ARTHASIDDHI CLASSES DATE: 02-09-25

12th (Science)
TIME: 1 Hr

Chemistry- MARKS: 14

SEAT NO:

Q.1 Solve the following:(Any One) 2

1 The normal boiling point of ethyl acetate is 77.06 °C. A solution of 50 g of a non-volatile solute in 150 g of ethyl
acetate boils at 84.27 °C. Evaluate the molar mass of solute if Kb for ethyl acetate is 2.77 °C kg molˉ¹.

Ans Given: Normal boiling point of ethyl acetate

= T0b = 77.06 °C
Biling point of solution

= Tb = 84.27 °C
Mass of nonvolatile solute = W2 = 50 g
Mass of ethyl acetate = W1 = 150 g
Kb of ethyl acetate = 2.77 °C kg mol¯1
To find: Molar mass of solute = M2
1000 Kb W2
Formula: M2 =
△Tb W1

Calculation: For solution of nonvolatile solute and ethyl acetate,

△ Tb = Tb – T0b
= 84.27°C – 77.06°C
= 7.21°C = 7.21 K
Kb = 2.77 °C kg mol-1 = 2.77 K kg mol-1
Now, using formula and substituting values.
1000 Kb W2
M2 =
△Tb W1
−1 −1
1000 g Kg ×2.77 K kg mol ×50g
M2 = = 128 g mol-1
7.21 K × 150 g

Ans.: The molar mass of nonvolatile solute is 128g g mol–1.

2 Derive the relationship between pH and pOH.

Ans

3 The hydroxyl ion concentration in an aqueous solution of NaOH is 2 × 10–4 mol dm–3. Calculate PH of the
solution.

Ans Given:

Hydroxyl ion concentration (OH¯) = 2 × 10¯4 mol dm¯3

pH and pOH relation: pH + pOH = 14
pOH = – log [OH¯]
 Calculate pOH:

pOH = – log (2 × 10¯4)

= – [log 2 + log 10¯4]
= – [0.3010 – 4]
= 4 – 0.3010 = 3.699
Calculate pH:
pH = 14 – pOH
= 14 – 3.699 = 10.301
The pH of the solution is 10.301.

4 Calculate the work done during the expansion of 2 moles of an ideal gas from 10 dm3 to 20 dm3 at 298 K in
vaccum.

Ans

5 Gold crystallises into face-centred cubic cells. The edge length of unit cell is 4.08× 10-8 [Link] the
density of gold. [Molar mass of gold = 197 g mol–1]

Ans Given, The edge length (a) of the unit cell =4.08× 10-8 cm

It crystallises in Face-centred cubic cells.

6 When gold crystallizes, it forms face-centred cubic cells. The unit cell edge length is 408 pm. Calculate the
density of gold. Molar mass of gold is 197 g/mol.
Or
Gold crystallises into face-centred cubic cells. The edge length of unit cell is 4.08 × 108 cm–8 Calculate the
density of gold. [Molar mass of gold = 197 g mol–1]

Ans Given: Edge length (a) = 408 pm = 408 × 10–12 m = 4.08 × 10–8 cm
Molar mass of gold = M = 197 g mol–1

NA = 6.022 × 1023 atoms mol–1

To find: Density (ρ)
Formula: Density (ρ) =
M n

3
a NA

Calculation: For an fcc lattice, number of atoms per unit cell is 4.

∴ n=4
From formula,
M n
Density, ρ = 3
a NA
−1
197 g mol × 4 atoms
∴ ρ = −8 3 23 −1
(4.08 × 10 ) cm × 6.022 × 10 atom mol

3 3 3
= 19.27 g/cm = 19.27 × 10 kg/m

Ans.: Density of gold is 19.27 g/cm3 = 19.27 × 103 kg/m3.

7 pH of a solution is 3.12. Calculate the concentration of H3O+ ion.

Ans Given: pH of solution = 3.12

To find: Concentration of H3O+ ion
Formula: pH = – log10 [H3O+]
Calculation: From formula,
pH = – log10[H3O+]

∴ log10[H3O+] = – pH
= – 3.12
= – 3 – 0.12 + 1 – 1
= (– 3 – 1) + 1 – 0.12

= – 4 + 0.88 = 4 .88
+
Thus [H3O ] = antilog [ 4 .88]
= 7.586 × 10–4 M

Ans.: The conentration H3O+ is 7.586 × 10–4 M.

8 Silver crystallizes in fee structure. If edge length of unit cell is 400 pm, calculate density of silver (Atomic mass
of Ag = 108).

Ans Given: Edge length (a) = 400 pm = 4.00 × 10–8 cm

Atomic mass of Ag = M = 108 g mol–1
To find: Density (ρ)
Formula: Density (ρ) =
M n

3
a NA

Calculation: For an fcc lattice, number of atoms per unit cell is 4.

∴ n=4
From formula,
M n
Density, ρ = 3
a NA
−1
108 g mol × 4 atoms
∴ ρ = −8 3 23 −1
(4.00 × 10 ) cm × 6.022 × 10 atom mol

= 11.2 g/cm3
Ans.: Density of silver is 11.2 g/cm3.

9 Three moles of an ideal gas are expanded isothermally from 15 dm3 to 20 dm3 at constant external pressure of
1.2 bar. Estimate the amount of work in dm3 bar and J.

