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Class 12 - Chemistry
Sample Paper - 02 (2023-24)

Maximum Marks: 70
Time Allowed: : 3 hours

General Instructions:

Read the following instructions carefully.

a. There are 33 questions in this question paper with internal choice.

b. SECTION A consists of 16 multiple-choice questions carrying 1 mark each.
c. SECTION B consists of 5 very short answer questions carrying 2 marks each.
d. SECTION C consists of 7 short answer questions carrying 3 marks each.
e. SECTION D consists of 2 case-based questions carrying 4 marks each.
f. SECTION E consists of 3 long answer questions carrying 5 marks each.
g. All questions are compulsory.
h. Use of log tables and calculators is not allowed.

Section A
1. CH3 = CH2 CH3 + H – I → CH3 CH2 CH2I + CH3 CHICH3 (major). This reaction is________.
a) Sandmeyer’s reaction
b) Finkelstein reaction
c) Markovnikov's reaction
d) Free radical halogenations
2. Salivary amylase is secreted by
a) Pancreas
b) Intestine
c) Salivary glands
d) Stomach
3. The major product formed when 3, 3-dimethyl butan-2-ol is heated with concentrated sulphuric acid is
a) 2, 3-dimethyl-2-butane
b) 2,3-dimethyl-1-butane
c) cis- and trans- isomers of 2,3-dimethyl-1-1butane
d) 3,3-dimethyl-1-butane
4. A mixture of benzaldehyde and formaldehyde on heating with aqueous NaOH solution gives:
a) Benzyl alcohol and methyl alcohol
b) Benzyl alcohol and sodium formate
c) Sodium benzoate and methyl alcohol
d) Sodium benzoate and sodium formate
5. The rate of reaction can be measured as
a) Rate of disappearance of reactant or rate of appearance of product
b) Rate of appearance of the product
c) Rate of appearance of reactant
d) Rate of disappearance of reactant

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6. Match the items of column I with appropriate entries of column II.
Column I Column II

(a) Non ideal solution with positive deviation (i) H2O (57%) + HI (43%)

(b) Maximum boiling azeotrope (ii) CHCl3 + (CH3)2CO

(c) Non ideal solution with negative deviation (iii) C2H5OH (95.4%) + H2O (4.6%)

(d) Minimum boiling azeotrope (iv) CCl4 + C6H5CH3

a) (a) - (iv), (b) - (i), (c) - (ii), (d) - (iii)

b) (a) - (iv), (b) - (iii), (c) - (ii), (d) - (i)
c) (a) - (i), (b) - (ii), (c) - (iii), (d) - (iv)
d) (a) - (ii), (b) - (iii), (c) - (i), (d) - (iv)
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7. C - Cl bond in chlorobenzene in comparison to C - Cl bond in methyl chloride is:
a) longer and stronger
b) shorter and weaker
c) longer and weaker
d) shorter and stronger
8. Number of moles of K2Cr2O7 reduced by one mole of Sn2+ ions is
a) 1/6
b) 3
c) 6
d) 1/3
9. Radioactive decay is an example of:
a) zero order
b) second order
c) 0.5 order
d) first order
10. Which of the following will undergo aldol condensation?
a) CH3CH2CHO
b) CH = CCHO
c) C6H5CHO
d) CH2 = CHCHO
CH
3

11. The correct IUPAC name of C H 3 − C − C H2 C H3 is

|
OH

a) 2-Methylbutan-2-ol
b) 3-Methylbutan-3-ol
c) 2,2-Dimethylpropanol
d) tert-butyl alcohol
12. If the starting amide has got four carbon atoms and the amine that is formed has got only 3 carbon atoms, then the
reaction is called______.
a) Gabriel synthesis

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b) Carbylamines reaction
c) Hoffmann bromamide reaction
d) Clemmensen reduction
Br2 H2 O2
13. Assertion (A): D(-)-Ribose on consecutive treatment with H2 O
,
F e2 (SO4 )
gives D(-)-erythrose.
3

