07.03.

2024
Part E: Numerical problems

Solution
Colligative Properties of Dilute solutions
1. The vapour pressure of pure benzene at a certain temperature is 0.850bar. A non-volatile,
non-electrolyte solid weighing 0.5 g when added to 39.0 g of benzene (molar mass 78 g mol-1).
Vapour pressure of the solution, then, is 0.845bar. What is the molar mass of the solid
substance?
Ans: M2 = 170 g mol–1

2. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50g of urea (NH 2CONH2) is dissolved in 850 g of
water. Calculate the vapour pressure of water for this solution and its relative lowering.

3. The boiling point of benzene is 353.23 K. When 1.80 g of a non-volatile solute was dissolved in
90 g of benzene, the boiling point is raised to 354.11 K. Calculate the molar mass of the solute.
Kb for benzene is 2.53Kkgmol–1
Ans: M2 = 58 gmol–1

4. 18 g of glucose, C6H12O6, is dissolved in 1 kg of water in a saucepan. At what temperature will water

boil at 1.013bar? Kb for water is 0.52K kg mol-1.
Ans: 373.202 K.

5. Boiling point of water at 750 mm Hg is 99.63°C. How much sucrose is to be added to 500 g of water such
that it boils at 100°C.
Ans: w2 = 121.67 g

6. 1.00 g of a non-electrolyte solute dissolved in 50 g of benzene lowered thefreezing point of benzene by

0.40 K. The freezing point depression constantof benzene is 5.12 K kg mol–1. Find the molar mass of
the solute.
Ans: M2 = 256 g mol-1

7. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate

(a) The freezing point depression and (b) the freezing point of the solution.
Ans: a. ΔTf = 2.2 K b. Freezing point of the aqueous solution = 273.15 K – 2.2 K = 270.95 K

8. Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in75 g of acetic acid to lower its
melting point by 1.5°C. Kf = 3.9 K kg mol-1
Ans: w2 = 5.08 g

9. 2 g of benzoic acid (C6H5COOH) dissolved in 25 g of benzene shows a depression in freezing point equal
to 1.62 K. Molal depression constant for benzene is 4.9 K kg mol–1. Find molar mass of benzoic acid.
Ans: M2 = 241.98 or 242 gmol-1

10. Calculate the osmotic pressure in Pascal exerted by a solution prepared by dissolving 1.0 g of polymer of molar
mass 185,000 in 450 mL of water at 37°C.
Ans: π = 31 Pa
11. 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic pressure of
such a solution at 300 K is found tobe 2.57 × 10-3 bar. Calculate the molar mass of the protein.
Ans: M2 = 61,022 g mol-1

Vant Hoff’s factor (i)

1. 0.6 mL of acetic acid (CH3COOH), having density 1.06 g mL–1, is dissolved in 1 litre of water.
The depression in freezing point observed for this strength of acid was 0.0205°C.
Calculate the van’t Hoff factor.
Ans: i= 1.041

Raoult’s law for binary liquid mixture

1. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively, at 350 K .
Find out the composition of the liquid mixture if total vapour pressure is 600 mm Hg. Also
find the composition of the vapour phase.

2. Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 298 K are 200 mm Hg and 415
mm Hg respectively. Calculate the vapour pressure of the solution prepared by mixing 25.5 g of CHCl3
and 40 g of CH2Cl2 at 298 K.
Ans: PTotal = 347.9 mm Hg

Henry’s Law
1. H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of
H2S in water at STP is 0.195 m, calculate Henry’s law constant.
Ans: KH =282 bar

Molality, Molarity and mole fraction

1. Calculate molality of 2.5 g of ethanoic acid (CH3COOH) in 75 g of benzene.
Ans: molality = 0.556 mol kg–1

2. Calculate the molarity of a solution containing 5 g of NaOH in 450 mL solution.

Ans: molarity= 0.278 mol L–1

3. Calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of C2H6O2 by mass.
Ans: mole fraction = 0.068
 ELECTROCHEMISTRY

NERNST EQUATION
1. Represent the cell in which the following reaction takes place
Mg(s) + 2Ag+(0.0001M) → Mg2+(0.130M) + 2Ag(s). Calculate its E(cell) if E0(cell) = 3.17 V.

Ans: E(cell) = 2.96 V.

2. Calculate the emf of the cell in which the following reaction takes place
Ni(s) + 2Ag+ (0.002 M) → Ni2+ (0.160 M) + 2Ag(s) Given that E0(cell) = 1.05 V

Ans: E(cell) = 0.914 V

3. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10.

