Chemistry holiday homework

Chapter. SOLUTION

Test 1

1. Why melting point of a substance is used as a criterion for

testing the purity of the substance?

2. Name two ways by which vapourpressure of a liquid can

be lowered.

3. Define the term osmotic pressure.

4. Define cryoscopic constant?

5. Why is osmotic pressure considered to be a colligative

property?

6. Why is ether not miscible in water?

7.. What type of mixtures of two liquids distill over at one

temperature and why?

8. Find the molality and molarity of a 15% solution

of when its density is 1.10

& molar mass=98amu.

9.. Calculate the molality of a solution containing 20.7

g of potassium carbonate dissolute in 500 ml of
solution, assume density of solution=1g/ml.

10. Two elements A and B form compounds having formula

AB2 and AB4 .When dissolved in 20 g of benzene ,1
g of lowers the freezing point by 2.3 K whereas 1.0g
lowers it by 1.3 K. The molar depression constant for
benzene is 5.1Kkgmol^-1. Calculate atomic masses of
A and B.

Test 2nd

1. Define the following terms:

i. Molality. ii. Molarity

2. What are constant boiling mixtures called?

3. What are the factors on which vapourpressure depends?

4.. Show graphically the depression in freezing point on adding

a non-volatile solute?

5.. Define the terms Mass percentage.

6.. 0.90 g of a non-electrolyte was dissolved in 87.90g

of benzene. This raised the boiling point of benzene by . If
the molecular mass of non-electrolyte is 103.0.Calculate
the molal elevation constant for benzene?

7. The density of 85% phosphoric acid .What is the

volume of a solution that contains 17 g of
phosphoric acid?

8. A 0.1539 molal aqueous solution of cane sugar (mol mass

= 342 g mol-1) has a freezing point of 271 K while
the freezing point of pure water is 273.15 K. What will
be the freezing point of an aqueous solution containing
5 g of glucose (mol. Mass = 180 g mol-1) per
100 g of solution.

9. Calculate the mass percentage of benzene (C6H6) and

carbon tetrachloride (CCl4) if 22g of benzene is dissolved
in 122 g of carbon tetrachloride.

10. a. Explain giving examples the term colligative molality.

Why do we sometimes get abnormal molecular masses of
the substances using colligative properties of the solutions?

b. The freezing point depression of 0.1 molal solution of

benzoic acid in benzene is 0.256 K. For benzene
kf is 5.12 K kg mol-1. Calculate the value of Van't Hoff
factor for benzoic acid in benzene. What conclusion can you
draw about the molecular state of benzoic acid in
benzene.

Test 3rd

1. What is meant by reverse osmosis?

2. What do you expect to happen when Red Blood Corpuscles

(RBC's) are placedin
i. 1% NaCl solution ii. 0.5% NaCl solution.

3. Define the term colligative properties?

4.. A personsuffering from high blood pressure should take less

common salt, why?

5. Define Henry's law about solubility of a gas in

a liquid.

6.. State Raoult's law for a binary solution containing

volatile components.

7.. One litre of sea water weight 1030g and contains about of
dissolved.Calculate the concentration of dissolved oxygenin ppm?

8.. Calculate the molarity of each of the following

solutions:

a. 30 g of in 4.3 L of solution

b. 30 mL of 0.5 M H2SO4 diluted to 500 mL.

9. Calculate the mass of a non-volatile solute (molar mass 40

g mol-1) which should be dissolved in 114 g octane to
reduce its vapourpressure to 80%.

10. Amongst the following compounds, identify which are

insoluble, partially soluble and highly soluble in water?

i. phenol ii. Toluene iii. formicacid iv. ethylene glycol. v.

chloroform. vi. pentanol.

Test 4th

1. What are isotonic solutions?

2. Calculate the osmotic pressure of 0.25M solution at 37°C

3. State any two characteristics of ideal solution?

4.. What are maximum boiling azeotropes? Give one example.

5. Urea forms an ideal solution with water. Determine the vapour

pressure of an aqueous solution containing 10% by mass
of urea at 40°C(Vapour pressure of water At40°C = 55.3
mm Hg)
6. At 300K, 36 g of glucose present in a litre of its
solution has an 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?