Ans Given: Initial volume (V1) = 15 dm3

Final volume (V2) = 20 dm3
External pressure (Pext) = 1.2 bar
To find: Amount of work in dm3 bar and Joule
Formula: W = – Pext ΔV = – Pext (V2 – V1)
Calculation: From formula,
W = – Pext ΔV = – Pext (V2 – V1)
W = – 1.2 bar (20 dm3 – 15 dm3)
= – 1.2 bar × 5dm3 = – 6 dm3 bar
Now, 1 dm3 bar = 100 J

Hence, W = – 6 dm3 bar ×

= – 600 J
Ans.: The work done is – 600 dm3 bar = – 600 J.

10 Silver crystallises in fcc structure. The edge length of the unit cell is found to be 408.7 pm. Calculate density of
the unit cell. (Given: Molar mass of silver is 108 g mol–1)

Ans Given: Edge length (a) = 408.7 pm = 408.7× 10¯12 m = 408.7× 10–10 cm,
Molar mass/Atomic mass of silver = 108 g mol–1
To find: Density (d)
Formula: (i) Mass of one atom =
Atomic mass

Avogardo Number

(ii) Volume of unit cell = a3

mass of unit cell
(iii) Density =
volume of unit cell

Calculation: For fcc lattice, number of atoms per unit cell is 4.

Atomic mass
Mass of one atom of silver =
Avogardo Number

= 17.9 × 10–23 g
108
= 23
6.023×10

Mass of unit cell = 4 × 10–23 = 71.7 × 10–23 g

Volume of unit cell = a3 = (408.7 × 10–10 cm)3 = 6.827× 10–23 cm3

mass of unit cell
Density =
volume of unit cell
−23
71.7×10 g
= −23 3
= 10.5 g
6.827×10 cm
11 For a certain reaction ∆H° is – 224 kJ and ∆S° = –153 J/K–1. At what temperature the cvhange over from
spontaneous to nonspontaneous will occur?

Ans Given: ∆H° = – 224 kJ

∆S° = – 153 J k–1 = – 0.153 kJ K–1
To find: Temperature (T) at which reaction become spontaneous
Formula: T=
ΔH°

ΔS°

−224 kJ
Calculation:T = ΔH°
= −1
= + 1464 K
ΔS° −0.153 kJ K

Since ∆H° and ∆S° are both negative, the reaction is spontaneous at
low temperatures. A change over will occur at 1464 K. The reaction is
spontaneous below 1464 K.
Ans.: The reaction will become spontaneous below 1464 K.

12 The boiling point of benzene is 353.23 K. When 1.80 gram of non-volatile solute was dissolved in 90 gram of
benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of solute. [K for benzene = 2.53 K kg
mol–1]

Ans

13 An element with molar mass 27 g/mol forms cubic unit cell with edge length of 405 pm. If density of the
element is 2.7 g/cm³. What is the nature of cubic unit cell? (fcc or ccp)

Ans P = nM

3
NA a

M = 27 g/mol
P = 2.7 g/cm3
a = 405 pm = 4.05 × 10-8 cm
a3 = 66.43 × 10-24 cm3
n×27
2.7 = −24 23
(66.43×10 )×(6.022×10 )

n=4
unit cell = face centered unit cell

14 Calculate the amount of CaCl2 (van't Hoff factor i = 2.47) dissolved in 2.5 L solution so that its osmotic pressure
at 300 K is 0.75 atmosphere.
[Given: Molar mass of CaCl2 is 111 g mol¯1, – 1 R = 0.082 L atm K¯1 mol¯1]

Ans 3.425 g

15 For the reaction N2 O4 → 2 NO2

(g) (g)

(ΔH° = + 57.24 kJ, ΔS° = 175.8 JK–1)

At what temperature the reaction will be spontaneous?

Ans Given: ∆H° = +57.24 kJ

∆S° = 175.8 J k–1 = 0.1758 kJ K–1
To find: Temperature (T) at which reaction become spontaneous
Formula: T=
ΔH°

ΔS°

Calculation:T = ΔH°
=
57.24 kJ

−1
= + 325.6 K
ΔS° 0.1758 kJ K

Since ∆H° and ∆S° are both positive, the reaction is spontaneous at
high temperatures. A change over will occur at 325.6 K. The reaction
is spontaneous above 325.6 K.
Ans.: The reaction will become spontaneous above 325.6 K.

16 Calculate the work done in kJ in a reaction if the volume of the reactant decreases from 8 dm3 to 4 dm3 against
43 bar pressure. [1 dm3 bar = 100 J]

Ans Given: Initial volume (V1) = 8 dm3

Final volume (V2) = 8 dm3
External pressure (P) = 43 bar
Conversion factor = 1 dm3 bar = 100 J
Formula:
W = – PΔV
Where, ΔV = V2 – V1
ΔV = 4 – 8 = – 4 dm3

W = – (43 × – 4)
 W = 172 dm3 bar
Since 1 dm3 bar = 100 J

W = 172 × 100
W = 17200 J
W = 17.2 kJ

∴ The work done in the reaction is 17.2 kJ.

17 An organic substance (M = 169 gram mol–1) is dissolved in 2000 cm3 of water. Its osmotic pressure at 12 °C
was found to be 0.54 atm. If R = 0.0821 L atm K–1, calculate the mass of the solute.