Br2 H2 O2
Reason (R): H2 O
,
2+
is used in Ruff degradation method and D(-)-ribose and D(-)-erythrose differ only in one
Fe

carbon atom.
a) Both A and R are true and R is the correct explanation of A.
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
14. Assertion: p-O2N - C6H5COCH3 is prepared by Friedel Crafts acylation of nitrobenzene.
Reason: Nitrobenzene easily undergoes electrophilic substitution reaction.
a) If both Assertion & Reason are true and the reason is the correct explanation of the assertion.
b) If both Assertion & Reason are true but the reason is not the correct explanation of the assertion.
c) If Assertion is true statement but Reason is false.
d) If both Assertion and Reason are false statements.
15. Assertion (A): In comparison to ethyl chloride it is difficult to carry out nucleophilic substitution on vinyl chloride.
Reason (R): Vinyl group is electron-donating.
a) Both A and R are true and R is the correct explanation of A.
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
16. Assertion (A): The bond angle in alcohols is slightly less than the tetrahedral angle.
Reason (R): In alcohols, the oxygen of –OH group is attached to sp3 hybridized carbon atom.
a) Both A and R are true and R is the correct explanation of A.
b) Both A and R are true but R is not the correct explanation of A.
c) A is true but R is false.
d) A is false but R is true.
Section B
17. Give the formulae of the following compounds:
a. Potassium tetrahydroxidozincate (II)
b. Hexaammineplatinum (IV) chloride
18. Explain the following observations:
i. Generally, there is an increase in the density of elements from titanium (Z = 22) to copper (Z = 29) in the first series
of transition elements.
ii. Transition elements and their compounds are generally found to be good catalysts in chemical reactions.
19. Answer the following:
1. How will you prove that a chemical reaction is of first order?
2. Why are reactions of higher-order less in number?
20. i. Gas (A) is more soluble in water than gas (B) at the same temperature. Which one of the two gases will have a higher
value of KH (Henry's constant) and why?
ii. In non-ideal solution, what type of deviation shows the formation of maximum boiling azeotropes?

OR

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Urea forms an ideal solution with water. Determine the vapour pressure of an aqueous solution containing 10% by mass
of urea at 40 C . (Vapour pressure of water at 40 C = 55.3 mm Hg)
0 0

21. Write reactions with conditions for the following conversions:

i. Methyl bromide to acidic acid.
ii. Benzene to toluene.
Section C
22. A voltaic cell is set-up at 250 C with following half cells Al|Al3+(0.001 M) and Ni|Ni2+(0.50 M)
Write an equation for the reaction that occurs when the cell generates an electric current and determine the cell potential.
[Given, E Θ

Ni
2+
= −0.25 V , and E
/Ni
Θ
= −1.66 V log(8 × 10
Al
3+
/Al
) = - 5.09690]
−6

23. In a pseudo first order hydrolysis of ester in water, the following results were obtained:
t/s 0 30 60 90

[Ester] molL-1 0.55 0.31 0.17 0.085

i. Calculate the average rate of reaction between the time interval 30 to 60 seconds.
ii. Calculate the pseudo first order rate constant for the hydrolysis of ester.
24. How the following conversions can be carried out?
i. Toluene to benzyl alcohol
ii. Benzene to 4-bromonitrobenzene
iii. Benzyl alcohol to 2-phenylethanoic acid

OR

State the products of the following reactions:

i. CH3CH2CH2OCH3 + HBr →
ii.

+HBr →

HI

iii. (CH3)3C - OC2H5​−

−→

25. i. Illustrate the following reaction giving suitable chemical equations: Cannizzaro reaction.
ii. How would you bring about the following conversions? Write the complete equations in each case.
a. Ethanal to 3-hydroxybutanal
b. Benzaldehydeto benzophenone
26. The electrical resistance of a column of 0.05 mol L-1 NaOH solution of diameter 1 cm and length 50 cm is 5.55 × 103
Ω . Calculate its resistivity, conductivity and molar conductivity.

