Class XI Session 2023-24

Subject - Chemistry
Sample Question Paper - 4

Time Allowed: 3 hours Maximum Marks: 70

General Instructions:

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

2. SECTION A consists of 16 multiple-choice questions carrying 1 mark each.

3. SECTION B consists of 5 very short answer questions carrying 2 marks each.

4. SECTION C consists of 7 short answer questions carrying 3 marks each.

5. SECTION D consists of 2 case-based questions carrying 4 marks each.

6. SECTION E consists of 3 long answer questions carrying 5 marks each.

7. All questions are compulsory.

8. The use of log tables and calculators is not allowed

Section A
1. 27°C in Kelvin is [1]

a) 227 K b) 246.15 K

c) 300.15 K d) 127.15 K
2. Among the following pairs of orbitals which orbital will experience the larger effective nuclear charge? (i) 2s and 3s, (ii) 4d and 4f, (iii) [1]
3d and 3p:

a) 4f, 3d, and 3s respectively b) 2s, 4d and 3p respectively

c) 2s, 4d and 3d respectively d) 4d, 3p and 2s respectively

3. During complete combustion of one mole of butane, 2658 kJ of heat is released. The thermochemical reaction for above change is [1]

a) C4 H10 (g) + O2 (g) → 4C O2 (g) + 5H2 O (l) Δc H = −1329.0

2C4 Hb)
kJ
10 (g)
mol
−1
+ 13O2 (g) → 8C O2 (g) + 10H2 O (l) Δc H = −2658.0 kJ

c) C4 H10 (g) + O2 (g) → 4C O2 (g) + 5H2 O (l) Δc H = −2658.0

C4 H10d)
kJ
(g)
mo
−1
+l O2 (g) → 4C O2 (g) + 5H2 O (l) Δc H = +2658.0 kJ mol

4. The formula E = hν is used to calculate [1]

a) wave number b) energy of the ejected electrons

c) radiation emitted by a black body d) energy of quantum

5. For an isolated system, ΔU = 0, what will be ΔS? [1]

a) ΔS > 0 b) ΔS will increase for some time and then reduce

c) ΔS < 0 d) ΔS =0

6. 2 × 108 atoms of carbon are arranged side by side. Calculate the radius of carbon atom if the length of this arrangement is 2.4 cm. [1]

a) 6.0 × 10-11 m b) 6.0 × 10-11 m

c) 3.0 × 10-11 m d) 5.7 × 10-11 m

7. Which of the following processes takes place in oxidation? [1]

a) Addition of hydrogen b) Removal of oxygen

c) Addition of oxygen d) Removal of chlorine

8. Which method is used for the separation of a mixture of sodium sulphate and sodium dichromate? [1]

a) Fractional crystallisation b) Sublimation

Page 1 of 11
 c) Steam distillation d) Simple distillation
9. The hydrocarbon which can react with sodium in liquid ammonia is________. [1]

a) CH3CH=CHCH3 b) C H3 C H2 C ≡ CH

c) CH 3 C H2 C H2 C ≡ CC H2 C H2 C H3 d) C H3 C H2 C ≡ CC H2 C H3

10. Where is nitrogen found in the periodic table? [1]

a) 3nd period, group 15 b) 2nd period, group 15

c) 2nd period, group 14 d) 2nd period, group 18

11. The sign of ΔG for a spontaneous and non-spontaneous process respectively are [1]

a) positive and negative b) negative and positive

c) zero and positive d) positive and zero

12. A liquid hydrocarbon is converted to a mixture of gaseous hydrocarbon by _______. [1]

a) hydrolysis b) oxidation

c) cracking d) distillation
13. Assertion (A): Cyclopentadienyl anion is much more stable than allyl anion. [1]
Reason (R): Cyclopentadienyl anion is aromatic in character.

a) Both A and R are true and R is the correct explanation b) Both A and R are true but R is not the correct
of A. explanation of A.

c) A is true but R is false. d) A is false but R is true.