Ans 7.80 g

Q.2 Solve the following:(Any One) 3

1 Unit cell of a metal has edge length 288 pm and density 7.86 g cm–3. Determine the type of the crystal lattice.
[Atomic mass of metal = 56 g mol–1]

Ans Given: Edge length (a) = 288 pm = 2.88 × 10–8 cm

Atomic mass = 56 g mol–1,

Density (ρ) = 7.86 g/cm3

To find: Type of crystal lattice
Formula: Density (ρ) =
M n

3
a NA

Calculation: From formula,

M n
Density, ρ = 3
a NA
−1
56 g mol × n
∴ 7.86 g cm–3 = 3
−1
−8 3 23
(2.88 × 10 ) cm × 6.022 × 10 atom mol
−3 −8 3 23 −1
7.86 g cm (2.88×10 ) cm × 6.022 × 10 atom mol

∴ n= −1
56 g mol
3 −1
7.86×(2.88) ×6.022×10
=
56

= 2.88 × 10–1
= 2.018

∴ Number of atoms in unit cell = 2

Since unit cell contains 2 atoms, it has body-cubic (bcc) lattice.
Ans.: The type of crystal lattice is body-centred cubic (bcc) lattice.

2 Predict the type of cubic lattice of a solid element having edge length of 400 pm and density is 6.25 g/mL.
(Atomic mass of element = 60)

Ans

3 An element with molar mass 27 g/mol forms cubic unit cell with edge length of 405 pm. If density of the
element is 2.7 g/cm3, what is the nature of cubic unit cell?
Ans Given: Edge length (a) = 405 pm = 4.05 × 10–8 cm
Molar mass = 27 g mol–1,

Density (ρ) = 2.7 g/cm3

To find: Nature of cubic unit cell
Formula: Density (ρ) =
M n

3
a NA

Calculation:From formula,
M n
Density, ρ = 3
a NA
−1
27 g mol × n
–3
∴ 2.7 g cm = −8 3 23 −1
(4.05 × 10 ) cm × 6.022 × 10 atom mol
−3 −8 3 23 −1
2.7 g cm (4.05×10 ) cm × 6.022 × 10 atom mol

∴ n= −1
27 g mol

= 4.00

∴ Number of atoms in unit cell = 4

Since unit cell contains 4 atoms, it has face-centred cubic (fcc) or
ccp structure.
Ans.: The nature of given cubic unit cell is face-centred cubic (fcc) or ccp
structure.

4 3.795 g of sulphur is dissolved in 100 g of carbon disulfide. This solution boils at 319.81 K. What is the
molecular formula of sulphur in solution? The boiling point of the solvent is 319.45 K. (Given that Kb for CS₂ =
2.42 K kg molˉ¹ and atomic mass of S = 32 u

Ans M = 1000 Kb W2

2
△Tb W1

W1 = 100 g, W2 = 3.795 g

△ Tb = (319.81 - 319.45)K = 0.36 K

−1 −1
1000 g kg ×2.42 K kg mol ×3.795 g
M2 =
0.36 K × 100 g

= 255.10 g mol-1
Atomic mass of S = 32 u
Therefore number of atoms in a molecule of sulphur
molar mass of S 255.1
= = = 7.92 ≈ 8
atomic mass of S 32

The molecular formula would be S8 in CS2

5 Δ H for the formation of ethane gas is – 84.4 kJ at 300 K. Calculate ΔU for the reaction.

Ans Δ H = – 84.4 kJ
Temperature, T = 300 K
Gas constant, R = 8.314 J/mol K = 0.008314 kJ/mol.K

Δ ng is the change in the number of gaseous moles between products and reactants.
Formation reaction of ethane gas:
2 C (s) + 3H2(g) → C2H6 (g)
Moles of gaseous reactants: 3 (from H2)
Moles of gaseous products: 1 (from C2H6)

Δ ng = Moles of gaseous products – Moles of gaseous reactants

=1–3=–2

Δ U = ΔH – Δng RT

Δ U = (– 84.4) – (– 2 × 0.008314 × 300)

Δ U = – 84.4 + (2 × 2.4942)

Δ U = – 84.4 + 4.9884

Δ U = – 79.41 kJ

6 A weak monobasic acid is 10% dissociated in 0.05 M solution. What is percent dissociation in 0.15 M solution?

Ans Given: α = 10% = 10

= 0.1, c1 = 0.05 M, c2 = 0.15 M, α 2 = ?
1 100

If α1 and α2 are the values of the degree of dissociation at two different concentrations c1 and c2 respectively,
then

Ka = α 21 c1 = α 22 c2

∴ α 2

1
c1 = α 22 c2

∴ 0.12 × 0.05 = α 2

2
× 0.15
2

∴ α 2

2
=
0.1 × 0.05

0.15
= 0.0033

α2 = 0.057 = 5.7%

∴ Percent dissociation = 5.7%

7 Derive the mathematical expression between molar mass of a non-volatile solute and elevation of boiling point.
OR
How will you determine molar mass of non volatile solute by elevation of boiling point?

Ans

8 Explain the relationship between Gibbs standard energy change of the reaction and equilibrium constant.

Ans i.

9 A metal crystallises into two cubic lattices namely face centred (fcc) and body centred (bcc), whose unit cell
edge lengths are 3.5 A and 3.0 A respectively. Find the ratio of the densities of fcc and bcc.

Ans Given: Edge length of fcc unit cell (a1) = 3.5 A,

Edge length of bcc unit cell (a2) = 3.0 A,
To find: Ratio of densities of fcc and bcc
ρ (fcc)
=
1

ρ2 (bcc)
 Formula: Density of unit cell = ρ =
M n

3
a NA

Calculation: For fcc unit cell, n = 4.

4×M
Density of fcc unit cell = ρ1 = 3
NA × (3.5 A)

For bcc unit cell, n = 2.

2×M
Density of bcc unit cell = ρ1 = 3
NA × (3.5 A)

∴ Ratio of densities of fcc and bcc unit cell is,

3
ρ NA ×(3.0A)
4×M
=
1
×
ρ 3
2×M
2
NA ×(3.5 A)
ρ1 54

ρ
= 42.875
= 1.259 ≅1.26
2

Ans.: The ratio of densities of fcc and bcc structures is 1.26.