Ans: E= −0.591 V

4. Write the Nernst equation and emf of the following cells at 298 K:
(i) Mg(s)|Mg2+(0.001M)||Cu2+(0.0001 M)|Cu(s)

(ii) Fe(s)|Fe2+(0.001M)||H+(1M)|H2(g)(1bar)| Pt(s)

(iii) Sn(s)|Sn2+(0.050 M)||H+(0.020 M)|H2(g) (1 bar)|Pt(s)

(iv) Pt(s)|Br2(l)|Br–(0.010 M)||H+(0.030 M)| H2(g) (1 bar)|Pt(s).

Standard Gibb’s Energy(ΔG0)

1. The standard electrode potential for Daniell cell is 1.1V. Calculate the standard Gibbs energy for the
reaction Zn(s) + Cu2+(aq) ⎯→ Zn2+(aq) + Cu(s)

Ans : ΔG0 = –21.227 kJ mol–1

2. The cell in which the following reaction occurs: 2Fe3+ + 2I- → 2Fe2+ + I2, E0 cell = 0.236 V at 298 K.
Calculate the standard Gibbs energy
Ans : ΔG0 = - 45.54 kJ mol–1

3. In the button cells, widely used in a watches and other devices in the following reaction take place
Zn(s) +Ag2O(s) +H2O(l) →Zn2+(aq) + 2Ag(s) + 2OH-(aq). Determine Δ𝐺0 for the reaction.
(E0Zn = -0.76V and E0Ag= +0.34V)

4. Calculate the ΔG0at 298K for the cell reaction. Fe2+(aq)+Ag+(aq)→ Fe3+(aq)+Ag(s)
(Given: E0cell=+0.03V and F=96500C)

5. 2Cr(s) + 3Cd2+(aq) → 2Cr3+(aq) + 3Cd, Calculate the ΔG0 and equilibrium constant of the
reactions. (E0Cr3+/Cr= - 0.74V and E0Cd2+/Cd = - 0.40V)
EQUILIBRIUM CONSTANT (K)
1. Calculate the equilibrium constant of the reaction: Cu(s) + 2Ag+(aq) → Cu2+(aq) + 2Ag(s)
E0(cell) = 0.46 V
Ans : KC = 3.92 × 1015

2. The cell in which the following reaction occurs: 2Fe3+ + 2I- → 2Fe2+ + I2, E0cell = 0.236 V at 298 K.
Calculate the equilibrium constant of the cell reaction.
Ans: Kc = 9.57 x 107

3. The equilibrium constant for the following cell reaction was found to be 6.509 x 10 8. Calculate the
standard cell potential Cd(s) + Sn+2(aq) )→ Cd+2(aq) + Sn(s) (R = 8.314 JK-1 mol-1 , F = 96500C)

LIMITING MOLAR CONDUCTIVITY(ʌ0m)

1. ʌ0m for NaCl, HCl and NaAc are 126.4, 425.9 and 91.0 S cm2 mol–1respectively.
Calculate ʌ0m for HAc.
Or
Limiting molar conductivity for sodium chloride, HCl, sodium acetate are 126.4, 425.9 and
91.0 S cm2 mol–1respectively. Calculate ʌ0m for acetic acid.

Ans: ʌ0m for acetic acid= 390.5 S cm2 mol–1

2. Calculate limiting molar conductivity of calcium sulphate , limiting molar conductance of calcium
and sulphate ions are 119 and 160 S cm2 mol-1 respectively.

3. Calculate limiting molar conductivity of calcium chloride, limiting molar conductance of calcium and
chloride ions are 119 and 76.3 S cm2 mol-1 respectively.

4. Calculate limiting molar conductivity of Magnesium sulphate, limiting molar conductance of

Magnesium and sulphate ions are 106.0 and 160 Scm2mol-1 respectively.

5. The molar conductivity at infinite dilution of Al (SO 4)3 is 858 Scm2 mol-1, Calculate the molar ionic
conductivity of Al3+ ion, Given that 𝜆° SO42- = 160 Scm² mol-1

DEGREE OF DISSOCIATION (α)

1. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 Scm–1. Calculate its degree of
dissociation if ʌ0m for acetic acid is 390.5 S cm2 mol–1.

Ans: α = 0.1233

2. The conductivity of a 0.01M solution of acetic acid at 298 K is 1.65 X 10 -4 Scm-1.

Calculate its degree of dissociation. (given ʌ0m for acetic acid=390.5 S cm2 mol-1)
DISSOCIATION CONSTANT (K)
1. The conductivity of 0.001028 mol L–1 acetic acid is 4.95 × 10–5 Scm–1. Calculate dissociation constant
for acetic acid if ʌ0m for acetic acid is 390.5 S cm2 mol–1.
Ans: K= 1.78 x 10-5 molL-1

2. The conductivity of a 0.01M solution of acetic acid at 298 K is 1.65 X 10-4 Scm-1.
Calculate dissociation constant for acetic acid. (Given ʌ0m for acetic acid=390.5 S cm2 mol-1)

3. The molar conductivity of 0.025 mol L–1 methanoic acid is 46.1 S cm2 mol–1.Calculate its degree
of dissociation and dissociation constant. Given λ0(H+)= 349.6 S cm2 mol–1 and
λ0(HCOO–) = 54.6 S cm2 mol–1

Ans: α = 0.114 K= 3.67 x 10-4 molL-1

4. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. if ʌ0m for acetic acid is 390.5 S cm2 mol–1,
what is its dissociation constant?