14. Assertion: Alkylbenzene is not prepared by Friedel-Crafts alkylation of benzene. [1]
Reason: Alkyl halides are less reactive than acyl halides.

a) If both Assertion & Reason are true and the reason is b) If both Assertion & Reason are true but the reason is
the correct explanation of the assertion. 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): Orbitals form the basis of the electronic structure of atoms. [1]
Reason (R): An atomic orbital is the wave function ψ for an electron in an atom.

a) Both A and R are true and R is the correct explanation b) Both A and R are true but R is not the correct
of A. explanation of A.

c) A is true but R is false. d) A is false but R is true.

16. Assertion (A): One mole of SO2 contains double the number of molecules present in one mole of O2. [1]
Reason (R): Molecular weight of SO2 is double to that of O2.

a) Both A and R are true and R is the correct explanation b) Both A and R are true but R is not the correct
of A. explanation of A.

c) A is true but R is false. d) A is false but R is true.

Section B

17. Glycine is an α-amino acid. It exists in the form of Zwitter ion as +NH3CH2COO-. [2]

Write the formula of its

i. conjugate acid
ii. conjugate base
18. Explain why cation are smaller and anions larger in radii than their parent atoms? [2]
19. Round up the following upto three significant figures: [2]
i. 34.216
ii. 10.4107
iii. 0.04597

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 iv. 2808
20. Rotation around carbon-carbon single bond of ethane is not completely free. Justify the Statement. [2]
OR
Despite their - I effect, halogens are o - and p-directing in haloarenes. Explain.
21. Calculate the energy of each of the photons which [2]

i. correspond to light of frequency 3 × 1015 Hz

0

ii. have wave length of 0.50 A

Section C
22. Arrange the following in order of increasing: [3]
i. dipole moment H2O, H2S, BF3
ii. covalent character LiCI, LiBr, LiI
iii. covalent character NaCI, MgCI2, AICI3

23. Answer: [3]

(i) Give the mathematical expression of heat capacity. [1]
(ii) Water can be lifted into the water tank at the top of the house with the help of a pump. Then why is it not considered to be [1]
spontaneous?
(iii) Define surroundings. [1]
24. At 60o C, dinitrogen tetroxide is fifty percent dissociated. Calculate the standard free energy change at this temperature and at one [3]
atmosphere.
25. Calculate the oxidation state of [3]
i. Mn in KMnO4 and
ii. N in NO . −

26. Correct the following electronic configuration of the elements in the ground state. [3]
i. 1s 2 1 2 2 2 2
2s , 2px , 2py , 2pz , 3s , 2px
1

ii. 1s 2 1 1 1 1
2s , 2px , 2py , 2pz

iii. 1s22s1, 2p6, 3s2, 3p6, 3d5

iv. 1s2 2s2, 2p6,3s2, 3p6, 3d4, 4s2
27. Write the general outer electronic configuration of s, p ,d and f-block elements? [3]
28. A sugar syrup of weight 214.2 g contains 34.2 g of sugar (C12H22O11). Calculate [3]

i. molal concentration, and

ii. mole fraction of sugar in the syrup
Section D
29. Read the text carefully and answer the questions: [4]
Once an organic compound is extracted from a natural source or synthesised in the laboratory, it is essential to purify it. Various methods
used for the purification of organic compounds are based on the nature of the compound and the impurity present in it. Finally, the purity
of a compound is ascertained by determining its melting or boiling point. This is one of the most commonly used techniques for the
purification of solid organic compounds. In crystallisation Impurities, which impart colour to the solution are removed by adsorbing over
activated charcoal. In distillation Liquids having different boiling points vaporise at different temperatures. The vapours are cooled and
the liquids so formed are collected separately. Steam Distillation is applied to separate substances which are steam volatile and are
immiscible with water. Distillation under reduced pressure: This method is used to purify liquids having very high boiling points.
(i) Which method can be used to separate two compounds with different solubilities in a solvent?​​
OR
Why chloroform and aniline are easily separated by the technique of distillation?
(ii) Distillation method is used to separate which type of substance?
(iii) Which technique is used to separate aniline from aniline water mixture?​​
30. Read the text carefully and answer the questions: [4]
When anions and cations approach each other, the valence shell of anions are pulled towards the cation nucleus and thus, the shape of the
anion is deformed. The phenomenon of deformation of anion by a cation is known as polarization and the ability of the cation to polarize

