SOLUTIONS

I.SECTION-A
1.What is meant by ‘reverse osmosis’?
2.What are isotonic solutions?
3.What are ‘azeotropes’?
4. What type of intermolecular attractive interaction exists in the pair of methanol and acetone?
5. What is the effect of change in temperature of a solution on its molality and molarity?
6.State Henry’s law and mention two of its important applications.
7.Why do gases nearly always tend to be less soluble in liquids as the temperature is raised?
8.Suggest the most important type of intermolecular attractive interaction in the following pairs:
(i) n-hexane and n-octane
(ii) I2 and CCl4.
(iii) NaClO4 and water
(iv) methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H6O)
9.(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.
10.How is osmotic pressure related to the concentration of a solute in a solution?Why are osmotic pressure
measurements more preferred compared to other colligative properties?
11.Explain why on addition of 1 mol of glucose to 1 litre of water, the boiling point of water increases.
12.a)Blood cells are isotonic with 0.9% sodium chloride solution. What happens if we place blood cells in a
solution containing
(i) 1.2% sodium chloride solution?
(ii) 0.4% sodium chloride solution?
(b) (i) Out of 1 M glucose and 2 M glucose, which one has a higher boiling point and why?
(ii) What happens when the external pressure applied becomes more than the osmotic pressure of solution?
13. Define
(i) Mole fraction
(ii) Raoult’s law
(iii) Molarity
(iv) Molal elevation constant (Kb)
14.What type of deviation is shown by a mixture of ethanol and acetone? Give reason.
15. (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?
SECTION-B NUMERICALS
1.19.5g of CH2FCOOH is dissolved in 500g of water. The depression in the freezing point of water observed
is 1.0°C. Calculate the Van’t Hoff factor and dissociation constant of fluoroacetic acid.
2.Calculate the depression in the freezing point of water when 10g of CH 3CH2CHClCOOH is added to 250g
of water. Ka = 1.4 x 10-3 Kg = 1.86 K kg mol-1.

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3.Determine the amount of CaCl 2 (i = 2.47) dissolved in 2.5 litre of water such that its osmotic pressure is
0.75 atm at 27°C.
4.The air is a mixture of a number of gases. The major components are oxygen and nitrogen with an
approximate proportion of 20% is to 79% by volume at 298 K. The water is in equilibrium with air at a
pressure of 10 atm. At 298 K if Henry’s law constants for oxygen and nitrogen are 3.30 x 107 mm and 6.51 x
107 mm respectively, calculate the composition of these gases in water.
5.Benzene and toluene form ideal solution over the entire range of composition. The vapour pressure of pure
benzene and toluene at 300 K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole fraction of
benzene in vapour phase if 80g of benzene is mixed with 100g of toluene.

6.Vapour pressure of water at 293 K is 17·535 mm Hg. Calculate the vapour pressure of water at 293 K when
25 g of glucose is dissolved in 450 g of water.

7.Henry’s law constant for the molality of methane in benzene at 298 K is 4.27 x 10 5 mm Hg. Calculate the
solubility of methane in benzene at 298 K under 760 mm Hg.
8.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)
9.100 mg of a protein is dissolved in just enough water to make 10.0 mL of solution. If this solution has an
osmotic pressure of 13.3 mm Hg at 25°C, what is the molar mass of the protein?
(R = 0.0821 L atm mol-1 K-1 and 760 mm Hg = 1 atm.)
10.Calculate the boiling point elevation for a solution prepared by adding 10 g CaCl 2 to 200 g of water,
assuming that CaCl2 is completely dissociated.
(Kb) for water = 0.512 K kg mol-1; Molar mass of CaCl2 = 111 g mol-1)
11.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 × 10 5 Pa at the same temperature.
12. 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.
13. .A solution containing 30g of non-volatile solute exactly in 90 g of water has a vapour pressure of 2.8 kPa
at 298 K. Further, 18g of water is then added to the solution and the new of vapour pressure becomes 2.9 kPa
at 298 K. Calculate
(i) molar mass of the solute.
(ii) vapour pressure of water at 298 K.
14.When 2.56 g of sulphur was dissolved in 100 g of CS2, the freezing point lowered by 0.383 K. Calculate
the formula of sulphur (Sx).
(Kf for CS2 = 3.83 K kg mol-1, Atomic mass of Sulphur = 32 g mol -1)
15. Calculate the freezing point of an acqueous solution containing 10.50 g of MgBr2 in 200 g of water.
(Molar mass of MgBr2 = 184 g) (Kf for water = 1.86 K kg mol-1)
16.Assuming complete dissociation, calculate the expected freezing point of a solution prepared by dissolving
6.00 g of Glauber’s salt, Na 2SO4.10H2O in 0.100 kg of water. (Kf for water = 1.86 K kg mol-1, Atomic masses
: Na = 23, S = 32, O = 16, H = 1)
17. 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)