Q.3 Answer the following Questions:(Any One) 3

1 State and explain Henry’s law .

Ans (i) Statement: Henry's law states that the solubility of a gas in a liquid is directly proportional to the pressure of
the gas over the solution.

Thus, S ∝ P or S = KHP
where, S is the solubility of the gas in mol L–1, P is the pressure of the gas in bar over the solution. KH, the
proportionality constant is called Henry's law constant and its unit is mol L¯1 bar¯1.
(ii) When P = 1 bar, KH = S Thus, KH is the solubility of the gas in a liquid when its pressure over the solution is 1
bar.

2 Obtain the relationship between ∆H and ∆U for gas phase reactions.

OR
Derive relationship between ∆H and ∆U for gaseous reaction.

Ans (i) At constant pressure, ∆H and ∆U are related as

...
∆H = ∆U + P∆V
(1)
(ii) For reactions involving gases, ∆V cannot be neglected. Therefore,
∆H = ∆U + P∆V = ∆H + P(V2 – V1)
...
∆H = ∆U + PV2 – PV1
(2)
where, V1 is the volume of gas phase reactants and V2 that of the gaseous products.
(iii) We assume reactant and product behave ideally. Applying ideal gas equation, PV = nRT.
Suppose that n1 moles of gaseous reactants produce n2 moles of gaseous products....
Then, (3)
PV1 = n1RT and PV2 = n2RT
(iv) Substitution of equation (3) into equation (2) yields
∆H = ∆U + n2RT – n1RT
= ∆U + (n2 – n1) RT
...
= ∆U + ∆ng RT
(4)
where, ∆ng is difference between the number of moles of products and those of reactants.

3 What is the value of ΔSsurr. for the following reaction at 298 K?

6CO2(g) + 6H2O(l) → C6H12O6(s) + 6O2(g)

[ΔG° = 2879 kJ mol–1, ΔS° = – 210 J K–1 mol–1]

Ans – 9451 J K–1

4 Calculate the number of atoms in fcc unit cell.

OR
A face centred cube (fcc) consists of how many atoms? Explain.
OR
Calculate the number of atoms in a unit cell of a metal crystallising in face centred cubic structure.

Ans (i) A face-centred cubic (fcc) unit cell has particles at the eight corners plus
particles at the centre of its six faces.
(ii) Each particle present at the corner of a given unit cell is shared with seven
other neighbouring unit cells. As a result, its contribution to the given unit cell
1
is only .
8

Thus, the number of particles present at corners per unit cell

1
= 8 corner atoms × atom per unit cell = 1
8

(iii) Each particle at the centre of the six faces is shared with one neighbouring
cube. Thus, 1/2 of each face particle belongs to the given unit cell. Thus, the
number of particles present at faces per unit cell
1
= 6 atoms at the faces × 2
atom per unit cell = 3
 Therefore, fcc unit cell has one corner particle plus 3 face particles, making
total of 4 particles per unit cell.

5 State and explain Hess's law of constant heat summation.

Ans (i) Hess's law of constant heat summation: Hess's law of constant heat
summation states that, "Overall the enthalpy change for a reaction is equal to
sum of enthalpy changes of individual steps in the reaction".
(ii) Illustration:
(a) The enthalpy change for a chemical reaction is the same regardless of the
path by which the reaction occurs. Hess's law is a direct consequence of the
fact that enthalpy is state function. The enthalpy change of a reaction
depends only on the initial and final states and not on the path by which the
reaction occurs.
(b) To determine the overall equation of reaction, reactants and products in
the individual steps are added or subtracted like algebraic entities.
(c) Consider the synthesis of NH3,
(1)
(2)

The sum of the enthalpy changes for steps (1) and (2) is equal to enthalpy
change for the overall reaction.

6 Explain the hydrolysis of salts of strong acid and weak base.

Ans Hydrolysis of salt of strong acid and weak base:

(i) CuSO4 is salt of strong acid H2SO4 and weak base Cu(OH)2. When CuSO4 is
dissolved in water, it dissociates completely as,

CuSO4(aq) → Cu 2+

(aq)
+ SO
2+

4(aq)

(ii) 2−
ions of salt have no tendency to react with water because the possible
SO4

product H2SO4 is strong electrolyte.

(iii) The reaction of Cu2+ ions with OH¯ ions from unionized CU(OH)2. The
hydrolytic equilibrium for CuSO4 is then written as,
2+
Cu(aq) + 4H2O(l) ⇌ Cu(OH)2(aq) + 2H3OO +

(aq)

(iv) Due to the presence of excess of H3O+ ions, the resulting solution of CuSO4
becomes acidic and turns blue litmus red.

7 What is osmotic pressure? How will you determine molar mass of solute from osmotic pressure?

Ans he excess of pressure on the side of the solution that stops the net flow of solvent into the solution through a
semipermeable membrane is called osmotic pressure.

8 Explain the common ion effect with an example.

Ans When a salt of a weak acid is added to the acid itself, the dissociation of the weak acid is suppressed further.
Acetic acid is a weak acid. It is not completely dissociated in an aqueous solution and hence the following
equilibrium exists.
CH3COOH(aq) H+(aq) + CH3COO¯(aq)
However, the added salt, sodium acetate, completely dissociates to produce Na+ and CH3COO ions.
CH3COONa(aq) → Na+(aq) + CH3COO(aq)
Hence, the overall concentration of CH3COO is increased, and the acid dissociation equilibrium is disturbed.
We know from Le chatelier's principle that when stress is applied to a system at equilibrium, the system adjusts
itself to nullify the effect produced by that stress. So, in order to maintain the equilibrium, the excess
CH3COO¯ions combine with H ions to produce much more unionized CH3COOH i.e., the equilibrium will shift
towards the left. In other words, the dissociation of CH3COOH is suppressed. Thus, the dissociation of a weak
acid (CH3COOH) is suppressed in the presence of a salt (CH3COONa) containing an ion common to the weak
electrolyte. It is called the common ion effect.

