation: (a) ‐ (iv), (b) ‐ (iii), (c) ‐ (ii), (d) ‐ (i)
7.

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 (b) Ethyl bromide + alcoholic KCN
Explanation: CH3CH2Br + KCN → CH3CH2CN + KBr

8.
(b) Mn2O7
Explanation: 2KMnO4 + 2H2SO4(Conc) ⟶ Mn2O7 + 2KHSO4 + H2O

9. (a) In photography
Explanation: Photography is an example of photochemistry used in our daily life. Reaction takes place in the presence of light
10.
(b) PhCOCH2CH3
Explanation: Hydration of given alkyne will occur according to Markovnikoff's rule leading to the formation of enol which will
tautomerise to give keto form.
The general reaction of alkyne hydrations shown below:

Same reaction will occur with

H3O+,Hg2+

PhC ≡ CMe−−−−−−−→? PhC(OH) = CHCH 3 ⇔ PhCOCH2CH3 .

11. (a) 1
Explanation: A chiral molecule is one that is not superimposable on its mirror image.
2‐Butanol is a small molecule with a chirality center. It is the simplest alcohol containing an asymmetric carbon. For a better
illustration, the four different substituents are shown in different colours.
Carbon atom C‐2 of 2‐butanol carries four different substituents H, CH3, OH, and CH2CH3. Exchange of any two of these
substituents would yield the opposite enantiomer. However, such an exchange does not occur spontaneously because it requires
a bond breakage. Therefore, enantiomers are different, stable, coexisting compounds.
12.
(b) 2 – pentanamine
Explanation: 2‐pentamine will have a chiral centre, therefore it can be resolved into enantiomers.
CH3CH2CH2C*HCH3NH2
The C* in 2‐pentan amine is the chiral center.
13.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Enamel is the hardest substance in the human body and contains the highest percentage of minerals, with water
and organic material composing the rest. The primary mineral is hydroxyapatite, which is crystalline calcium phosphate.
Magnesium is not present in human enamel. However, magnesium is an essential mineral for human health. Magnesium is a
cofactor for more than 300 enzyme systems and is involved in both aerobic and anaerobic energy generation and in glycolysis,
either directly as an enzyme activator or as part of the magnesium‐ATP complex. Magnesium is required for mitochondria to
carry out oxidative phosphorylation. It plays a role in regulating potassium fluxes and in the metabolism of calcium.
14. (a) Both A and R are true and R is the correct explanation of A.
Explanation: Both A and R are true and R is the correct explanation of A.
15.
(c) A is true but R is false.
Explanation: For the same alkyl group, the boiling point of haloalkanes decreases in the order RI > RBr > RCl > RF. This is due to
the increase in van der Waals forces when the size and mass of the halogen atom increases. For isomeric haloalkanes, the boiling
point decrease with an increase in branching.
16. (a) Both A and R are true and R is the correct explanation of A.

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 Explanation: Saytzeff's rule: The alkene formed in the greatest amount is the one that corresponds to the removal of the
hydrogen from the β‐carbon having the fewest hydrogen substituent. In the case of 2o and 3o alcohols, Saytzeff's rule is
followed. H2SO4
H3C − CH2 − CH − CH3 −−−−→ H3C − CH = CH − CH3 + CH3 − CH2 − CH = CH2 + H2O
| (Major) (Minor)
OH

Section B

17. Electronic configuration of Co: [Ar]4s23d7

Electronic configuration of Co2+ : [Ar]4s03d7

Cl− Cl‐ does not cause pairing of electrons because it is weak field ligand. Hence,

18. a. Fe has higher melting point than Cu. This is because Fe ( 3d 64s2) has four unpaired electrons in 3d‐subshell while Cu

(3d104s1) has only one electron in the 4s‐subshell. Hence, metallic bonds in Fe are much stronger than those in Cu.

b. Co2+ has a configuration as [Ar]3d7, thus, Co2+ has 3 unpaired electron in d orbital while Ni 2+ has a configuration as [Ar]3d8,

Ni2+ has 2 unpaired electron. Thus, Ni2+ has lower magnetic moment than Co2+.
19. Answer the following:
log[Ro] k
(i) The slope value obtained in the plot of Vs. time for a first‐order reaction is .
[Ro] 2.303

(ii) It is first order with respect to N 2O5.