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18. A solution containing 15 g urea (molar mass = 60 g mol -1) per litre of solution in water has the same
osmotic pressure (isotonic) as a solution of glucose (molar mass = 180 g mol -1) in water. Calculate the mass of
glucose present in one litre of its solution.
19. A 5% solution (by mass) of cane-sugar in water has freezing point of 271 K. Calculate the freezing point
of 5% solution (by mass) of glucose in water if the freezing point of pure water is 273.15 K.
[Molecular masses : Glucose C6H12O6 : 180 amu; Cane-sugar C12H22O11 : 342 amu]
20.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.
21. 1.00 g of a non-electrolyte solute dissolved in 50 g of benzene lowered the freezing point of benzene by
0.40 K. Find the molar mass of the solute. (Kf for benzene = 5.12 K kg mol-1)
22.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)
23.15.0 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)
24.A solution prepared by dissolving 8.95 mg of a gene fragment in 35.0 mL of water has an osmotic pressure
of 0.335 torr at 25°C. Assuming the gene fragment is a non-electrolyte, determine its molar mass.
25. 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)
26.What concentration of nitrogen should be present in a glass of water at room temperature? Assume a
temperature of 25° C, a total pressure of 1 atmosphere and mole fraction of nitrogen in air of 0.78.
[KH for nitrogen = 8.42 × 10-7 M/mm Hg]
27.100 mg of a protein is dissolved in enough water to make 10.0 mL of a solution. If this solution has an
osmotic pressure of 13.3 mm Hg at 25°C, what is the molar mass of protein?
(R = 0.0821 L atm mol-1 K-1 and 760 mm Hg = 1 atm)
28.The vapour pressure of pure liquids A and B at 400 K are 450 and 700 mmHg respectively. Find out the
composition of liquid mixture if total vapour pressure at this temperature is 600 mmHg.
29.18 g of glucose, C6H12O6 (Molar mass – 180 g mol-1) is dissolved in 1 kg of water in a sauce pan. At what
temperature will this solution boil? (Kb for water = 0.52 K kg mol-1, boiling point of pure water = 373.15 K)
30.A 1.00 molal aqueous solution of trichloroacetic acid (CCl 3COOH) is heated to its boiling point. The
solution has the boiling point of 100.18°C. Determine the van’t Hoff factor for trichloroacetic acid. (K b for
water = 0.512 K kg mol-1)
31.A 10% solution (by mass) of sucrose in water has freezing point of 269.15 K. Calculate the freezing point
of 10% glucose in water, if 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)
32.An aqueous solution of 2 percent non-volatile solute exerts a pressure of 1.004 bar at the boiling point of
the solvent. What is the molecular mass of the solute?
[Vapour pressure of water = 1.013 bar]
33.Calculate the mass of a non-volatile solute (molecular mass 40) which should be dissolved in 114 g octane
to reduce the vapour pressure to 80%.