Page 3 of 11
 the anion is called as polarizing power of cation. Due to polarization, sharing of electrons occurs between two ions to some extent and the
bond shows some covalent character.
The magnitude of polarization depends upon a number of factors.
(i) Out of AlCl3 and AlI3 which halides show maximum polarization?
(ii) Out of AlCl3 and CaCl2 which one is more covalent in nature?
(iii) The non-aqueous solvent like ether is added to the mixture of LiCl, NaCl and KCl. Which will be extracted into the ether?
OR
Out of CaF2 and CaI2 which one has a minimum melting point?
Section E
31. Attempt any five of the following: [5]
(i) Write the IUPAC name given below: [1]

(ii) Why does the iodination of benzene is carried out in the presence of nitric acid or iodic acid? [1]
(iii) Although benzene is highly unsaturated it does not undergo addition reactions. [1]
(iv) Why is benzene extraordinarily stable though it contains three double bonds? [1]
(v) [1]
Write an IUPAC name:

(vi) Why do alkynes not show geometrical isomerism? [1]

(vii) How will you distinguish between acetylene and ethylene? [1]

32. What is the pH of 0.001 M aniline solution? The ionisation constant of aniline is 4.27 × 10-10. [5]
Calculate the degree of ionisation of aniline in the solution. Also calculate the ionisation constant of the conjugate acid of aniline.
OR
The ionization constant of benzoic acid is 6.46 × 10 −5
and Ksp for silver benzoate is 2.5 × 10 −13
. How many times is silver benzoate more

soluble in a buffer of pH 3.19 compared to its solubility in pure water?

33. Answer: [5]
(i) i. Which of the two: O2NCH2 CH2O- or CH3CH2O- is expected to be more stable and why? [2.5]

ii. Show the polarization of carbon-magnesium bond in the following structure: CH3—CH2—CH2—CH2—Mg—X. [2.5]

OR
i. Write the structural formula of [2.5]
i. o-ethylanisole,
ii. p-nitroaniline,
iii. 2, 3-dibromo-1-phenylpentane,
iv. 4-ethyl-1-fluoro-2-nitrobenzene
ii. Give condensed and bond line structural formulas and identify the functional groups present, if any, for: [2.5]
a. 2, 2, 4-Trimethylpentane
b. 2-Hydroxy-1, 2, 3-propanetricarboxylic acid
c. Hexanedial?

Page 4 of 11
 Solution
Section A

1.
(c) 300.15 K
Explanation: The relation between Kelvin (K) & oC is given by the expression, K = (o C + 273.15)
∴ plugging in 27 (given) for oC in the above expression we get,
K = (27 + 273.15) = 300.15
∴ 27o C = 300.15 K
2.
(b) 2s, 4d and 3p respectively
Explanation: Nuclear charge is defined as the net positive charge experienced by an electron in the orbital of a multi-electron
atom. The closer the orbital, the greater is the nuclear charge experienced by the electron (s) in it.
(i) 2s is closer to the nucleus than 3s.Hence 2s will experience larger effective nuclear charge.
(ii) 4d will experience greater nuclear charge than 4f since 4d is closer to the nucleus than 4f.
(iii) 3p will experience greater nuclear charge since it is closer to the nucleus than 3f because 3p is closer to nucleus than 3f.

3.
(b) 2C H (g) + 13O (g) → 8C O (g) + 10H O (l) Δ H = −2658.0 kJ mol
4 10 2 2 2 c
−1

Explanation: Enthapy of combustion is the energy released when 1mole of a hydrocarbon (butane ) reacts completely in
presence of excess of oxygen. The chemical equation for exothermic reaction for combustion of one mole of butane is
represented as;
−1
2C4 H10 (g) + 13O2 (g) → 8C O2 (g) + 10H2 O (l) Δc H = −2658.0 kJ mo l