ELECTROLYSIS
1. A solution of CuSO4 is electrolysed for 10 minutes with a current of 1.5 amperes. What is the mass of
copper deposited at the cathode?

Ans: 0.2938 g.

2. A solution of NiNO3 is electrolysed between platinum electrodes using a current of 5 amperes

for 20 minutes. What mass of Ni is deposited at the cathode?

3. Consider the reaction: Cr2O72– + 14H+ + 6e– → 2Cr3+ + 8H2O

What is the quantity of electricity in coulombs needed to reduce 1 mol of Cr2O72–?
Ans: 578922 C

4. If a current of 0.5 ampere flows through a metallic wire for 2 hours, then how many electrons would
flow through the wire?
Ans: 2.25 x 1022 electrons

MOLAR CONDUCTIVITY (ʌm)

1. Calculate the molar conductance of 0.15M acetic acid solution if its conductivity at 298K is
1.6X 10-4 Scm-1

2. The resistance of 0.1 M solution is found to be 2.5 X 10 3 Ω. Calculate the molar conductance. Given
cell constant= 1.15 cm-1

3. The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm–1. Calculate its molar conductivity

4. Conductivity of 0.00241 M acetic acid is 7.896 × 10–5 S cm–1. Calculate its molar conductivity
CELL CONSTANT
1. The resistance of 0.1 M KCI solution is found to be 520 𝛺 and shows a conductivity value of 0.248 S cm-1.
Find the value of cell constant.

2. The resistance of a conductivity cell containing 0.001M KCl solution at 298 K is 1500 Ω. What is the cell constant
if conductivity of 0.001M KCl solution at 298K is 0.146 × 10–3 S cm–1.

CONDUCTIVITY ( К )
1. The resitance of a 1M salt solution occupying volume between two platinum electrodes 1.8 cm
apart and 5.4 cm2 in area was found be 32𝛺. Calculate the conductivity of a solution.

2. The resistance of 0.01M acetic acid solution is found to be 220 𝛺, when measured in a cell has two
electrodes of area of cross section 3.8 cm2 placed 10.5cm apart. Calculate conductivity.

3. 1 M solution of a salt surrounding two platinum electrodes 2.1 cm apart and 4.2 cm2 in area was found
to offer a resistance of 50 ohm. Calculate the conductivity of solution.

CHEMICAL KINETICS
ACTIVATION ENERGY
1. The rate constants of a reaction at 500K and 700K are 0.02s –1 and 0.07s–1 respectively.
Calculate the values of Ea.
Ans: Ea = 18230.8 J or 182.308 kJmol-1

2. The rate of the chemical reaction doubles for an increase of 10 K in absolute temperature
from 298 K. Calculate Ea
Ans: Ea = 52.9 kJ mol-1

3. The specific reaction rate of a reaction triples when the temperature changes from 30°C to 50°C.
Calculate the energy of activation of the reaction (R =8.314 JK-1 mol-1 )

4. A reaction is found to have a rate constant 3.46 X 10-5 at 250C and rate constant 4.87 X 10-3 at 650C.
Calculate activation energy for the reaction (R =8.314 JK-1 mol-1 )

5. The rate of a particular reaction doubles when temperature changes from 27 0C to 370C.
Calculate the energy of activation.

6. Rate constant of a reaction at 300 K and 400 K are 0.0345 s-1 and 0.1365 s-1 respectively. Calculate the
activation energy for the reaction. (Given R= 8.314 JK-1mol-1)

7. Rate constant of a first order reaction increases four times when the temperature changes from 270C to
470C. Calculate its activation energy. (Given R =8.314 JK-1 mol-1 )
 8. The energy of activation of a reaction is 60 kJ mol -1. If its rate constant at 310 K is 2 x 10-4 s-1. Calculate
the rate constant at 320K. (Given: R= 8.314 J K-1 mol-1)

9. The first order rate constant for the decomposition of ethyl iodide by the reaction
C2H5I(g) → C2H4 (g) + HI(g)
at 600K is 1.60 × 10–5 s–1. Its energy of activation is 209 kJ/mol. Calculate the rate constant of the
reaction at 700K.