9 The standard enthalpy of combustion of formaldehyde is Δc H° = – 517 kJ. How much heat will be evolved in
the formation of 22g of CO2?

Ans 285.5 kJ

10 Define acids and bases according to Bronsted-Lowry theory. Derive relationship between pH and pOH
 Ans J. N. Bronsted and T. M. Lowry (1923) proposed a more general theory known as the Bronsted-Lowry proton
transfer theory. According to this theory acids and bases are defined as follows:
Acid: Acid is a substance that donates a proton (H⊕) to another substance.
Base: Base is a substance that accepts a proton (H⊕) from another substance

11 Calculate the pH of buffer solution composed of 0.01 M weak base BOH and 0.02 M of its salt ВА. [Kb = 1.8 ×

10–5 for weak base]

Ans 8.95

12 State whether entropy change is positive or negative in the following example.

Vaporisation of a liquid.

Ans (i) A system's disorder or variability is measured by its entropy (S). More molecular chaos is indicated by a
higher entropy value.
(ii) The process by which a liquid turns into a gas is called vaporisation. Liquid molecules acquire energy during
this phase transition and separate, spreading into a greater volume gas molecules.
(iii) Effect on Entropy:
(a) Molecules are densely packed and have limited mobility in the liquid phase.
(b) Molecules in the gaseous phase are widely separated and free to go in any direction.
(c) Entropy rises during vaporisation because gases are more random and disordered than liquids.

(iv) Since molecular disorder increases, the entropy change (ΔS) is positive for the vaporization of a liquid.

Q.4 Answer the following Questions:(Any One) 2

1 Define
i. Extensive and intensive properties
ii. Isobaric and adiabatic processes

Ans i.A property which depends on the amount of matter present in a system is called an extensive property.A
property which is independent of the amount of matter in a system is called intensive property.
ii.A process in which there is no exchange of heat between system and surroundings is an adiabatic process.

2 A weak monobasic acid is 10% dissociated in 0.05 M solution.

What is percent dissociation in 0.15 M solution ?
Ans

3 Write any four application of buffer solution.

Ans Application of buffer solution:

Buffer solution finds extensive applications in a variety of fields. Some of its
applications are given.
(i) In biochemical system: pH of blood in our body is maintained at 7.36-7.42
due to (HCO3–+ H2CO3) buffer. A mere change of 0.2 pH units can cause
death. The saline solution used for intravenous injection must contain buffer
system to maintain the proper pH of the blood.
(ii) Agriculture: The soils get buffered due to presence of salts such as
carbonate, bicarbonate, phosphates and organic acids. The choice of
fertilizers depends upon pH of soil.
(iii) Industry: Buffers play an important role in paper, dye, ink, paint and drug
industries.
(iv) Medicine: Penicillin preparations are stabilized by addition of sodium citrate
as buffer. When citric acid is added to milk of magnesia [Mg(OH)2]
magnesium citrate is formed, which is a buffer.
(v) Analytical chemistry: In qualitative analysis, a pH of 8 to 10 is required for
precipitation of cations IIIA group. It is maintained with the use of (NH4OH +
NH4Cl) buffer.

4 Write different statements of the first law of thermodynamics.

OR
Write any two statements of first law of thermodynamics.

Ans (i) the total energy of a system and surroundings remains constant when the
system changes from an initial state to final state.
(ii) Energy of the universe remains constant.
(iii) The total internal energy of an isolated system is constant.
(iv) Energy is neither created nor destroyed and can only be converted from one
form to another.

5 Calculate the mole fraction of solute, if the vapour pressure of pure benezene at certain temperature is 640
mmHg and vapour pressure of solution of a solute in benzene is 600 mmHg

Ans

6 State whether entropy change is positive or negative in the following example:

Melting of ice

Ans (i) Ice, in its solid state, has a highly ordered structure with lower entropy due to
the strong hydrogen bonding between molecules.
 (ii) When ice melts into liquid water, the molecules gain enegry, allowing them to
move more freely and increasing the overall disorder of the system.
(iii) Since entropy is a measure of disorder, the transition from solid to liquid

results in a positive change in entropy (ΔS > 0).

(iv) Therefore, during the melting of ice, the entropy change is positive.

7 Explain impurity defect in stainless steel with diagram.

Ans Nonstoichiometric defects:

(i) Nonstoichiometric defect arises when the ratio of number of atoms of one
kind to that of other kind or the ratio of number of cations to anions becomes
different from that indicated by its chemical formula.
(ii) In this defect, stoichiometry of the compound is changed. However, the
change in stoichiometry does not cause any change in the crystal structure.
(iii) There are two types of nonstoichiometric defects:
(a) Metal deficiency defect (b) Metal excess defect

8 Explain buffer action of sodium acetate-acetic acid buffer.

Ans 1. The sodium acetate-acetic acid buffer acts by utilizing the equilibrium between the weak acid (acetic
acid) and its conjugate base (acetate ion from sodium acetate).
2. When an acid is added to the buffer, the acetate ions neutralize the extra H⁺ ions, forming more acetic
acid and thus preventing a decrease in pH.
3. Conversely, when a base is added, the acetic acid donates H⁺ ions to neutralize the base, forming water
and acetate ions, preventing an increase in pH. This mechanism allows the buffer to maintain a relatively
constant pH level.