4.
(d) energy of quantum
Explanation: Max Planck theorized that energy was transferred in chunks known as quanta, equal to hν. The variable h is a
constant equal to 6.63 × 10-34 J·s and the variable ν represents the frequency in 1/s.
This equation allows us to calculate the energy of photons, given their frequency.
If the wavelength is given, the energy can be determined by first using the wave equation (c = λ × ν) to find the frequency,
then using Planck’s equation to calculate energy.
5. (a) ΔS > 0
△U = 0

Explanation: For an isolated system, and for a spontaneous process, Total entropy change must be positive.

qrev △H △U +p△V 0+p△V

△S = = = =
T T T T

i. e. T △S > 0

Moreover, Or △S > 0

6. (a) 6.0 × 10-11 m

Explanation: Total Length = 2.4 cm
Total number of atoms along the length = 2 × 108
Therefore diameter of each atom = 2.4

8
= 1.2 × 10-8 cm
2×10

= 0.60 × 10-8 cm = 6.0 × 10-11m.

−8

And the radius of the atom = 1.2×10

Page 5 of 11
 7.
(c) Addition of oxygen
Explanation: Addition of oxygen takes place in oxidation.
8. (a) Fractional crystallisation
Explanation: Fractional crystallisation
9.
(b) CH CH C ≡ CH
3 2

Explanation: Terminal alkynes react with Na in the presence of liquid NH3 to form higher alkynes. The alkyne contains acidic
H at the end (i.e. the H bonded to C1 of the chain). Therefore, it is easily replaced with highly electropositive metals such as
Na in liquid ammonia, to form sodium alkaline ion which can react further in the presence of a suitable catalyst to yield higher
alkynes/hydrocarbons.
10.
(b) 2nd period, group 15
Explanation: Nitrogen is the seventh element on the periodic table. It is located in period 2 and group 15. It is at the top of the
periodic table, between carbon and oxygen.
11.
(b) negative and positive
Explanation: ΔG gives a criteria for spontaneity at constant pressure and temperature.
i. If ΔG is negative (< 0), the process is spontaneous.
ii. If ΔG is positive (>0), the process is non-spontaneous.

12.
(c) cracking
Explanation: Pyrolysis of higher alkanes into a mixture of lower alkanes, alkenes, etc. is called cracking. Preparation of oil gas
from kerosene oil and petrol gas from petrol is based upon the process of cracking.
13. (a) Both A and R are true and R is the correct explanation of A.

Explanation:

Here the resonance approach is a poor predictor of stability. The Huckel rule. based on molecular orbital theory is a much
better predictor of stability for this aromatic and antiaromatic system.
14.
(d) If both Assertion and Reason are false statements.
Explanation: Assertion: Di, tri alkylated benzenes are also formed in addition to monoalkylated benzene and the separation of
these products is difficult. Alkylbenzene is prepared by Friedel-Craft's alkylation of benzene followed by the reduction of acyl
benzene to the alkylbenzene. This gives mono alkylated products.
Reason: The carbonyl C atom is more electrophilic than C atom of alkyl halides.
Hence, both Assertion and Reason are are false statements.
15.
(b) Both A and R are true but R is not the correct explanation of A.
Explanation: Whenever an electron is described by a wave function, the electron occupies that orbital. Since many such wave
functions are possible for an electron, many atomic orbitals are possible in an atom corresponding to it. Orbitals form the basis
of the electronic structure of atoms. Each orbital has a definite energy. All the information about the electron in an atom is
stored in its orbital wave function ψ and quantum mechanics make it possible to extract this information out of ψ .
16.
(d) A is false but R is true.

Page 6 of 11
 Explanation: One mole of any substance corresponds to 6.023 × 1023 entities irrespective of its weight.
Molecular weight of SO2 = 32 + 2 × 16 = 64g
Molecular weight of O2 = 2 × 16 = 32g
Therefore Molecular weight of SO2 is double to that of O2.
Section B
17. Conjugate acid +NH3CH2COOH

Conjugate base NH2CH2COO-

18. A variation in size of a cation or anion is due the difference in effective nuclear charge on the outermost electrons. In cation, on
loss of an electron the effective nuclear charge experienced is more by the remaining valence electrons. They are more tightly held
towards centre, thereby the size of the cation decreases. On the other hand in anion, the effective nuclear charge on valence
electrons decrease with addition of each new electron. Moreover, there are more inter-electron repulsions in the valence shell. The
combination of these two effects eventually increase the size of anion.