7. Define the term azeotrope?

8. Henry's law constant for the molality of methane

in benzene at 298 K is 4.27×105mmHg. Calculate the
solubility of methane in benzene at 298 K under 760
mm Hg.

9. a. Define the relationship between lowering of vapour

pressure and mole fraction of the volatile liquid.

b. i. Benzoic acid completely dimerises in benzene. What will be

the vapour pressure of a solution containing 61g of
benzoic acid per 500g benzene when the vapour pressure of pure
benzene at the temperature of experiment is 66.6torr.

ii. What would have been the vapourpressure in the absence

of dimerisation?

iii. Derive a relationship between mole fraction and vapourpressure

of a component of an ideal solution in the liquid phase and
vapourphase.

Test 5th

1. The vapour pressure of ethanol and methanol are 44.5 mm Hg and 88.7 mm Hg,
respectively. An ideal solution is formed at the same temperature by mixing 60 g of
ethanol and 40 g of methanol. Calculate the total vapour pressure of the solution and
the mole fraction of methanol in the vapour.

2. The vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non-
volatile solid weighing 2.175 g is added to 39.0 g of benzene. The vapour pressure of
the solution is 600 mm Hg. What is the molar mass of the solid substance?

3. Addition of 0.643 g of a compound to 50 mL of benzene (density : 0.879 g mL–1) lower

the freezing point from 5.51°C to 5.03°C. If Kf for benzene is 5.12 K kg mol–1, calculate
the molar mass of the compound.
4. (a) The vapour pressure of n-hexane and n-heptane at 273 K are 45.5 mm Hg and 11.4
mm Hg, respectively. What is the composition of a solution of these two liquids if its
vapour pressure at 273 K is 37.3 mm Hg.

(b) The mole fraction of n-hexane in the vapour above a solution of n-hexane and n-
heptane is 0.75 at 273 K. What is the composition of the liquid solution.

5. A solution containing 30 g of a nonvolatile solute in exactly 90 g water has a vapour

pressure of 21.85 mm Hg at 25°C. Further 18 g of water is then added to the solution.
The resulting solution has vapour pressure of 22.18 mm Hg at 25°C. Calculate (a) molar
mass of the solute, and (b) vapour pressure of water at 25°C.

6. The freezing point of ether was lowered by 0.60°C on dissolving 2.0 g of phenol in 100
g of ether. Calculate the molar mass of phenol and comment on the result. Given : Kf
(ether) = 5.12 K kg mol–1.

7. A solution contains 3.22 g of HClO2 in 47.0 g of water. The freezing point of the
solution is 271.10 K. Calculate the fraction of HClO2 that undergoes dissociation to H+
and ClO2–. Given : Kf(water)= 1.86 K kg mol–1.

8. A 0.1 molar solution of NaCl is found to be isotonic with 1% urea solution. Calculate
(a) Van't Hoff factor, and (b) degree of dissociation of sodium chloride. Assume density
of 1% urea equal to 1 g cm–3.

9. The addition of 3 g of a substance to 100 g CCl4 (M = 154 g mol–1) raises the boiling
point of CCl4 by 0.60°C.

If Kb (CCl4) is 5 K mol–1 kg, calculate (a) the freezing point depression (b) the relative
lowering of vapour pressure (c) the osmotic pressure at 298 K and (d) the molar mass
of the substance. Given : Kf (CCl4) = 31.8 K kgmol–1 and (solution) = 1.64 g cm–3.

10. To 500 cm3 of water 3.0 × 10–3 kg of acetic acid is added. If 23% of acetic acid is
dissociated, what will be the depression of freezing point? Kf and density of water are
1.86 K kg mol–1 and 0.997 g cm–3,resp.

11. A 0.01 m aqueous solution of K3[Fe(CN)6] freezes at –0.062°C. What is the apparent
percentage of dissociation? [Kf for water = 1.86]

12. The degree of dissociation of Ca (NO3)2 in a dilute aqueous solution containing 7 g

of the salt per 100 g of water at 100°C is 70%. If the vapour pressure of water at 100°C is
760 mm, calculate the vapour pressure of the solution.
13. A solution containing 0.122 kg of benzoic acid in 1 kg of benzene (b. pt. 353 K) boils
at 354.5 K. Determine the apparent molar mass of benzoic acid (which dimerizes) in
the solution and the degree of dimerization.