20. In pure alcohol and water, the molecules are held tightly by a strong hydrogen bonding. The interaction between the molecules of
alcohol and water is weaker than alcohol‐alcohol and water‐water interactions. As a result, when alcohol and water are mixed, the
inter‐molecular interactions become weaker and the molecules can easily escape. This increases the vapour pressure of the
solution, which in turn lowers the boiling point of the resulting solution.
OR
The various quantities known to us are as follows:

p10 = 0.850 bar; p = 0.845 bar; M1 = 78g mol‐1; w2 = 0.5 g; w1 = 39 g

Substituting these values in equation of relative lowering of vapour pressure, we get 0.850
bar −0.845 bar 0.5g×78gmo l−1
=
0.850 bar M2×39g

Therefore, M2 = 170 g mol‐1

21. i.

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 ii.

Section C

22. i. Oxidation half cell reaction; Ni(s) → Ni2+ (aq) + 2e‐ (At anode) Reduction half cell reaction; 2Ag+(aq) + 2e‐ → + 2Ag(s) (At
cathode)
Ni (s) + 2Ag+ Ni E E E
Overall cell reaction; (aq)→ 2+ (aq) + 2Ag (s); Therefore, c∘ell = c∘athode − a∘node = +0.80 V ‐ (‐0.25 V)
= 1.05 V ii. By applying Nernst
equation, we have;

Ecell = Eocell ‐ 0.0591 [Ni2+]

= 1.05 + 0.0295 = 1.0795 V.

Δ[Ester] (0.17−0.31)
23. i. Rav
= 4.67 × 10−3 s−1
ii. At t = 30 s, [R]=0.31 M, [R]0=0.55 M

log
k = 2.303t log = 2.303 ( 0.550.31

) k = 2.303 log(1.774) = 2.303 × 0.2490

30
k = 1.91 × 10−2s−1
At t = 60 s, [R] = 0.17 M
log
k = 2.303 ( 0.55 ) = 2.303 × 0.5099
60 0.17

= 1.96 × 10−2s−1
At t = 90 s, [R] = 0.085 M

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 log
k = 2.303 ( 0.55 ) = 2.303 × (0.8109)
90 0.085

k = 2.07 × 10−2s−1
24. The mechanism of hydration of ethene to form ethanol involves three steps.
Step 1:

Protonation of ethene to form carbocation by electrophilic attack of H 3O+:

Step 2:
Nucleophilic attack of water on carbocation:

Step 3:
Deprotonation to form ethanol:

OR
i. 2‐Chloropropane to 1‐propanol
a. alc. KOH heat,
b. HBr peroxide
c. alc. KOH, heat
iii. Isopropyl alcohol to iodoform
I2/NaOH heat iii. Chlorobenzene

to p‐nitrophenol

a. Conc. HNO3+ conc. H2SO4

b. aq NaOH (15%), 433 K (c) dil. HCl
25.

Since (D) is a carboxylic acid with one carbon only, it is HCOOH. As it is obtained from (C) acidification, (C) COONa and (A) is HCHO
which on treatment with strong base (NaOH) gives CH 3OH & HCOONa. This is Cannizzaro reaction in which formaldehyde undergoes
self oxidation and reduction(disproportion) on treatment with concentrated alkali. The reactions are as follows:‐

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26. At anode: 2Fe(s) → 2Fe2+ + 4e−

E0(Fe2+/ Fe) = ‐0.44 V

Cathode: O2(g) + 4H +(aq) + 4e− → 2H2O(l); E0cell (H+O2/H2O) = 1.23V

The overall reaction being:

2Fe(s) + O2(g) + 4H +(aq) →2Fe2+(aq) + 2H2O(l); E0cell = 1.67V

The ferrous ions are further oxidized by atmosphere oxygen to ferric ions which came out as rust in the form of hydrated ferric oxide
(Fe2O3.nH2O)
The method to prevent rusting of iron is by Barrier protection.
27. i. When ethyl chloride is treated with aqueous KOH, it undergoes hydrolysis to form ethanol and KCl.
KOH(aq)

CH3 − CH2 − Cl−−−−−−−→CH3 − CH2 − OH + KCl

Ethyl chloride (Hydrolysis) Ethanol ii. When
methyl bromide is treated with sodium in the presence of dry ether, ethane and NaBr is
formed. This reaction is known as the Wurtz reaction.
Dry ether
2CH3 − Br + 2Na−−−−−−−−−→CH3 − CH3 + 2NaBr
Methyl bromide (wurtz reaction) Ethane
iii. When methyl chloride is treated with KCN, it undergoes a nucleophilic substitution reaction to give methyl cyanide and KCl.
CH3 − Cl + KCN−−−−−−−−−−−−−→CH3 − CN + KCl
Methyl chloride nucleophilic substitution Methyl cyanide