19. Given number Rounded off (upto three significant figures)

(i) 34.216 34.2

(ii) 10.4107 10.4

(iii) 0.04597 0.0460

(iv) 2808 2810

20. Ethane contains carbon-carbon sigma (σ ) bond and electron distribution of sigma molecular orbital is symmterical around the
internuclear axis of the C-C bond which is not distributed due to rotation about its axis and permits free rotation around C-C bond.
However, the rotation around C—C single bond is not completely free due to repulsion between electron clouds of C-H bonds on
adjacent carbon atoms. Such type of repulsive interaction is called torsional strain.
OR
Halogens present on benzene ring have -I and R effect. -I effect deactivates the ring by withdrawing electron, but +R effect
increases the electron density on ortho and para positions. Hence, halogens are ortho and para directing.

21. i. Energy of photon (E) = hv

h = 6.626 × 10-34 J s; v = 3 × 1015 Hz = 3 × 1015 s-1
E = (6.626 × 10-34 Js) × (3× 1015 s-1) = 1.986 × 10-18 J
ii. Energy of photon (E) = hv = h c

h = 6.26 × 10-34 Js; c = 3 × 108 ms-1

0
λ = 0.50 = 0.5 × 10-10 m
A
−34 8 −1

= 3.98 × 10-15 J
(6.626× 10 Js)×(3× 10 ms )
E= −10
(0.5× 10 m)

Section C
22. i. BF3 is a symmetrical molecule. It has zero dipole moment. oxygen being more electronegative than S, bond moment of O - H
is more than S - H. So, the dipole moments are in the order of
BF3 < H2S < H2O
ii. The anion size in increasing order is
CI- < Br- < I-
Hence, LiCI is least covalent and Lil most. The order is
LiCI < LiBr < Lil
iii. Cation size in decreasing order is
Na+ > Mg2+ > AI3+

Page 7 of 11
 Thus, AI3+ ion has a maximum polarisation effect and Na+ ion has the least. Thus, the covalent order is
NaCI < MgCI2 < AICI3

23. Answer:
(i) The mathematical expression of heat capacity is
q = c × m × ΔT
where c = heat capacity
m = mass and
ΔT= temperature change.

(ii) A spontaneous process should occur continuously by itself after initiation. But this is not so in the given case because
water will go up so long as the pump is working.
So, this process is not considered as a spontaneous process.
(iii)Surroundings: The surroundings include everything other than the system.
For example, if we are studying the reaction between two substances A and B kept in a beaker, the beaker containing the
reaction mixture is the system and the room where the beaker is kept is the surroundings.
24. According to the question, at 60o C, dinitrogen tetroxide is fifty percent dissociated.
Reaction:
N2 O4 (g) ⇌ 2NO 2 (g)

If N2O4 is 50 % dissociated,
1−0.5
xN =
2 O4 1+0.5

2×0.5
⇒ xNO =
2
1+0.5
0.5 1
pN = × 1 atm, pNO = × 1 atm
2 O4 1.5 2 1.5

The equilibrium constant Kp is given by

2
( pNO )
2 1.5
Kp = = = 1.33 atm
p 2
N2 O4 (1.5) (0.5)

Since
Δr Go = –RT ln Kp

Δr Go = -8.314 JK-1 mol-1 × 333 K × 2.303 × 0.1239 = -763.8 kJ mol-1

25. i. 1. Let the oxidation state of Mn atom be x, other atom like O-atom have -2 while K-atom have +1.