9 Define
(i) Isomorphism
(ii) Polymorphism

Ans (i) Isomorphism is the phenomenon by which two or more substances have the
same crystal structure.
(ii) Polymorphism is the phenomenon by which a single substance exists in two
or more forms or crystalline structures.

10 Write the consequences of Schottky defect with reasons.

OR
What are the consequences of Schottky defect?

Ans Consequences of Schottky defect are:

(i) As the number of ions decreases, mass decreases. However, volume remains unchanged. Hence, the density
of a substance decreases.
(ii) The number of missing cations and anions is equal, Hence, the electrical neutrality of the compound is
preserved.

11 What is extensive property? Give examples.

Ans A property which depends on the amount of matter present in a system is called an extensive property.
e.g. Mass, volume, internal energy, heat capacity, number of moles, etc.

12 State second law of thermodynamics in terms of entropy.

Ans The second law of thermodynamics states that the total entropy of the system and its surroundings (universe)
increases in a spontaneous process.
For the process to be spontaneous,
∆ STotal = ∆ Ssystem + ∆Ssurr > 0

13 Write the mathematical equation for the first law of thermodynamics for
(i) adiabatic process (ii) isochoric process

Ans Adiabatic process:

(i) The mathematical expression of first law of thermodynamics is ΔU = Q + W

(ii) In adiabatic process, there is no exchange of heat between system and its
surroundings. Hence, Q = 0

Δ U=0+W

∴ Δ U = +W or – ΔU = – W
(iii)Thus, an increase in internal energy of the system is the work done on it. If the
work is done by the system on the surroundings at the expense of its internal
energy, the internal energy accompanying the adiabatic process would
decrease.
Isochoric process.
 (i) The mathematical expression of first law of thermodynamics is ΔU = 0 + W.

(ii) Usually, chemical reactions are carried out in the open containers under

constant atmospheric pressure. In such reactions, ΔV ≠ 0.

Since, W = – Pext ΔV

Δ U = QP – Pext ΔV

QP = ΔU + Pext ΔV

14 Write the overall reactions taking place at the cathode in a lead accumulator cell during discharging of the cell.

Ans The electrons produced at the anode travel through the external circuit and re-enter the cell at the cathode. At
the cathode, PbO2 is reduced to Pb2+ ions in the presence of H+ ions. Subsequently, Pb2– ions so formed
combine with SO2+ ions from H2SO4 to form insolube PbSO4 that gets coated on the electrode.

15 Distinguish between isothermal process and adiabatic process.

Ans
Isothermal process Adiabatic process

(i) It is a process in which temperature It is a process in which there is no

of the system remains constant exchange of heat between system
throughout the transformation. and surroundings.

System is completely insulated

(ii) Heat flows from the system
with respect to heat from the
surroundings to and vice versa. (Q ≠ 0).
surroundings (Q = 0).

(iii) Temperature remains constant Temperature may increase or

(ΔT = 0). decrease (ΔT ≠ 0).

(iv) Change in internal energy is zero Internal energy may increase or

(ΔU = 0). decrease (ΔU ≠ 0).

16 Derive an expression for maximum work obtainable during isothermal reversible expansion of an ideal gas from
initial volume (V₁) to final volume (V2).

Ans 1. Consider the expansion of n moles of an ideal gas enclosed in a cylinder fitted with a weightless
andfrictionless piston at a constant temperature T.
2. ​Let the pressure of the gas be P which is equal to the external pressure.
3. ​Let the external pressure be reduced by an infinitesimally small amount dp so that the new external
pressure becomes (P-dp).
4. Let the corresponding small increase in volume by dv.
5. ​Therefore amount of work done in the expansion of the gas, dw = - [(p dp)dv] = -[pdv -[Link]] ..(i)
6. ​Since dp and dv are very small, their product ([Link]) will be much smaller and can be neglected ∴
dw = -pdv ...(ii)
7. During expansion of the gas, if the initial volume V1 changes to volume V2 then total amount of work
alone (Wmax) can be obtained by integrating the work, dw between the two limits, V1 and V2.
17 Explain metal deficiency defect with example.

Ans Metal deficiency defect:

(i) This defect is possible only in compounds of metals that show variable
oxidation states.
(ii) In some crystals, positive metal ions are missing from their original lattice
sites. The extra negative charge is balanced by the presence of cation of the
same metal with higher oxidation state than that of missing cation.
(iii) In the compound NiO, one Ni2+ ion is missing creating a vacancy at its lattice
site. The deficiency of two positive charges is made up by the presence of
two Ni3+ ions at the other lattice sites of Ni2+ ions. The composition of NiO
then becomes Ni0.97 O1.0.

18 2000 mmol of an ideal gas expanded isothermally and reversibly from 20 L to 30 L at 300 K, calculate the work
done in the process (R = 8.314 JK–1 mol–1).

Ans
19 Write the mathematical equation for the first law of thermodynamics for
(i) isothermal process (ii) adiabatic process

Ans Isothermal process:

(i) The mathematical expression of first law of thermodynamics is ΔU = Q + W.
(ii) Temperature is constant in an isothermal process, and therefore, internal

energy is constant. Hence, ΔU = 0.