28. We have,
Zn(s) + 2Ag+(aq) → Zn2+(aq) + 2Ag(s)
At Cathode (Reduction):
2Ag+(aq) + 2e− → 2Ag(s)
At Anode (Oxidation):
Zn(s) → Zn2+(aq) + 2e−
The cell will be represented as:
Zn(s)|Zn2+(aq)||Ag+(aq)|Ag(s)
i. From half cell reaction, Zinc acts as Anode, i.e. zinc electrode will be negatively charged. ii. The current will flow from silver to
zinc in the external circuit and inside the solution, ions are responsible as shown in the half cell reaction. Zn 2+ is formed in the
anode container and goes to the solution and in the cathode container, Ag + goes from solution to the silver metal(cathode) and
gets deposited. To maintain the concentration of ions in both the containers, salt bridge is used which contain an electrolyte i.e.
KCl. iii. At anode : Zn(s) → Zn2+(aq) + 2e−
At cathode: Ag+(aq) + e → Ag(s)
Section D
29. Read the text carefully and answer the questions:
The unique behaviour of Cu, having a positive E° accounts for its inability to liberate H 2 from acids. Only oxidising acids (nitric and

hot concentrated sulphuric) react with Cu, the acids being reduced. The stability of the half‐filled d sub‐shell in Mn2+ and the

completely filled d10 configuration in Zn2+ are related to their E° values, whereas E° for Ni is related to the highest negative ΔhydH°.

An examination of the E(oM 3+/M 2+) values the low value for Sc reflects the stability of Sc3+ which has a noble gas configuration. The

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 comparatively high value for Mn shows that Mn2+(d5) is particularly stable, whereas a comparatively low value for Fe shows the

extra stability of Fe3+ (d5). The comparatively low value for V is related to the stability of V 2+ (half‐filled t2g level).

(i)
Due to the removal of an electron from the stable d10 configuration of Zn2+.
OR
Transition metals despite having high E° oxidation, are poor reducing agents because of their high heat of vaporization, high
ionisation energies and low heats of hydration.

(ii)
Cr2+ is reducing as its configuration changes from d4 to d3, the having a half‐filled t2g level. On the other hand, the change

from Mn3+ to Mn2+ results in the half‐filled (d5) configuration which has extra stability.

(iii)
The Stability of Cu2+ is more than Cu+ as stability depends on the hydration energy of the ions when they bond to the water

molecules. The Cu2+ ion has a greater charge density than Cu+ ion and thus forms much stronger bonds releasing more
energy.
30. Read the text carefully and answer the questions:
The boiling point elevation and the freezing point depression of solutions have a number of practical applications. Ethylene glycol
(CH2OH⋅CH2OH) is used in automobile radiators as an antifreeze because it lowers the freezing point of the coolant. The same
substance also helps to prevent the radiator coolant from boiling away by elevating the boiling point. Ethylene glycol has a low
vapour pressure. We can also use glycerol as an antifreeze. In order for boiling point elevation to occur, the solute must be
nonvolatile, but no such restriction applies to freezing point depression. For example, methanol (CH 3OH), a fairly volatile liquid that
boils only at 65oC is sometimes used as antifreeze in automobile radiators.
(i) CH3OH is a better reagent for depression in freezing point but not for elevation in boiling point.
(ii) The depression in freezing point will be the same in both the solutions because both are non‐electrolytes and gives the
same number of solutes.
(iii)Glycol will be better than glycerol because it is more volatile than glycerol.
OR
The sequence of the economy to use these compounds as antifreeze is Methanol > Glycol > Glycerol. Section E
31. Attempt any five of the following:
(i) A starch has two components: amylose and amylopectin. Amylose is water soluble.
(ii) Primary structure of proteins tells about the sequence in which various amino acids are linked with each other.
(iii)Deficiency of A cause Xerophthalmia and E causes muscular weakness.
(iv)Sucrose on dydrolysis gives equimolar mixture of D‐glucose and D‐fructose.
H+

C12H22O11 + H2O −−→ C6H12O6 + C6H12O6

Sucrose Glu cos e Fructose

(v) Lactose is present in milk as sugar. Two monosaccharide units (i.e., glucose and galactose) are present in it. Such
oligosaccharides are called disaccharides.
(vi)Glycosidic linkage: It is the linkage which joins two monosaccharides through oxygen atom. It is present in carbohydrates.
Peptide Linkage: It is the linkage which joins two amino acids through ‐ CO‐NH‐ bond. It is present in proteins.