27. p-Dichlorobenzene has higher m.p. than those of o- and m-isomers. Discuss.
28. Determine the value of equilibrium constant (K ) and ΔG for the following reaction.
c
θ

+ 2+
N i(s) + 2Ag (aq) → N i (aq) + 2Ag(s)

θ −1
E = 1.05 V (1 F = 96500 C mol )

Section D
29. Read the text carefully and answer the questions:
Observe the graph of transition metal and their melting points

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i. Why does W (tungsten) has highest melting point?

OR

Why are transition metals less electropositive than ‘s’-block elements?

ii. Which element in 3d series has lowest enthalpy of atomisation and why?
iii. Why is mercury liquid?
30. Read the text carefully and answer the questions:
The colligative properties of electrolytes require a slightly different approach than the one used for the colligative
properties of non-electrolytes. The electrolytes dissociate into ions in solution. It is the number of solute particles that
determines the colligative properties of a solution. The electron solutions, therefore, show abnormal colligative
properties. To account for this effect we define a quantity called the van't Hoft factor, given by
Actual number of particles in solution after dissociation
i= Number of formula units initially dissolved in solution

i = 1 (for non-electrolytes);
i > 1 (for electrolytes, undergoing dissociation)
i < 1 (for solutes, undergoing association).
i. 0.1M K4[Fe(CN)6] is 60% ionized. What will be its van't Hoff factor?
ii. When a solution of benzoic acid dissolved in benzene such that it undergoes in molecular association and its
molar mass approaches 244. In which form Benzoic molecules will exist?
iii. How does van't Hoff factor i and degree of association a are related if benzoic acid undergoes dimerisation in
−​α
benzene solution? (i = 1 2
or i = 1 + α)

OR

What do you mean by colligative properties of solutions?

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Section E
31. Attempt any five of the following:
1. Which vitamin is linked with anti-sterility?
2. What is the difference between a glycosidic linkage and a peptide linkage?
3. Why must vitamin C be supplied regularly in diet?
4. Write a reaction which shows that all the carbon atoms in glucose are linked in a straight chain.
5. What type of substance is phenylanine hydroxylate? Write its importance.
6. Deficiency of which vitamin causes scurvy?
7. Write the name of bond between the two - amino acids.

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32. i. For the complex [Fe(H2O)6]3+, write the hybridisation, magnetic character and spin nature of the complex. (Atomic
number of Fe = 26)
ii. Draw one of the geometrical isomers of the complex [Pt(en)2Cl2]2+ which is optically inactive.

OR

a. Amongst the following, the most stable complex is:

i. [Fe(H2O)6]3+

ii. [Fe(NH3)6]3+

iii. [Fe(C2O4)3]3-

iv. [FeCl6]3+
b. What will be the correct order for the wavelength of absorption in the visible region for the following:
[Ni(NO2)6]4-, [Ni(NH3)6]2+, [Ni(H2O)6]2+
33. i. Write the structures of main products when benzene diazonium chloride reacts with the following reagents:
a. H3PO2 + Hp
b. CuCN/KCN
c. H2O
ii. Arrange the following in the increasing order of their basic character in an aqueous solution: C2H5NH2, (C2H5)2NH,
(C2H5)3N. Give justification.

OR

Give plausible explanation for each of the following:

i. Why are amines less acidic than alcohols of comparable molecular masses?
ii. Why do primary amines have higher boiling point than tertiary amines?
iii. Why are aliphatic amines stronger bases than aromatic amines?