0=Q+W

∴ W = – Q or – W = Q
(iii) Thus, the heat absorbed by the system is entirely used for doing work on the
surroundings. When work is done on the system by the surroundings it results
in release of heat.
Adiabatic process:
(i) The mathematical expression of first law of thermodynamics is ΔU = Q + W

(ii) In adiabatic process, there is no exchange of heat between system and its
surroundings. Hence, Q = 0

Δ U=0+W

∴ Δ U = +W or – ΔU = – W
(iii) Thus, an increase in internal energy of the system is the work done on it. If the
work is done by the system on the surroundings at the expense of its internal
energy, the internal energy accompanying the adiabatic process would
decrease.

20 Write the overall reactions taking place at the anode in a lead accumulator cell during discharging of the cell.

Ans When the cell provides current, spongy lead is oxidised to Pb2+ ions and negative charge accumulates on lead
plates. The Pb2+ ions so fomed combine with SO2-4 ions from H2SO4 to form insoluble PbSO4. The net
oxidation is the sum of these two processes.

21 Derive the relationship between molar mass, density of the substance and unit cell edge length.

Ans

22 Explain the following terms:

i. Substitutional impurity defect
ii. Interstitial impurity defect

Ans Substitutional impurity defect: In this defect, the foreign atoms are found at the lattice sites in place of host
atoms. The regular atoms are displaced from their lattice sites by impurity atoms.
For example : Solid solutions of metals (alloys): Brass is an alloy of Cu and Zn. In brass, host Cu atoms are
replaced by the impurity of Zn atoms. The Zn atoms occupy regular sites of Cu atoms as shown in the figure.
 Brass
Interstitial impurity defect: In this defect, the impurity atoms occupy interstitial spaces of lattice structure. For
example in steel, Fe atoms occupy normal lattice sites. The carbon atoms are present in interstitial spaces, as
shown in the figure. Stainless steel

Stainless Steel

23 Write features of reversible process.

Ans Features of reversible process:

(i) The driving and opposing forces differ by an infinitesimal amount.

(ii) The process can be reversed by an infinitesimal change in conditions.
(iii) A reversible process proceeds infinitely slowly and takes place in infinite
number of steps.
(iv) At the end of every step of the process, the system attains mechanical
equilibrium with the surroundings.

24 Derive the equation of Raoult's law of binary solution containing non-volatile solute.

Ans Statement of Raoult's Law:

Raoult's law states that the partial vapor pressure of a volatile solvent in a solution is directly proportional to its
mole fraction in the solution.
For a binary solution with:
Solvent (A) - Volatile
Solute (B) - Non-volatile
Since the solute is non-volatile, only the solvent contributes to the vapor pressure.
Raoult's law Expression:
According to Raoult's Law, the vapor pressure of the solvent in the solution is:
PA = X A P0 A
where:
PA = Vapor pressure of the solvent in the solution.
P0A = Vapor pressure of the pure solvent.
XA = Mole fraction of the solvent (XA = 1 – XB)
Thus,
PA = (1 – XB)P0A
PA = P A – XB P0 A
Lowering of Vapor Pressure:
The lowering of vapor pressure due to the non-volatile solute is:

Δ P = P0 A – PA
Substituting PA = P0A – XBP0A

Δ P = P0A – (P0A – XBP0A)

Δ P = XB P 0 A
Relative Lowering of Vapor Pressure:
Dividing both sides by P0A,
ΔP

0
= XB
P
A

Since the mole fraction of solute (XB) is

nB
XB = nA + nB

where nA and nB are the number of moles of solvent and solute, respectively, we get:
ΔP nB

0
= nA + nB
P
A

For a dilute solution, where nB << nA, we approximate,

ΔP nB

0
≈ nA
P
A

The relative lowering of vapor pressure is directly proportional to the mole fraction of the non-volatile solute.

25 Classify the following solids into different types:

 (i) Silver (ii) P4 (iii) Diamond (iv) NaCl

Ans (i) Silver Metallic solid

(ii) P4 - Molecular solid
(iii) Diamond - Covalent network solid
(iv) NaCl Ionic solid

26 One mole of an ideal gas is expanded isothermally and reversibly from 10 L to 15 L at 300 K. Calculate the work
done in the process.

Ans

27 The electrical conductivity of a semiconductor increases with increasing temperature. Give reason.

Ans (i) The electrical conductivity of a semiconductor increases with increasing

temperature.
(ii) This is because, the number of electrons with sufficient energy so as to get
promoted to the conduction band increases as temperature rises. Thus, at
higher temperatures, there are more mobile electrons in the conduction band
and more vacancies in the valence band than at lower temperature.

28 Derive an expression to calculate molar mass of non volatile solute by osmotic pressure measurement.

Ans For very dilute solution

n2 RT
Where π =
V

π = Osmotic Pressure
n2 = Number of moles of solute
R = Gas constant
T = Absolute temperature
V = Volume of solution
W2 (Mass of solute)
n2 =
M2 (Molar mass of solution)

W2 RT
M2 =
π V
This formula can be used for the calculation of molar mass of a nonionic solute (i.e., nonelectrolyte),
measurement. by osmotic pressure

29 Distinguish between Crystalline solid and Amorphous solid.

Ans
Crystalline Solids Amorphous solid

The constituent particles are

The constituent particles are
arranged in a regular and periodic
arranged randomly.
manner.

They do not have sharp melting

They have sharp and characteristic
point. They gradually soften over a
melting points.
range of temperature.

They are anisotropic, i.e., have

They are isotropic, i.e., have same
different physical properties in a
physical properties in all directions.
different directions.

They have long-range order. They have only short range order.

e.g. Ice, NaCl etc. e.g. Glass, rubber, plastics, etc.

Q.5 Answer the following Questions:(Any One) 4

1 Derive the expression for PV work.

OR
Derive the equation: W = – Pext ΔV.