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 (vii)Monosaccharide ‐ Glucose, Fructose etc.
Disaccharide ‐ Sucrose, maltose etc.
Polysaccharide ‐ Cellulose, starch etc.

32. i. [Cr(C2O4)3]3‐

ii. [PtCl2(en)2]2+

iii. [Cr(NH3)2Cl2(en)]+
OR

Ni is in the +2 oxidation state i.e., in d8 configuration.

There are 4 CN‐ ions. Thus, it can either have a tetrahedral geometry or square planar geometry. Since CN ‐ ion is a strong field
ligand, it causes the pairing of unpaired 3d electrons.

It now undergoes dsp2 hybridization. Since all electrons are paired, it is diamagnetic. In case of [NiCl 4]2‐, CN‐ ion is a weak field

ligand. Therefore, it does not lead to the pairing of unpaired 3d electrons. Therefore, it undergoes sp 3 hybridization.

Since there are 2 unpaired electrons in this case, it is paramagnetic in nature.

H+

33. A. i. C2H5N ≡ C + 2H2O −−→ C2H5NH2 + HCOOH

Ethyl isocyanide Ethyl a mine Methanoic acid

ii.
B. The following reactions lead to the identification of A and B:
CH3 CH3
| |

CH3 − C − CH3 + HNO2 → CH3 − C − CH3 + N2 + H2O

| |
NH2 OH

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 (A) (C)

CH3 − C − CH2 − CH3 + HNO2 → CH3 − C − CH2 − CH3 + N2 + H2O

| |
NH2 OH
(B) (D)

C.
‘C’ is resistant to oxidation because tertiary alcohols do not undergo oxidation. It gives turbidity immediately with Lucas reagent.
‘D’ responds to Lucas reagent within 5 minutes because it is secondary alcohol and turbidity appears after 5 minutes.
ZnCI2(Anhyd.)

CH3 − CH − CH2 − CH3 + HCI −−−−−−−−−→ CH3 − CH − CH2 − CH3

| |
OH CL
Butan ‐ 2 ‐ ol 2−Chlorobutane

I2/NaOH

CH3 − C H − CH2 − CH3 −−−−−−→

| (NaOI)
OH
(D)Bu tan−2−ol
I2/NaOH

CH3 − C − CH2 − CH3 −−−−−−→

||
O
2−Bu tanone
CHI3 + CH3CH2COONa + 3NaI + 2H2O
Iodoform Sodium Pr oponoate
OR
a. i. Due to the electron‐withdrawing effect of the acetyl group, the lone pair of electrons on N‐atom is attracted by the acetyl
group. As a result, the lone pair of electrons on N‐atom is not exclusively available for donation to the benzene ring and
hence, activating the effect of the ‐ NH2 group is reduced.

ii. In aromatic amines, the lone pair of electrons present on nitrogen takes part in resonance and hence, not available for
donation. Alsoaniline is more stable than anilinium ion. Hence aniline has a very little tendency to accept a proton to form
anilinium ion. However, in aliphatic amines, the lone pair is easily available for donation. That's why aliphatic amines are more
basic than aromatic amines.
iii. Nitration is usually carried out with a mixture of conc. HNO 3 and cone. H2SO4. So in the presence of these acids, aniline gets

protonated to form anilinium ion. Therefore, the reaction mixture consists of aniline + and anilinium ion. ‐NH2 group in aniline

is o,p‐directing and activating, whereas the +NH3group in anilinium ism‐directing and deactivating. Now, nitration of aniline
mainly gives p‐nitroaniline due to steric hindrance at a‐position and the nitration of anilinium ion gives mnitroaniline.

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b. i. Gabriel phthalimide reaction Phthalimide on treatment with ethanolic KOHgives potassium phthalimide which on heating with
a suitable alkyl halide gives N‐substituted phthalimide, which upon subsequent hydrolysis with alkali gives primary amines.

This reaction is called Gabriel phthalimide reaction.

ii. Coupling reaction Arenediazonium salts react with highly reactive (i.e. electron‐rich) aromatic compounds such as aniline,
phenols to form brightly coloured azo compounds, Ar‐N = N‐Ar. This reaction is called a coupling reaction. e.g. Benzene
diazonium chloride reacts with aniline in faintly acidic medium (pH 4‐ 5) at 273·278K, in which the molecule at its
paraposition is coupled with the diazonium salt to form p‐aminoazobenzene.
This is an example of a coupling reaction.

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