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Class 12 - Chemistry
Sample Paper - 02 (2023-24)

Solution

Section A
1. (c) Markovnikov's reaction
Explanation: This is an electrophilic addition reaction following Markovnikov's rule.
2. (c) Salivary glands
Explanation: Salivary amylase is an enzyme secreted by salivary glands.
3. (a) 2, 3-dimethyl-2-butane
Explanation: 2, 3-dimethyl-2-butane
4. (b) Benzyl alcohol and sodium formate
Explanation: They will undergo Cannizzaro reaction as neither benzaldehyde nor formaldehyde has alpha hydrogen.
HCHO will be more reactive towards Cannizzaro compared to benzaldehyde because of less steric hindrance.
So, OH- nucleophile will attack HCHO first, and then the hydride shift from HCHO to benzaldehyde will occur and thus
HCHO will oxidize to HCOO- ion and benzaldehyde will reduce to benzyl alcohol.
5. (a) Rate of disappearance of reactant or rate of appearance of product
Explanation: rate of reaction = (+) rate of appearance of products = (-) rate of disappearance of reactants
6. (a) (a) - (iv), (b) - (i), (c) - (ii), (d) - (iii)
Explanation: (a) - (iv), (b) - (i), (c) - (ii), (d) - (iii)
7. (d) shorter and stronger
Explanation: In chlorobenzene, the hybridization of carbon attached to Cl is sp2, and in methyl chloride hybridization of
C attached to Cl is sp3. In sp2 hybridization, s-character is 33% and in sp3 s-character is 25%. The sp2 hybridized carbon
with a greater s-character is more electronegative and can hold the electron pair of C—X bond more tightly than sp3-
hybridized carbon in haloalkane with less s-character resulting in a short bond length of C-Cl bond. Since it is difficult to
break a shorter bond than a longer bond, means it is stronger. Also in chlorobenzene, the electron pairs on Cl atom are in
conjugation with π-electrons of the ring, so C—Cl bond acquires a partial double bond character due to resonance which
makes the bond stronger.
8. (d) 1/3
Explanation: The balanced chemical reactions (ionic reactions)for the reduction of K 2 C r2 O7 by Sn
2+
are:
2− + − 3+
C r2 O + 14H + 6e → 2C r + 7H2 O
7

2+ 4+ −
( Sn → Sn + 2e ) × 3

Balanced Net reaction : 3Sn 2+

+ C r2 O7
2−
+ 14H
+
→ 3S n
4+ 3+
+ 2C r + 7H2 O​

Thus according to the balanced reaction: 1 mole of C r 2 O7

2−
will be reduced by 3 moles of Sn2+
1
Thus 1 mole of Sn2+ will reduce = = moles of C r2 O7
2−

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9. (d) first order
Explanation: first order
10. (a) CH3CH2CHO
Explanation: CH3CH2CHO will give aldol reaction because of the presence of alpha hydrogen in it.

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11. (a) 2-Methylbutan-2-ol
CH
3

Explanation: The correct IUPAC name of C H 3 − C − C H2 C H3 is 2-Methylbutan-2-ol

|
OH

12. (c) Hoffmann bromamide reaction

Explanation: In Hoffmann bromamide degradation reaction, the amine formed has one carbon less than the amide.
RCONH2 + Br2 +4NaOH → RNH2 + Na2CO3 + 2NaBr + 2H2O
13. (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.
14. (d) If both Assertion and Reason are false statements.
Explanation: In an electrophilic substitution reaction, the nitro group strongly deactivates the benzene ring.
Nitrobenzene does not undergo Friedel Craft acylation reaction.
15. (c) A is true but R is false.
Explanation: CH2​=CH−Cl has some partial double bond character between carbon and a chlorine atom. So,
nucleophilic substitution is difficult to carry as it is difficult to break the partial double bond in vinyl chloride than ethyl
chloride CH3​CH2​−Cl where there is no double bond character.
The vinyl group is not electron-donating. The carbon halogen bond in vinyl halides has some double-bond character and
thus a little difficult to break.
16. (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.
Section B
17. a. The formula of Potassium tetrahydroxidozincate (II)
K2 [Zn(OH)4]
b. The formula of Hexaammineplatinum (IV) chloride
Pt[(NH3)6]Cl4

