Ch – 1 Solutions

1. (a) Explain why on addition of 1 mol glucose to 1 litre water the boiling point of water increases.
(b) Henry’s law constant for CO2 in water is 1.67 × 108 Pa at 298 K. Calculate the number of moles of
CO2 in 500 ml of soda water when packed under 2.53 × 105 Pa at the same temperature.
2.(a) 30 g of urea (M = 60 g mol-1) is dissolved in 846 g of water. Calculate the vapour pressure of water
for this solution if vapour pressure of pure water at 298 K is 23.8 mm Hg.
(b) Write two differences between ideal solutions and non-ideal solutions.
(c) A 10% solution (by mass) of sucrose in water has a freezing point of 269.15 K. Calculate the
freezing point of 10% glucose in water if the freezing point of pure water is 273.15 K.
Given: (Molar mass of sucrose = 342 g mol-1) (Molar mass of glucose = 180 g mol-1)
3. (a) What is van’t Hoff factor? What types of values can it have if in forming the solution, the solute
molecules undergo: (i) Dissociation? (ii) Association?
b) What type of deviation is shown by a mixture of ethanol and acetone? Give reason.
(c) A solution of glucose (molar mass = 180 g mol-1) in water is labelled as 10% (by mass). What would
be the molality and molarity of the solution?(Density of solution = 1.2 g mL-1)
4. (a) The vapour pressures of benzene and toluene at 293 K are 75 mm Hg and 22 mm Hg respectively.
23.4 g of benzene and 64.4 g of toluene are mixed. If the two form an ideal solution, calculate the
mole fraction of benzene in the vapour phase assuming that the vapour pressures are in equilibrium
with the liquid mixture at this temperature.
(b) What is meant by +ve and -ve deviations from Raoult’s law and how is the sign of ΔH solution related
to +ve and -ve deviations from Raoult’s law?
5. (a) Explain the following:
(i) Henry’s law about dissolution of a gas in a liquid
(ii) Boiling point elevation constant for a solvent
(b) A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in 500 g of water.
This solution has a boiling point of 100.42°C. What mass of glycerol was dissolved to make this
solution?(Kb for water = 0.512 K kg mol-1)
6. a) Define the following terms:
(i) Mole fraction (ii) Ideal solution
(b) 15.0 g of an unknown molecular material is dissolved in 450 g of water. The resulting solution freezes
at – 0.34°C. What is the molar mass of the material?(Kf for water = 1.86 K kg mol-1)
7. (a) Differentiate between molarity and molality in a solution. What is the effect of temperature change on
molarity and molality in a solution?
(b) What would be the molar mass of a compound if 6.21 g of it dissolved in 24.0 g of chloroform form
a solution that has a boiling point of 68.04°C. The boiling point of pure chloroform is 61.7°C and the
boiling point elevation constant, Kb for chloroform is 3.63°C/m.
8. (a) Define the terms osmosis and osmotic pressure. Is the osmotic pressure of a solution a colligative
property? Explain.How is osmotic pressure related to the concentration of a solute in a solution?
(b) Calculate the boiling point of a solution prepared by adding 15.00 g of NaCl to 250.0 g of water.
(Kb for water = 0.512 K kg mol-1, Molar mass of NaCl = 58.44 g)
c) A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in 500 g of
water. This solution has a boiling point of 100.42 °C while pure water boils at 100 °C. What mass
of glycerol was dissolved to make the solution?
9. Define reverse osmotic.State the conditions for it. State some applications of it.
10. (i) On mixing liquid X and liquid Y, volume of the resulting solution decreases. What type of
deviation from Raoult’s law is shown by the resulting solution? What change in temperature would
you observe after mixing liquids X and Y?
(ii) What happens when we place the blood cell in water (hypotonic solution)? Give reason.
11. Define azeotropes. What type of azeotrope is formed by positive deviation from Raoult’s law? Given an
example.
12. a) What is meant by positive deviations from Raoult’s law? Give an example. What is the sign of
∆mixH for positive deviation?
b) Differentiate between molarity and molality of a solution. How can we change molality value of a
solution into molarity value?
13. a) State Raoult’s law for the solution containing volatile components. What is the similarity between
Raoult’s law and Henry’s law?
b) Why do gases nearly always tend to be less soluble in liquids as the temperature is raised?
c) Explain why aquatic species are more comfortable in cold water rather than in warm water.
14.Non-ideal solutions exhibit either positive or negative deviations from Raoult’s law. What are these
deviations and why are they caused? Explain with one example for each type.
15. (a) Explain the following phenomena with the help of Henry’s law.
(i) Painful condition known as bends.
(ii) Feeling of weakness and discomfort in breathing at high altitude.
(b) Why does soda water bottle kept at room temperature fizzes on opening?
16. a) An aqueous solution of sodium chloride freezes below 273 K. Explain the lowering in freezing points
of water with the help of a suitable diagram.
b) Calculate the mass of compound (molar mass = 256 g mol-1) to be dissolved in 75 g of benzene to
lower its freezing point by 0.48 K (Kf = 5.12 K kg mol-1).
17. Give reasons: (a) Cooking is faster in pressure cooker than in cooking pan. (b) Red Blood Cells (RBC)
shrink when placed in saline water but swell in distilled water.
18. i) Give reasons for the following:
(a) Measurement of osmotic pressure method is preferred for the determination of molar masses of
macromolecules such as proteins and polymers. (b) Aquatic animals are more comfortable in cold
water than in warm water. (c) Elevation of boiling point of 1 M KCl solution is nearly double than
that of 1 M sugar solution.
ii) Why helium is mixed with Nitrogen and Oxygen in diving cylinders?
Ch – 2Electrochemistry