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34.Calculate the boiling point of solution when 4 g of MgSO4 (M =120 g mol-1) was dissolved in 100 g of
water, assuming MgSO4 undergoes complete ionization.
(Kb for water = 0.52 K kg mol-1)
35.A 5 percent solution (by mass) of cane-sugar (M.W. 342) is isotonic with 0.877% solution of substance X.
Find the molecular weight of X.
36. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate
(i) the freezing point depression and
(ii) the freezing point of the solution
(Given : Kf of water = 1.86 K kg mol-1)
37.A solution is prepared by dissolving 10 g of non-volatile solute in 200 g of water. It has a vapour pressure
of 31.84 mm Hg at 308 K. Calculate the molar mass of the solute.
(Vapour pressure of pure water at 308 K = 32 mm Hg)
38. 3.9 g of benzoic acid dissolved in 49 g of benzene shows a depression in freezing point of 1.62 K.
Calculate the Van’t Hoff factor and predict the nature of solute (associated or dissociated).
(Given : Molar mass of benzoic acid = 122 g mol -1, Kf for benzene = 4.9 K kg mol-1)
39.Some ethylene glycol, HOCH2CH2OH, is added to your car’s cooling system along with 5 kg of water. If
the freezing point of a water-glycol solution is -15.0°C, what is the boiling point of the solution?
(Kb = 0.52 K kg mol-1 and Kf = 1.86 K kg mol-1 for water)
40.The partial pressure of ethane over a saturated solution containing 6.56 × 10 -2 g of ethane is 1 bar. If the
solution were to contain 5.0 × 10-2 g of ethane, then what will be the partial pressure of the gas?
41.If N2 gas is bubbled through water at 293K, how many millimoles of N2 gas would dissolve in 1 litre of
water? Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry’s law constant for N 2 at 293K
is 76.48 k bar.
42.The partial pressure of ethane over a saturated solution containing 6.56 × 10 -2 g of ethane is 1 bar. If the
solution contains 5.0 × 10-2 g of ethane, then what will be the partial pressure of the gas?
43.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?
44.What mass of NaCl must be dissolved in 65.0 g of water to lower the freezing point of water by 7.5°C?
The freezing point depression constant (Kf) for water is 1.86°C/m. Assume Van’t Hoff factor for NaCl is 1.87.
(Molar mass of NaCl = 58.5 g)
45.15 g of an unknown molecular substance was dissolved in 450 g of water. The resulting solution freezes at
-0.34° C. What is the molar mass of the substance?
(Kf for water = 1.86 K kg mol-1)
46.What mass of ethylene glycol (molar mass = 62.0 g mol -1) must be added to 5.50 kg of water to lower the
freezing point of water from 0° C to -10.0° C? (K, for water = 1.86 K kg mol -1)?
47.A solution prepared by dissolving 1.25 g of oil of winter green (methyl salicylate) in 99.0 g of benzene has
a boiling point of 80.31°C. Determine the molar mass of this compound. (B.P. of pure benzene = 80.10°C and
Kb for benzene = 2.53°C kg mol -1)
48.15.0 g of an unknown molecular material was dissolved in 450 g of water. The resulting solution was found
to freeze at -0.34 °C. What is the molar mass of this material? (Kf for water = 1.86 K kg mol-1)
49. At 300 K, 36 g glucose present per litre in its solution has osmotic pressure of 4·98 bar. If the osmotic
pressure of the solution is 1·52 bar at the same temperature, what would be its concentration?
50.Calculate the molarity of 30 mL of 0.5 M H2SO4 diluted to 500 mL.
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51.Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal aqueous
solution.Calculate
(a) molality
(b) molarity and
(c) mole fraction of KI if the density of 20%(mass/mass) aqueous KI solution is 1·202 gmL -1.
52. A solution containing 30 g of non-volatile solute exactly in 90 g of water has a vapour pressure of 2.8 kPa
at 298 K. Further 18 g of water is added to this solution. The new vapour pressure becomes 2.9 kPa at 298 K.
Calculate
(i) the molecular mass of solute and
(ii) vapour pressure of water at 298 K.
53.H2 S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of H 2S in
water at STP is 0.195 m, calculate Henry’s law constant.
54.Concentrated nitric acid used in the laboratory work is 68% nitric acid by mass in aqueous solution. What
should be the molarity of such a sample of acid if the density of the solution is 1·504 g mL -1 ?
55.Calculate the percentage composition in terms of mass of a solution obtained by mixing 300 g of a 25%
and 400 g of a 40% solution by mass.
56.A sample of drinking water was found to be severely contaminated with chloroform (CHCl 3), supposed to
be a carcinogen. The level of contamination was 15 ppm (by mass).
(i) express this in percent by mass.
(ii) determine the molality of chloroform in the water sample.
57.Heptane and octane form an ideal solution. At 373 K, the vapour pressures of the two liquid components
are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure of a mixture of 26.0 g of heptane
and 35.0 g of octane?
58.An aqueous solution of 2 percent non-volatile solute exerts a pressure of 1·004 bar at the boiling point of
the solvent. What is the molecular mass of the solute ?
59.The vapour pressure of water is 12.3 kPa at 300 K. Calculate vapour pressure of 1 molal solution of a non-
volatile solute in it
60. Two elements A and B form compounds having formula AB 2 and AB4. When dissolved in 20g of benzene
(C6H6), 1 g of AB2 lowers the freezing point by 2.3 K whereas 1.0 g of AB 4 lowers it by 1.3 K. The molar
depression constant for benzene is 5.1 K kg mol -1. Calculate atomic masses of A and B.
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ELECTROCHEMISTRY
I. SECTION-A
1. From the given cells: Lead storage cell, Mercury cell, Fuel cell and Dry cell
Answer the following:
(i) Which cell is used in hearing aids?
(ii) Which cell was used in Apollo Space Programme?
(iii) Which cell is used in automobiles and inverters?
(iv) Which cell does not have long life?
2. Depict the galvanic cell in which the reaction
Zn(s) + 2Ag+(aq) —-> Zn 2+(aq) + 2Ag (s) takes place. Further show:
(i) Which of the electrode is negatively charged?
(ii) The carriers of the current in the cell.
(iii) Individual reaction at each electrode.