18. i. As we move from left to right along a 1st transition series (from Ti to Cu), the atomic radii decrease due to increase in
nuclear charge. Therefore, atomic volume decreases with increase in atomic mass.
As density = mass / volume, therefore, the density of transition metals increases from Titanium (22Ti) to Copper
(29Cu).
ii. Transition metals are good catalysts because of their ability to adopt multiple oxidation states and to form complexes.
Transition metals because of their variable valencies and vacant d-orbitals form unstable intermediate compounds
and provide a new path with the lower activation energy for the reaction.
19. Answer the following:
[R]
1. For a first order reaction, the equation is : k
2.303 o
= log
t [R]

A constant value of k justify's the first order of the reaction.

2. A reaction takes place due to the collide of molecules. The chances for a large number of molecules or ions to collide
simultaneously are less. Hence, the reactions of higher order are less.
20. Solubility is inversely proportional to KH, i.e. Henry's constant of the gas.
i. Greater the value of KH, lower is the solubility of the gas. As gas (A) is more soluble in water than gas (B) at the
same temperature, hence the gas (A) has a lower value of KH. In other words, gas (B) has a higher value of KH than
gas (A) at the same temperature.
ii. In non-ideal solutions, the solutions that show large negative deviation from Raoult's law form maximum boiling
azeotropes. e.g. Mixture of nitric acid and water.

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OR

10% by mass with mean 10 g urea is dissolved in 100 g solution.

Mass of solvent (water) = 100-10=90 g
No. of moles of urea =
10
= 0.167 mole
60

No. of moles of water = 90

18
= 5 mole

Mole fraction of water (x

5
H2 O ) =
5+0.167

= 0.968

∴ Vapour pressure of solution = P . xH

2
O

= 55.3 mm Hg × 0.968 = 53.53 mm Hg

21. Steps involved in the conversions are given below:

i. Methylbromide to Acetic acid
+
H2 O/H

C H3 Br + KCN → C H3 C N −−−−−→ C H3 C OOH

ii. Benzene to Toluene

Section C
22. For the electrochemical cell,
Half cell reactions are:
At cathode(Reduction):
2+ −
Ni (aq) + 2e → N i(s)

At Anode(Oxidation):
3+ −
Al(s) → Al (aq) + 3e

The cell reaction is

2+ 3+
2Al(s) + 3N i (aq) → 2Al (aq) + 3N i(s);

(Here n=6)
Standard emf of the reaction is:
Θ Θ Θ
E = E − E
cell Ni
2+
/Ni
3+
Al /Al

= -0.25V - (-1.66V) = 1.41V

From Nernst equation, we have,
2
3+
[Al ]
Θ 0.0591V
Ecell = E − log
cell 6 2+
3
[N i ]

2
−3
( 10 )
0.0591V
Ecell = 1.14V − log
3
6
(0.50)
−6
0.0591V 8×10
Ecell = 1.14V − log
6 1
0.0591V
Ecell = 1.14V − [log 8 − 6 log 10]
6
0.0591V
= 1.14V − [0.9031 − 6 × 1]
6
0.0591V
= 1.14V − [−5.0969]
6

∴ Ecell = 1.4602 V

d[Ester]
23. i. Average rate of reaction between the time interval, 30 to 60 seconds,= dt
0.31−0.17 0.14 −3 −1 −1
= = = 4.67 × 10 mol L s
60−30 30

ii. For a pseudo first order reaction,

[R]
2.303 0
k = log
t [R]

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For t= 30s,k
2.303 0.55 −2 −1
1 = log = 1.911 × 10 s
30 0.31

For t= 60s, k 2
=
2.303

60
log
0.55

0.17
= 1.957 × 10
−2
s
−1

For t= 90s,
2.303 0.55 −2 −1
k3 = log = 2.075 × 10 s
90 0.085

= 1.981 X 10-2 s-1

k1 +k2 +k3
Then, average rate constant,k =
3

24. i. Toluene to benzyl alcohol

a. Chlorine, sunlight
b. aq KOH, heat
ii. Benzene to 4-bromonitrobenzene
a. Bromine, ferric bromide,
b. Conc. HNO3 + conc. H2SO4​
iii. Benzyl alcohol to 2-phenylethanoic acid
a. Thionyl chloride
b. alc KCN (c) H+/water

OR

i. CH3CH2CH2OCH3 + HBr → C H 3 C H2 C H2 OH+ CH3Br

Propanol

ii.

iii.