Ans (i) Consider a certain amount of gas at constant pressure P is enclosed in a

 cylinder fitted with frictionless, rigid movable piston of area A. Let volume of
the gas be V1 at temperature T. This is shown in the diagram.

(ii) On expansion, the force exerted by a gas is equal to area of the piston
multiplied by pressure with which the gas pushes against piston. This
pressure is equal in magnitude and opposite in sign to the external
atmospheric pressure that opposes the movement and has its value – Pext
Thus,
f = – Pext × A ... (1)
where, P ext is the external atmospheric pressure.
(iii) If the piston moves out a distance d, then the amount of work done is equal to
the force multiplied by distance.
W=f×d ... (2)
Substituting equation (1) in (2) gives
W = – Pext × A × D ... (3)
(iv) The product of area of the piston and distance it moves is the volume change
(ΔV) in the system..
ΔV = A × d ... (4)
Combining equation (3) and (4), we get
W = – Pext ΔV
W = – Pext (V2 - V1) Where V2 is the final volume of the gas.

2 Derive the relationship between relative lowering of vapour pressure and molar mass of solute.

Ans (i) The relative lowering of vapour pressure is equal to the mole fraction x2 of
solute in the solution. That is,
0
P1 − P1

= = x2 ... (1)
ΔP

0 0
P1 P1

(ii) The mole fraction of a component of solution is equal to its moles divided by
n2
the total moles in the solution. Thus, x2 = n1 + n2
where, n1 and n2 are the
moles of solvent and solute respectively, in the solution.
(iii) In dilute solutions, n1 >> n2 and n1 + n2 ≈ n1. Thus, the mole fraction x2 is then
given by,
n2
x2 = n1
... (2)
(iv) From equations (1) and (2),
n2
= ... (3)
ΔP

0 n1
P1

(v) Suppose that we prepare a solution by dissolving W2 g of a solute in W1 g of

solvent. The moles of solute and solvent in the solution are then,
W2 W1
n2 = and n1 = ... (4)
M2 M1

where, M1 and M2 are molar masses of solvent and solute, respectively.

(vi) Substitutions of equation (4) into equation (3) yields.
W2 /M2
x2 = =
ΔP

0
P1 W1 /M1
0
P1 − P1 W2 M1
= =
ΔP
∴
0 0
P1 P1 W1 M2

3 Derive the expression for the maximum work.

Ans (i) Consider n moles of an ideal gas enclosed in a cylinder fitted with frictionless
movable rigid piston. It expands isothermally and reversibly from the initial
volume V1 to final volume V2 at temperature T. The expansion takes place in a
number of steps as shown in the figure.
 (ii) When the volume of a gas increases by an infinitesimal amount dV in a single
step, the small quantity of work done
dW = – Pext dV ... (1)
(iii) As the expansion is reversible, P is greater by a very small quantity dp than
Pext. Thus, P – Pext = dP or Pext = P – dP ... (2)
Combining equations (1) and (2),
dW= – (P – dP) dV = – PdV + [Link]
Neglecting the product [Link] which is very small, we get
dW = – PdV ... (3)
(iv) The total amount of work done during entire expansion from volume V1 to V2
would be the sum of infinitesimal contributions of all the steps. The total work
is obtained by integration of Equation (3) between the limits of initial and final
states. This is the maximum work, the expansion being reversible. Thus,

=–

Hence, Wmax = – Pdv ... (4)

(v) Using the ideal gas law, PV = nRT,

=
Wmax

= – nRT (∵ T is constant)

= – nRT In

= – nRT (In V2 – In V1)

= – nRT In

∴
Wmax = – 2.303 nRT log10 ... (5)

(vi)
At constant temperature, P1V1 = P2V2 or

Replacing in equation (5) by , we get,

Wmax = – 2.303 nRT log10 ... (6)

Equations (5) and (6) are expressions for work done in reversible isothermal
process.

4 Derive an expression of Ostwald’s dilution law for weak acid.

Ans (i) Consider an equilibrium of weak acid HA that exists in solution partly as the
undissociated species HA and partly H+ and A– ions. Then

HA(aq) ⇌ H +

(aq)
+A −

(aq)

(ii) The acid dissociation constant is given as:

+ −
[H ][A ]

Ka = ... (i)
[HA]

(iii) Suppose 1 mol of acid HA is initially present in volume V dm3 of the solution.

At equilibrium, the fraction dissociated would be α , where α is degree of

dissociation of the acid. The fraction of an acid that remains undissociated

would be (1 - α )

HA(aq) ⇌ H +

(aq)
+A
−

(aq)

Amount present at equilibrium (mol) (1 – α ) α α

 Concentration at equilibrium (mol dm–3) 1−α α α

V V V

(iv) Thus, at eqilibrium [HA] = 1−α

mol dim–3,
V

[H+] = [A–] = mol dm–3

α

(v) Substituting these in equation (1),

(α/V)(α/V) 2
α
Ka = = ... (2)
(1−α)/V (1−α)V

(vi) If c is the intial concentration of an acid in mol dm–1 then c = 1/V.

2
α c
Replacing 1/V in equation (2) by e, we get Ka = ... (3)
1−α

(vii)For the weak acid HA, α is very small, or (1 – α ) ≅1.

With this equation (2) and (3) becomes:

Ka = α 2/V and Ka = α 2c ... (4)

√Ka

α = c
or α = √Ka , V ... (5)
The equation (5) implies that the degree of dissociation of a weak acid is
inversely proportional to the square root of its concentration or directly
proportional to the square root of volume of the solution containing 1 mol of
the weak acid.

5 Calculate the standard enthalpy of formation of CH3OH(1) from the following data

Ans