5
3. Given the standard electrode potentials, K+/K= -2. 93 V, Ag+/Ag = 0.80 V,
Hg2+/Hg =0.79V, Mg2+/Mg=-2.37V, Cr3+/Cr=0.74V.
Arrange these metals in their increasing order of reducing power.
4. Write the overall reaction of recharging the lead storage battery, highlighting all the reactions that are
involved at the anode and cathode .
5. Define conductivity and molar conductivity for the solution of an electrolyte. Discuss their variation with
concentration.(with diagram)
6. Predict the products of electrolysis in each of the following.
(i) An aqueous solution of AgNO3 with silver electrodes.
(ii) An aqueous solution of AgNO3 with platinum electrodes.
(iii) A dilute solution of H2SO4 with platinum electrodes.
(iv) An aqueous solution of CuCl2 with platinum electrodes.
7.The chemistry of corrosion of iron is essentially an electrochemical phenomenon. Explain the reactions
occurring during the corrosion of iron in the atmosphere.
8.Express the relation among cell constant, resistance of the solution in the cell and conductivity of the
solution. How is molar conductivity of a solution related to its conductivity?
9. State Kohlrausch law of independent migration of ions. Why does the conductivity of a solution decrease
with dilution? Write an expression for the molar conductivity of acetic acid at infinite dilution according to
Kohlrausch law.
10. Define molar conductivity of a substance and describe how for weak and strong electrolytes, molar
conductivity changes with concentration of solute. How is such change explained?
11. What are the two classifications of batteries? What is the difference between them?
12. What is meant by Limiting molar conductivity
13. Define electrochemical cell. What happens if external potential applied becomes greater than E 0cell of
electrochemical cell?
14. When is Ecell equal to zero?
15.What are the advantages of fuel cells over other cells ?
SECTION-B NUMERICALS
1.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 .
2.The cell in which the following reaction occurs:
2Fe3+ (aq) + 2I– (aq) —> 2Fe2+ (aq) +I2 (s) has E°cell=0.236 V at 298 K. Calculate the standard Gibbs energy
and the equilibrium constant of the cell reaction.
3.The molar conductivity of 0.025 mol L -1 methanoic acid is 46.1 S cm 2 mol-1. Calculate its degree of
dissociation and dissociation constant Given λ°(H+)=349.6 S cm2 mol-1 and λ°(HCOO-) = 54.6 S cm2 mol-1
4.Consider the reaction: Cr2O72-+ 14H+ + 6e- —> 2Cr3+ + 7H2O What is the quantity of electricity in
coulombs needed to reduce 1 mol of Cr2O72- ?
5. How much electricity in terms of Faraday is required to produce :
(i) 20·0 g of Ca from molten CaCl 2
(ii) 40·0 g of Al from molten Al 2O3 ?