10. The rate constant of a reaction at 250K and 400K are 0.01 s -1 and 0.03 s-1 respectively. Calculate the
energy of activation of the reaction(R =8.314 JK-1 mol-1)

11. The rate constant of a first order reaction at 600K is 1.60 x 10-5 s-1. Its energy of activation is
209 KJ/mol. Calculate the rate constant of the reaction at 700K. (Given: R= 8.314 J K-1 mol-1)

12. The rate constant of first order reaction becomes 5 times when the temperature is raised from 350K to
400 K. calculate the activation energy(Ea) for the reaction.

13. The specific reaction rate of a reaction doubled when temperature changes from 30 0C to 500C.
Calculate the energy of activation of the reaction(R =8.314 JK -1 mol-1)

14. The decomposition of hydrocarbon follows the equation k = (4.5 × 10s) e -28000K/T . Calculate Ea

FIRST ORDER KINETICS & HALF-LIFE PERIOD

1. A first order reaction has a rate constant 1.15 X 10-3 s-1 . How long will 5 g of this reactant take to
reduce to 3 g?

Ans: t= 444 s

2. The rate constant for a first order reaction is 60 s. How much time will it take to reduce the initial
concentration of the reactant to its 1/16 value?
Ans: t= 4.6 x 10-2 s

3. For a first order reaction, show that time required for 99% completion is twice the time required for
the completion of 90%of reaction.

4. In first order reaction, the concentration of a reactant decreases from 400 mol L-1 to 25 mol L-1 in 200
seconds. Calculate the rate constant for the reaction.

5. Calculate the rate constant of the first order reaction, If 70% of chemical reaction is completed in
23mins.

6. Half -life period of a first order reaction is 30 seconds. Calculate the time required for the 2/3rd
completion of the reaction.

7. The Initial concentration of N2O5 in the following first order reaction N2O5(g) →4NO2(g) + ½ O2(g)
was 1.24 x 10-2 mol L-1 at 318K. then [NO2] after 60 minutes was 0.20 x 10-2 mol L-1 at 318 K.
Calculate the rate constant of the reaction at 318K.

8. Rate constant[k] of decay of a radioactive species is found to be 5.5 x 10-14 s-1. Then
find half life period and the time for 99.9 % decay of radioactive species.
 9. A first order reaction takes 40 min for 30% decomposition. Calculate t1/2

10. 60 % of first order reaction was completed in 60 minutes, calculate the time taken for 50% completed.

11. Half life period of a first order reaction is 30 minutes. Calculate the time required for 90%
Completion of the reaction.

12. The half life period of a first order reaction is 69.3 min. Calculate the time required for 75% completion
of the reaction

13. For the first order reaction, half-life period of the reaction is 120 minutes; calculate the time
taken to complete 90% of the reaction.

14. If a first order reaction rate is 80% complete in 60 minute. Find the half -life period (t1/2) of the
reaction.

15. The rate constant of a certain reaction is 10 min -1. Calculate the half-life period of this reaction in
seconds.

16. A first order reaction is found to have a rate constant, k = 5.5 × 10-14 s-1.Find the half-life of the
reaction.

17. Calculate the half-life of a first order reaction from their rate constants
given below: (i) 200 s–1 (ii) 2 min–1 (iii) 4 years–1

RATE OF REACTION AND ORDER OF REACTION

1. For the reaction R → P, the concentration of a reactant changes from 0.03Mto 0.02M in 25 minutes.
Calculate the average rate of reaction using units of time both in minutes and seconds.

2. In a reaction, 2A → Products, the concentration of A decreases from 0.5 mol L to 0.4 mol L in
10 minutes. Calculate the rate during this interval?

3. The conversion of molecules X to Y follows second order kinetics. If concentration of X is increased to

three times how will it affect the rate of formation of Y?

4. For a reaction, A + B → Product; the rate law is given by, r = k [A]1/2 [B]2. What is the order
of the reaction?

5. From the rate expression for the following reactions,determine their order of reaction
and the dimensions of the rate constants.
(i) 3 NO(g) → N2O(g) Rate = k[NO]2

(ii) H2O2(aq) + 3 I- + 2 H+ → 2 H2O (l) + I-3 Rate = k[H2O2][I-]

(iii) CH3CHO(g) → CH4 (g) + CO(g) Rate = k [CH3CHO]3/2

(iv) C2H5Cl(g) → C2H4 (g) + HCl(g) Rate = k [C2H5Cl]

6. For the reaction:
2A + B → A2B
the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial rate of the reaction
when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1.

7. A reaction is second order with respect to a reactant. How is the rate of reaction affected if the
concentration of the reactant is (i) doubled (ii) reduced to half?

8. A reaction is first order in A and second order in B.

(i) Write the differential rate equation.

(ii) How is the rate affected on increasing the concentration of B three times?

(iii) How is the rate affected when the concentrations of both A and B are doubled?