1 × ( +1) + (1 × x) + 4 × (- 2) = 0
1 + x + (-8) = 0
1+x-8=0
x-7=0
∴ x = +7
Hence, the oxidation number of Mn in MnO4 is +7.

ii. N in NO . −

Let the oxidation number of N in NO be x and other atom like O- atom is -2.
−
3

∴ Sum of the oxidation numbers of all the atoms in NO = x + 3(-2) = x - 6 −

But the sum of oxidation numbers of all the atoms in NO ion is equal to the charge present on it i.e., -1
−

∴ x - 6 = -1

or x = +5
Thus, the oxidation numbers of N in NO is +5. −
3

26. i. 1s 2 2 2 2
2s , 2px , 2py , 2pz , 3s
2 2

ii. 1s 2 2 1
2s , 2px , 2py , 2pz
1 1

iii. 1s2 2s2, 2p6, 3s2, 3p6, 4s2, 3d2

iv. 1s2 2s2, 2p6, 3s2, 3p6, 3d5, 4s1
27. The general outer electronic configuration are:

Page 8 of 11
 (i) s-Block elements : ns1-2 where n = 2 - 7
(ii) p-Block elements : ns2 np1-6 where n = 2 - 6
(iii) d-Block elements : (n-1)d1-10 ns0-2 where n = 4 - 7
(iv) f-Block elements : (n-2)f0-14 (n-1)d0-1 ns2 where n = 6 - 7
28. i. Weight of sugar syrup = 214.2 g
Weight of sugar in syrup = 34.2 g
weight of water in syrup = 214.2 - 34.2 = 180.0 g
Moles of sugar = = 0.1 (Molar mass = 342)
34.2

342

Molality = 0.1

180
× 1000 = 0.56 m
ii. Moles of sugar = 34.2

342
= 0.1
Moles of water = 180

18
= 10
Mole fraction of sugar = 0.1

10+0.1

= 0.0099
Section D
29. Read the text carefully and answer the questions:
Once an organic compound is extracted from a natural source or synthesised in the laboratory, it is essential to purify it. Various
methods used for the purification of organic compounds are based on the nature of the compound and the impurity present in it.
Finally, the purity of a compound is ascertained by determining its melting or boiling point. This is one of the most commonly
used techniques for the purification of solid organic compounds. In crystallisation Impurities, which impart colour to the solution
are removed by adsorbing over activated charcoal. In distillation Liquids having different boiling points vaporise at different
temperatures. The vapours are cooled and the liquids so formed are collected separately. Steam Distillation is applied to separate
substances which are steam volatile and are immiscible with water. Distillation under reduced pressure: This method is used to
purify liquids having very high boiling points.
(i) Fractional crystallizationis used to separate two compounds with different solubilities in a solvent.
OR
Chloroform and aniline are easily separated by the technique of distillation because chloroform and aniline have
sufficient difference in their boiling points.
(ii) volatile liquids from nonvolatile impurities.
the liquids having sufficient difference in their boiling points.
(iii)Aniline is separated from aniline water mixture by steam distillation as one of the substances in the mixture is water and
the other, a water insoluble substance.
30. Read the text carefully and answer the questions:
When anions and cations approach each other, the valence shell of anions are pulled towards the cation nucleus and thus, the
shape of the anion is deformed. The phenomenon of deformation of anion by a cation is known as polarization and the ability of
the cation to polarize the anion is called as polarizing power of cation. Due to polarization, sharing of electrons occurs between
two ions to some extent and the bond shows some covalent character.
The magnitude of polarization depends upon a number of factors.
(i) AlI3 halides show maximum polarization. The most covalent halide is AlI3.
Since lesser, the electronegativity difference, the more covalent is the aluminum halide.
(ii) AlCl3 is more covalent in nature.
(iii)LiCl will be extracted into the ether.
OR
CaI2 has a minimum melting point.
Section E
31. Attempt any five of the following:
(i)

Page 9 of 11
 (ii) The iodination of benzene is usually brought about by refluxing benzene with iodine and conc. HNO3 or HIO3.
HNO3 or HIO3 oxidises HI to I2 and prevents the backward reaction to occur.

(iii)It is due to delocalization of -electrons in benzene it is highly stable.