HI

(CH3)3C - OC2H5​−
−→

25. i. Clemmensen reduction The carbonyl group of aldehydes and ketones is reduced to -CH2 group on treatment with
zinc-amalgam and concentrated hydrochloric acid. This reaction is known as Clemmensen reduction.

e.g. .

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ii. a. Ethanal to 3-hydroxybutanal
4 3 2 1

2C H3 − C HO C H3 − C H − C H2 − C HO
Ethanal |

OH

3−hydroxybutanal

b. Benzaldehyde to benzophenone

26. Given,
concentration of NaOH = 0.05M
diameter = 1 cm,
length = 50 cm,
resistance= 5.55 × 103 Ω
= 0.785 cm2
2
Area of cross section, A = πr = 3.14 × ( 2 1
)
2
3

Resistivity, ρ = RA
= 5.55×10 ×0.785

50
= 87.135Ω cm
l

Conductivity,σ = = 0.01148 =
1 1 −2 −1
= 1.148 × 10 Scm
ρ 87.135

= 229.6 Scm2 mol-1

−2

Molar conductivity of solution Λ m =

σ×1000

M
= 1.148×10

0.05
×1000

27.

p-Dichlorobenzene is more symmetrical than o-and m-isomers. For this reason, it fits more closely than o-and m-isomers
in the crystal lattice. Therefore, more energy is required to break the crystal lattice of p-dichlorobenzene. As a result, p-
dichlorobenzene has a higher melting point and lower solubility than o-and m-isomers.
28. We have,
+ 2+
N i(s) + 2Ag (aq) → N i (aq) + 2Ag(s)

For the reaction n = 2,E θ

cell
= 1.05 V
θ θ
ΔG = −nF E

θ
ΔG = −2 × 96500 C × 1.05 V

θ −1
ΔG = −202.65 kJ mol

For Equilibrium constant, we have,

θ
ΔG = −2.303 RT log Kc
Θ
ΔG
log Kc = −
2.303RT
202650
= −
2.303×8.314×298

Kc = Antilog(35.5161)

35
Kc = 3.284 × 10

Section D
29. i. It is due to presence of most number of unpaired electrons and there is more frequent metal-metal bonding in 5d
series than 3d and 4d series.

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OR

It is due to smaller atomic size and higher ionisation enthalpies.

ii. Zinc has lowest enthalpy of atomisation due to weak metallic bond which is due to absence of unpaired
electrons.
iii. It is due to larger size, absence of unpaired electron and weak interatomic attraction and weaker metallic bond.
30. i. We know, x =
i−1

n−1

Where, n = 5 and x = 0.6 (∵ 60% = 60

100
= 0.6 ionized)
i−1
So, 0.6 = 5−1

0.6 × 4 = i - 1
2.4 = i - 1
2.4 + 1 = i
i = 3.4
ii. Benzoic molecules exist as a dimer.
−​α
iii. i = 1 2

OR

The properties of solutions that depend on the ratio of the number of solute particles to the number of solvent
molecules in a solution and not on the nature of the chemical species is termed as colligative properties.
Section E
31. Attempt any five of the following:
1. Vitamin E.
2. 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.
3. Vitamin 'C' is water soluble vitamin and hence excess of it is readily excreted in the urine so, it cannot be stored in
our body and hence, it should be regularly supplied in the diet.
4. On prolonged heating with HI, glucose gives n-hexane which suggest that all the six carbon atoms in glucose are
linked linearly.
Δ

HOH2 C (C HOH) C HO + HI −
→ C H3 (C H2 ) C H3
4 4
Glu cos e n−hexane

5. It is an enzyme whose deficiency causes mental redardation.

6. Vitamin C
7. α - amino acids are connected by peptide linkage.
32. i. In [Fe(H2O)6]3+, Fe exists in +3 oxidation state having a valence shell electronic configuration of 3d54s0.