6
6. One half-cell in a voltaic cell is constructed from a silver wire dipped in silver nitrate solution of unknown
concentration. Its other half-cell consists of a zinc electrode dipping in 1.0 M solution of Zn(NO3)2. A voltage
of 1.48 V is measured for this cell. Use this information to calculate the concentration of silver nitrate solution
used.
(E0Zn2+/Zn=−0.76V,E0Ag+/Ag = + 0.80 V)
7.The conductivity of 0.20 M solution of KCl at 298 K is 0.0248 S cm -1. Calculate its molar conductivity.
8.The resistance of a conductivity cell containing 0.001 M KCI solution at 298 K is 1500 Ω What is the cell
constant if conductivity of 0.001 M KCI solution at 298 K is 0.146 x 10-3 S cm-1?
9.Conductivity of 0.00241 M acetic acid is 7.896 x 10 -5 S cm-1. Calculate its molar conductivity. If Λm0, for
acetic acid is 390.5 S cm 2 mol-1, what is its dissociation constant?
10.How much charge is required for the following reductions:
(i) 1 mol of Al3+ to Al?
(ii) 1 mol of Cu2+ to Cu ?
(iii) 1 mol of Mn04- to Mn2+?
11. A voltaic cell is set up at 25°C with the following half cells :
Al/Al3+ (0.001 M) and Ni/Ni2+ (0.50 M)
Write an equation for the reaction that occurs when the cell generates an electric current and determine the cell
potential.
E0Ni2+/Ni=−0.25V and E0Al3+/Al=−1.66V
(Log 8 × 10-6 = -0.54)
12.How much electricity is required in coulomb for the oxidation of
(i) 1 mol of H2O to O2 (ii) 1 mol of FeO to Fe2O3
13.A solution of Ni(NO3)2 is electrolyzed between platinum electrodes using a current of 5 amperes for 20
minutes. What mass of Ni is deposited at the cathode?
14. In the button cell, widely used in watches, the following reaction takes place
Zn(s) + Ag2O(s) → Zn2+(aq) + 2Ag(s) + 2OH–(aq)
Determine E0 and ΔG0 for the reaction.
(Given E0Ag+/Ag = +0.80V, E0Zn2+/Zn = -0.76 V)
15.The molar conductivity of a 1.5 M solution of an electrolyte is found to be 138.9 S cm 2 mol-1. Calculate the
conductivity of this solution.
16.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]
17.The standard electrode potential (E°) for Daniel cell is +1.1 V. Calculate the ΔG° for the reaction
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
(1 F = 96500 C mol-1).
18.The conductivity of 0.001 M acetic acid is 4 × 10 -5 S/cm. Calculate the dissociation constant of acetic acid,
if molar conductivity at infinite dilution for acetic acid is 390 S cm 2/mol.
19.Calculate the time to deposit 1.27 g of copper at cathode when a current of 2A was passed through the
solution of CuSO4.
(Molar mass of Cu = 63.5 g mol -1,1 F = 96500 C mol-1)
20.Calculate the degree of dissociation (a) of acetic acid if its molar conductivity (Λm) 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