1. What is the effect of adding a catalyst on

(a) Activation energy (Ea), and(b) Gibbs energy (ΔG) of a reaction?
2. Two half-cell reactions of an electrochemical cell are given below :
MnO–4(aq) + 8H+ (aq) + 5e– → Mn2+ (aq) + 4H2O (l), E° = + 1.51 V
Sn2+ (aq) → 4 Sn4+ (aq) + 2e–, E° = + 0.15 V
Construct the redox equation from the two half-cell reactions and predict if this reaction favours
formation of reactants or product shown in the equation.
3. a)Express the relation among the cell constant, the resistance of the solution in the cell and the
conductivity of the solution. How is the conductivity of a solution related to its molar conductivity?
b) Given that the standard electrode potentials (E°) of metals are:
K+/K = -2.93 V, Ag+/Ag = 0.80 V, Cu2+/Cu = 0.34 V,
Mg2+/Mg = -2.37 V, Cr3+/Cr = -0.74 V, Fe2+/Fe = -0.44 V.
Arrange these metals in increasing order of their reducing power.
4. a) The chemistry of corrosion of iron is essentially an electrochemical phenomenon. Explain the
reactions occurring during the corrosion of iron in the atmosphere.
Or
What is corrosion? Explain the electrochemical theory of rusting of iron and write the reactions
involved in the rusting of iron.
b) Determine the values of equilibrium constant (Kc) and ΔG° for the following reaction:
Ni(s) + 2Ag+ (aq) → Ni2+ (aq) + 2Ag(s),E° = 1.05 V(1F = 96500 C mol-1)
5. a) The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm2 mol-1.
Calculate the conductivity of this solution.
Or
The conductivity of 0.001 M acetic acid is 4 × 10-5 S/m. Calculate the dissociation constant of acetic
acid if Λ0m,for acetic acid is 390 S cm2 mol-1.
b) A zinc rod is dipped in 0.1 M solution of ZnSO4. The salt is 95% dissociated at this dilution at 298 K.
Calculate the electrode potential.[ E°Zn2+ /Zn = – 0.76 V]
6. a) Write the name of the cell which is generally used in inverters. Write the reactions taking place at
cathode and anode in lead storage battery when the battery is in use. What happens on charging
the battery?
b) State Kohlrausch law of independent migration of ions. Why does the conductivity of a solution
decrease with dilution?
7.Define the following terms:
(i) Fuel cell. Explain the electrode reactions involved in the working of H2 – O2 fuel cell.
(ii) Limiting molar conductivity (Λ°m)
(iii) Molar conductivity (Λm)
(iv) Secondary batteries.
8. a) Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation
with change in temperature.
b) Set up Nernst equation for the standard dry cell. Using this equation show that the voltage of a dry
cell has to decrease with use.
c) Define limiting molar conductivity. Why conductivity of an electrolyte solution decreases with the
decrease in concentration but molar conductivity increases with the decrease concentration.
9. a) State Faraday’s first law of electrolysis. How much charge in terms of Faraday is required for the
reduction of 1 mol of Cu2+ to Cu.
Or
Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was passed through
the solution of CuSO4.
(b) Calculate emf of the following cell at 298 K : Mg(s) | Mg2+ (0.1 M) || Cu2+ (0.01) | Cu (s)
[Given E0cell = +2.71 V, 1 F = 96500 C mol-1]
c) Calculate the degree of dissociation (a) of acetic acid if its molar conductivity (Λ m) is
39.05 S cm2 mol-1.Given: λ°(H+) = 349.6 S cm2 mol-1 and λ°(CH3COO–) = 40.9 S cm2 mol-1
10. a) Write the name of the cell which is generally used in transistors. Write the reactions taking place
at the anode and the cathode of this cell.
b)Following reactions may occur at cathode during the electrolysis of aqueous CuCl2 solution using
Pt electrodes:

Based on their standard electrode potential values, which reaction is feasible at cathode and why?
11. A copper-silver cell is set up. The copper ion concentration in it is 0.10 M. The concentration of silver
ion is not known. The cell potential is measured 0,422 V. Determine the concentration of silver ion
in the cell.Given:E°Ag+/Ag = + 0.80 V, E° Cu2+/Cu = + 0.34 V.
Or
Calculate the emf of the following cell at 298 K: Fe(s) | Fe2+ (0.001 M) || H+ (1M) | H2(g) (1 bar), Pt(s)
(Given E°cell = +0.44V)
12. a) Why an electrochemical cell stops working after some time? The reduction potential of an electrode
depends upon the concentration of solution with which it is in contact.
b) Calculate Λ°m for acetic acid.Given that Λ°m (HCl) = 426 S cm2 mol-1, Λ°m (NaCl) = 126 S cm2 mol-1
Λ°m (CH3COONa) = 91 S cm2 mol-1
13. (a) Define the term degree of dissociation. Write an expression that relates the molar conductivity of a
weak electrolyte to its degree of dissociation.
(b) Define electrochemical cell. What happens if external potential applied becomes greater than E 0cell
of electrochemical cell?
14. a) Why is alternating current used for measuring resistance of an electrolytic solution?
b) What advantage do the fuel cells have over primary and secondary batteries?
15. a) What is Nernst equation? write the Nernst equation for the reaction.
2Cr(s) + 3Cd2+ (aq) → 2Cr3+ (aq) + 3Cd (s)
b) What is the purpose of using salt bridges in galvanic cells?
c) What do you understand about normal hydrogen electrodes? Why is it important?
Ch – 3Chemical Kinetics
1. a) Define: i)‘Rate of a reaction’,ii) Order of a reaction’,iii) Rate constant (K),iv) Elementary step
in a reaction, v) Activation energy of a reaction.
b) Differentiate between average rate and instantaneous rate of a reaction.
2. Express the rate of the following reaction in terms of the formation of ammonia:
N2(g) + 3H2(g) → 2NH3(g)
Write the unit of rate constant for a zero-order reaction.
Or
What do you understand by the rate law and rate constant of a reaction? Identify the order of a reaction
if the units of its rate constant are:(i) L-1 mol s-1 (ii) L mol-1 s-1
3. A reaction is of first order in reactant A and of second order in reactant B. How is the rate of this
reaction affected when: (i) the concentration of B alone is increased to three times,
(ii) the concentrationsof A as well as B are doubled?
Or
A reaction is of second order with respect to a reactant. How will the rate of reaction be affected if the
concentration of this reactant is: (i) doubled, (ii) reduced to half?
4. The thermal decomposition of HCO2H is a first order reaction with a rate constant of 2.4 × 10-3 s-1
at a certain temperature. Calculate how long will it take for three-fourths of initial quantity of
HCO2H to decompose. (log 0.25 = -0.6021)
5. (a) For a reaction A + B → P, the rate law is given by, r = k[A]1/2 [B]2.
What is the order of this reaction?
(b) 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.
Or
If the half-life period of a first order reaction in A is 2 minutes, how long will it take [A] to reach
25% of its initial concentration?
c) Rate constant k for a first order reaction has been found to be 2.54 × 10-3 sec-1. Calculate its 3/4th
life, (log 4 = 0.6020).
Or
The rate constant for a first order reaction is 60 s-1. How much time will it take to reduce the initial
concentration of the reactant to its l/10th value?
6. a) Write three differences between ‘order of reaction’ and ‘molecularity of reaction’.
b) A first order gas phase reaction : A2B2(g) → 2A(g) + 2B(g) at the temperature 400°C has the rate
constant k = 2.0 × 10-4 sec-1. What percentage of A2B2 is decomposed on heating for 900 seconds?
(Antilog 0.0781 = 1.197).
7.i) Define the following terms:(a) Pseudo first order reaction.(b) Half life period of reaction (t 1/2).
ii) How does a change in temperature affect the rate, of a reaction? How can this effect on the rate