26 F in the ground state

Fe3+ ions

Thus, for the complex, [Fe(H2O)6]3+,

Hybridization: sp3d2
Magnetic character: Paramagnetic
Spin: High spin complex.
ii. The complex, [Pt(en)2Cl2]2+ contains + two symmetrical didentate ligands, ethylenediamine (en) and exists in two
geometrical isomers, as and trans. Trans isomer being symmetrical does not show optical isomerism and hence, this

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isomer is optically inactive. While cis being unsymmetrical shows optical isomerism.

Hence, the structure of geometrical isomer (i.e. trans-isomer) of the complex [Pt(en)2Cl2]2+ which is optically
inactive is as follows:

trans [Pt(en)2Cl2]2+ isomer optically inactive (Superimposable mirror images)

OR

a. Complexes containing didentate or polydentate ligands are more stable than those containing monodentate ligands. In
each of the given complex, Fe is in +3 state.
As C2O42- is didentate chelating ligand, hence is the most stable complex.
b. As metal ion is fixed, the wavelength of absorption will decided by the field strengths (CFSE values) of the ligands.
From the spectrochemical series, the order of CFSE is: H2O < NH3 < NO2
Thus, the energies absorbed for excitation will be in the order:
[Ni(NH3)6]2+< [Ni(H2O)6]2+ < [Ni(NO2)6]4-
As wavelength and energy are inversely related.The wavelengths absorbed will be in the opposite order:
[Ni(NH3)6]2+> [Ni(H2O)6]2+ > [Ni(NO2)6]4-
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33. i.

a.

b.

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c.

ii. The relative basic strength of C2H5NH2, (C2H5)2NH and (C2H5)3N depends upon the stabilisation of their
corresponding conjugate acids (formed as a result of accepting a proton from water by a number of factors such a; B-
bonding, steric hindrance of the alkyl groups and +I-effect of the alkyl groups. All these factors are favourable for
2o amines, therefore, ((C2H5)2NH is a stronger base than C2H5NH2 and ((C2H5)3N. Since. C2H5 group is large, it
exerts some steric hindrance to H-bond.
Therefore, stabilisation of the conjugate acid derived from (C2H5)3N is due to mainly by +I-effect which is greater
than the stabilisation of the conjugate acid derived from C2H5NH2 by H-bonding.

is more stable than

Thus, (C2H5)3N is more basic than C2H5NH2. Hence, the overall basic strength of the three amines increases in the
order: C2H5NH2 < (C2H5)3N < (C2H5)2NH.

OR

i. Loss of a proton from an amine gives RNH– ion while the loss of a proton from alcohol gives RO- ion as shown
below :
R - NH2 → R - NH- + H+

R - O - H → R - O- + H+
As O is more electronegative than N, RO– can accommodate the negative charge more easily than the RNH– can.
As, RO– is more stable than RNH– the former is formed more. As a result, amines are less acidic than alcohols.
ii. A primary amine is engaged in intermolecular association due to hydrogen bonding between the nitrogen of one nad
hydrogen of other while tertiary amine does not have intermolecular association due to the absence of hydrogen atom
therefore the boiling point of primary amine is more than tertiary amine.

iii. a. The basic nature of amines is a result of the presence of l.p. of electron on the N atom. Also, the electron density
is increased on N due to the +I effect of the alkyl group.
b.
In aryl amines, the l.p. on N is involved in resonance with the benzene ring and hence less available for
protonation.

c.
In aliphatic amines, there is no such delocalisation and hence it is more basic.

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