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21.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.
22.The electrical resistance of a column of 0.05 M NaOH solution of diameter 1 cm and length 50cm is
5.55 × 103 ohm. Calculate its resistivity, conductivity and molar conductivity.
23. Calculate E0cell for the following reaction at 298 K:
2Al(s) + 3Cu2+ (0.01M) → 2Al3+ (0.01M) + 3Cu(s)
Given: Ecell = 1.98 V
24.The cell in which the following reaction occurs :
2Fe3+ (aq) + 2I– (aq) → 2Fe2+ (aq) + I2 (s) has E0cell = 0.236V at 298K. Calculate the standard Gibbs energy
and the equilibrium constant of the cell reaction.
(Antilog of 6.5 = 3.162 × 106; of 8.0 = 10 × 108; of 8.5 = 3.162 × 108)
25.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)
26.A current was passed for 5 hours through two electrolytic cells connected in series. The first cell contains
AuCl3 and second cell CuSO4 solution. If 9.85 g of gold was deposited in the first cell, what amount of copper
gets deposited in the second cell? Also calculate magnitude of current in ampere.
Given: Atomic mass of Au = 197 amu and Cu = 63.5 amu
27.Calculate ΔrG0 for the reaction
Mg (s) + Cu2+ (aq) → Mg2+ (aq) + Cu (s)
Given : E0cell = + 2.71 V, 1 F = 96500 C mol-1.
28.The resistance of 0.01 M NaCl solution at 25° C is 200 Ω. The cell constant of the conductivity cell used is
unity. Calculate the molar conductivity of the solution.
29.Calculate the mass of Ag deposited at cathode when a current of 2 amperes was passed through a solution
of AgNO3 for 15 minutes.
[Given: Molar mass of Ag = 108 g mol -1 1F = 96,500 C mol-1)
30.Calculate ΔrG° and log Kc for the following reaction at 298 K.
2Cr(s)+3Cd2+(aq)⟶2Cr3+(aq)+3Cd(s)
[Given : E0Cell = +0.34 V, IF = 96500 C mol-1]
31.Calculate ΔrG° and log K. for the following reaction at 298 K.

32. A voltaic cell is set up at 25°C with the following half cells :
Ag+ (0.001 M) | Ag and Cu2+ (0.10 M) | Cu What would be the voltage of this cell?
(E0cell = 0.46 V)
33.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
34.Resistance of a conductivity cell filled with 0.1 mol L-1 KCl solution is 100 Ω. If the resistance of the same
cell when filled with 0.02 mol L -1 KCl solution is 520 Ω, calculate the conductivity and molar conductivity of
0.02 mol L-1 KCl solution. The conductivity of 0.1 mol L -1 KCl solution is 1.29 × 10-2 Ω-1 cm-1.
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35.Calculate the standard cell potential of the galvanic cell in which the following reaction takes place
Fe2+ (aq) + Ag+ (aq) → Fe3+ (aq) + Ag (s) Calculate the ΔrG° and equilibrium constant of the reaction also.
(E0Ag+/Ag = 0.80 V; E0Fe3+/Fe2+ = 0.77 V)
36.For the cell reaction
Ni(s) | Ni2+(aq) || Ag+(aq) | Ag(s)
Calculate the equilibrium constant at 25 °C. How much maximum work would be obtained by operation of
this cell?
EoNi2+/Ni = 0.25 V and EoAg+/Ag = 0.80 V
37.The resistance of a conductivity cell containing 0.001 M KCl solution at 298 K is 1500 Ω. What is the cell
constant if conductivity of 0.001 M KCl solution at 298 K is 0.146 × 10 -3 S cm-1?
38.The conductivity of 0.001 mol L -1 solution of CH3COOH is 3.905 × 10-5 S cm-1. Calculate its molar
conductivity and degree of dissociation (α).
Given: λ0(H+) = 349.6 S cm2 mol-1 and λ0 (CH3COO–) = 40.9 S cm2 mol-1
39.The resistance of 0.01 M NaCl solution at 25°C is 200 Ω. The cell constant of the conductivity cell is unity.
Calculate the molar conductivity of the solution.
40. Calculate the potential of hydrogen electrode in contact with a solution whose pH is 10
KINETICS

SECTION-A
1.State a condition under which a bimolecular reaction is kinetically a first order reaction.
2. Write the rate equation for the reaction 2A + B → C if the order of the reaction is zero.
3. For which type of reactions, order and molecularity have the same value?
4. In a reaction, if the concentration of reactant A is tripled, the rate of reaction becomes twenty-seven times.
What is the order of the reaction?
5. For a reaction A + B → Products, the rate law is – Rate = k [A][B]3/2. Can the reaction be an elementary
reaction? Explain.
6. For a certain reaction a large fraction of molecules has energy more than the threshold energy, yet the rate
of reaction is very slow. Why?
7. For a general reaction A ⎯→ B, the plot of concentration of A vs time is given in Fig. Answer the 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?