(iv)Due to resonance, benzene is extraordinarily stable.
(v)

(vi)Alkynes have a linear structure. Alkynes have triple bond. So, rotation is not possible. Hence, alkynes cannot show
geometrical isomerism.
(vii)Acetylene forms precipitate with ammoniacal silver nitrate solution, ethylene does not react with these reagents.
32. C6H5NH2 + H2O ⇌ C +
6 H5 NH 3 + OH-
+ −
[C6 H5 NH ][OH ]
3
Kb =
[ C6 H5 NH 2 ]

− 2
[OH ]
=
[ C6 H5 NH 2 ]

−−−−−−−−−−−−−−− −
[OH-] = √K
−−−− − −10
b
⋅ C = √4.27 × 10 × 0.001

[OH-] = 6.534 × 10-7

pOH = -log[OH-] = -log[6.534 × 10-7]
pOH = -0.8152 + 7 = 6.18
From, pH + pOH = 14
pH = 14 - 6.18 = 7.82

Kb =
Cα⋅Cα
[(1 − α) ≈ 1 for weak base]
C(1−α)
−
−−
Kb
Kb = C α = α = √
2

Degree of ionisation,
−−−−−−−
= 6.53 × 10-4
−10
4.27×10
α = √
0.001

Ka of conjugate acid of aniline,

Kw
Ka =
Kb

= 2.34 × 10-5
−14
10
=
−10
4.27×10

OR
− +
C6 H5 C OOAg → C6 H5 C O O + Ag

Solubility of water. Suppose solubility in water = x mol L-1 then

[C6H5COO-] = [Ag+] = x mol L-1
−−−−−−−− −
x2 = Ksp or x = √K
−−− −13
sp = √2.5 × 10

−7 −1
= 5 × 10 mol L

Solubility in buffer of pH = 3.19

pH = 3.19 means − log[H +
] = 3.19
¯
¯¯
or log[H +
] = −3.19 = 4.81 or [H +
] = 6.457 × 10
−4
M

C6H5COO- ions now combine with the H+ ions to form benzoic acid but [H+] remains almost constant because we have buffer
solution. Now
− +
C6 H5 C OOH ⇌ C6 H5 C O O + H
− + +
[ C6 H5 COO ][ H ] [ C6 H5 COOH] [H ] −4
6.457×10
∴ Ka =
[ C6 H5 COOH]
or −
=
Ka
=
−5
= 10 .... (i)
[ C6 H5 COO ] 6.46×10

Page 10 of 11
 Suppose solubility in the buffer solution is 'y' mol L-1. Then as most of the benzoate ions are converted into benzoic acid
molecules (which remain almost ionized), we have
y = [Ag+] = [C6H5COO-] + [C6H5COOH] = [C6H5COO-] + 10[C6H5COO-] = 11[C6H5COO-] using equation (i)
y
− − +
∴ [C6 H5 C O O ] = ∴ Ksp = [C6 H5 C O O ][Ag ]
11
y
2.5 × 10
−3
=
11
× y or y 2
= 2.75 × 10
−12
or y = 1.66 × 10 −6

y −6

x
=
1.66×10

−7
= 3.32
5×10

Note that in case of salts of weak acids, the solubility is more in the acidic solution than in water. The reason, in general, may be
explained as follows: Taking example of C6H5COOAg, we have
− +
C6 H5 C OOAg ⇌ C6 H5 C O O + Ag

In acidic solution, the anions (C6H5COO- in the present case) undergo protonation in presence of acid. Thus, C6H5COO- ions are

removed. Hence, equilibrium shifts forward producing more Ag+ ions. Alternatively, as C6H5COO- ions are removed, Qsp

decreases. In order to maintain solubility product equilibrium (Qsp = Ksp), Ag+ ion concentration must increase. Hence, solubility
is more.
33. Answer:
(i) i. is more stable then because NO2 group has -I-effect
and hence it tends to disperse the -ve charge on the O-atom. In contrast, CH3CH2 has + I-effect. It, therefore, tends
to intensify the -ve charge and hence destabilizes it.
ii. Carbon is more electronegative than magnesium.So, Mg has a partially positive charge and C has a partially negative
charge because a bonded pair of electrons attracted towards carbon.
δ− δ+

C H3 − C H2 − C H2 − C H2 < −M g − X

OR

i. i.

ii.

iii.

iv.

ii.

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