7. For a reaction: H2 + Cl2 ⟶2HCl

constant of a reaction be represented quantitatively?

Rate = k, (i) Write the order and molecularity of this reaction.(ii) Write the unit of k.
8. A first order reaction has a rate constant of 0.0051 min-1. If we begin with 0.10 M concentration of
the reactant, what concentration of reactant will remain in solution after 3 hours?
[Antilog 0.3986 = 2.503]
9. For a decomposition reaction the values of rate constant k at two different temperatures are given below:
k1 = 2.15 × 10-8 L mol-1 s-1 at 650 K, k2 = 2.39 × 10-7 L mol-1 s-1 at 700 K
Calculate the value of activation energy for this reaction.(R = 8.314 J K-1 mol-1)
Or
The rate of a reaction becomes four times when the temperature changes from 293 K to 313 K.
Calculate the energy of activation (Ea) of the reaction assuming that it does not change with
temperature. [R = 8.314 JK-1 mol-1, log 4 = 0.6021]
10. (a) A reaction is first order in A and second order in B.
(i) Write differential rate equation.(ii) How is rate affected when concentration of B is tripled?
(iii) How is rate affected when concentration of both A and B is doubled?
(b) What is molecularity of a reaction?
11. a) With the help of diagram explain the role of activated complex in a reaction.
b) For the hydrolysis of methyl acetate in aqueous solution, the following results were obtained:
t/s 0 30 60

[CH3COOCH3]/mol L-1 0.60 0.30 0.15

(i) Show that it follows pseudo first order reaction, as the concentration of water remains constant.
(ii) Calculate the average rate of reaction between the time interval 30 to 60 seconds. (Given log 2
= 0.3010, log 4 = 0.6021).
12. a) For which type of reactions, order and molecularity have the same value?
b) For a zero order reaction will the molecularity be equal to zero? Explain.

13. For a general reaction A ⎯→ B, the plot of concentration of A vs time is given in Fig. Answer the
c) Why is the probability of reaction with molecularity higher than three very rare?

following question on the basis of graph.

(a) What is the order of the reaction?(b) What is the slope of the curve?
(c) What is the unit of the rate constant?
14. a) What happens to the most probable kinetic energy and the energy of activation with increase in
temperature?
b) With the help of an example explain what is meant by pseudo first order reaction.