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8. Why is the probability of reaction with molecularity higher than three very rare?
9.Thermodynamic feasibility of the reaction alone cannot decide the rate of the reaction. Explain with the help
of one example.
10.Why is molecularity applicable only for elementary reactions and order is applicable for elementary as well
as complex reactions?
SECTION-B NUMERICALS
1. The time required for 10% completion of the first order reaction at 298 K is equal to that required for its
25% completion at 308 K. If the value of A is 4 × 1010 s-1, calculated at 318 K and E a.
2. The decomposition of A into product has value of k as 4.5 × 10 3 s-1 at 10°C and energy of activation 60
kJ mol-1. At what temperature would k be 1.5 × 104 s-1 ?
3. Sucrose decomposes in acid solution into glucose and fructose according to the first order rate law, with
t1/2 = 3.00 hours. What fraction of sample of sucrose remains after 8 hours?
4. Consider a certain reaction A →Products with k = 2.0 × 10 -2 s-1.Calculate the concentration of A
remaining after 100s ,if the initial concentration of A is1.0 mol L -1.
5. The following data were obtained during the first order thermal decomposition of SO 2Cl2 at a constant
volume.

Calculate the rate of the reaction when total pressure is 0.65 atm.
6. For the decomposition of azoisopropane to hexane and nitrogen at 543 K, the following data are
obtained.

Calculate the rate constant

7. During nuclear explosion, one of the products is 90Sr with half-life of 28.1 years. If 1 µg of 90Sr was
absorbed in the bones of a newly born baby instead of calcium, how much of it will remain after 10 years
and 60 years if it is not lost metabolically ?
8. The half-life for radioactive decay of 14C is 5730 years. An archaeological artifact containing wood had
only 80% of the 14C found in a living tree. Estimate the age of the sample.
9. In a reaction between A and B, the initial rate of reaction (r0 ) was measured for different initial
concentrations of A and B as given below:

What is the rate law,order with respect to A and B and rate constant of the reaction?
10. The decomposition of NH3 on platinum surface is zero order reaction. What are the rates of production of
N2 and H2 if k=2.5 x 10-4 mol l-1 s-1
11. For the reaction ; 2A + B → A2B, the reaction rate = k [A][B]2 with k =2·0 x 10-6
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 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. Also
calculate the reaction rate when [A] is reduced to 0·06 mol L -1.
12. 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?
13. For the reaction R—>P, the concentration of reactant changes from 0.03 M to 0.02 M in 25 minutes.
Calculate the average rate of reaction using units of time both in minutes and seconds.
14. 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)
15. 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?
16. 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)
17. The rate constant of a reaction at 500 K and 700K are 0.02 s-1and 0.07 s-1respectively. Calculate the
value of activation energy, E n (R = 8.314 J K-1 mol-1)
18. 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?
19. 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?
20. The rates of most reactions double when their temperature is raised from 298 K to 308 K. Calculate their
activation energy. [R = 8.314 JK-1 mol-1]
21. For a first order reaction, show that time required for 99% completion is twice the time required for
completion of 90% reaction
22. The rate of a reaction increases four times when the temperature changes from 300 K to 320 K. Calculate
the energy of activation of the reaction, assuming that it does not change with temperature. (R = 8.314 J
K-1 mol-1)
23. A first order reaction is 15% completed in 20 minutes. How long will it take to complete 60% of the
reaction ?
24. Time required to decompose SO2Cl2 to half of its initial amount is 60 minutes. If the decomposition is a
first order reaction, calculate the rate constant of the reaction.
25. The decomposition of A into products has a value of K as 4.5 × 10 3 s-1 at 10°C and energy of activation
60 kJ mol-1. At what temperature would K be 1.5 × 104 s-1?

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