Given : ∆vapH1m (benzene) = 394.57 J g–1.

14. A solution containing 0.011 kg of barium nitrate in 0.1 kg of water boils at 100.46°C.
Calculate the degree of ionization of the salt. Kb(water) = 0.52 K kg mol–1.

15. When 3.24 g of mercuric nitrate Hg (NO3)2 dissolved in 1 kg of water, the freezing
point of the solution is found to be – 0.0558°C. When 10.84 g of mercuric chloride
HgCl2 is dissolved in 1 kg of water, the freezing point of the solution is –0.0744°C. Kf

= 1.86 mol–1 K kg. Will either of these dissociate into ions in an aqueous solution ?

16. The vapour pressure of solution containing 6.69 g of Mg(NO3)2 dissolved in 100 g of
water is 747 Torr at

373 K. Calculate the degree of dissociation of the salt in the solution.

17. At 353 K, the vapour pressure of pure ethylene bromide and propylene bromide
are 22.93 and 16.93 k Nm–2, respectively, and these compounds form a nearly ideal
solution. 3 mol of ethylene bromide and 2 mole of propylene bromide are equilibrated
at 553 K and a total pressure of 20.4 k Nm–2 .(a) What is the composition of the liquid
phase?

(b) What amount of each compound is present in the vapour phase?

18. The vapour pressure of two pure liquids, A and B, that form an ideal solution are
300 and 800 torr, respectively, at temperature T. A mixture of the vapour of A and B for
which the amount fraction of A is

0.25 is slowly compressed at temperature T. Calculate :

(a) The composition of the first drop of the condensate,

(b) The total pressure when this drop is formed,

(c) The composition of the solution whose normal boiling point is T.

(d) The pressure when only the last bubble of vapour remains.

(e) The composition of the last bubble.

19. Sea water is found to contain 5.85% NaCl and 9.50% MgCl2 by weight of solution.
Calculate its normal boiling point assuming 80% ionisation for NaCl and 50%
ionisation of MgCl2 [Kb (H2O) = 0.51 kg mol–1 K].

20. Find the freezing point of a glucose solution whose osmotic pressure at 25°C is
found to be 30 atm.

Kf (water) = 1.86 kg.mol–1. K.

21. The latent heat of fusion of ice is 80 calories per gram at 0°C. What is the freezing
point of a solution of KCl. in water containing 7.45 grams of solute 500 grams of water,
assuming that the salt is dissociated to

the extent of 95%?

22. A certain mass of a substance, when dissolved in 100 g C6H6, lowers the freezing
point by 1.28°C. The same mass of solute dissolved in 100 g water lowers the freezing
point by 1.40°C. If the substance has normal molecular weight in benzene and is
completely ionised in water, into how many ions does it dissociate in water? Kf for
H2O and C6H6 are 1.86 and 5.12 K kg mol–1.

23. The cryoscopic constant for acetic acid is 3.6 K kg/mol. A solution of 1 g of a
hydrocarbon in 100 g of acetic acid freezes at 16.14°C instead of the usual 16.60°C. The
hydrocarbon contains 92.3% carbon. What is the molecular formula?

24. A radiator was filled with 10 L of water to which 2.5 L of methanol (density = 0.8
g.mL–1) were added. At 9 : 00 pm, the vehicle is parked outdoors where the
temperature is 0°C. The temperature is decreasing at a uniform rate of 0.5°C / min.
Upto what time will there be no danger to the radiator of the car. Kf (water) = 1.86
kg.mol–1 K. Assume methanol to be non-volatile.

25. At 300 K, two solutions of glucose in water of concentration 0.01 M and 0.001 M are
separated by semipermeable membrane. Pressure needs to be applied on which
solution, to prevent osmosis? Calculate the magnitude of this applied pressure?

26. At 10°C, the osmotic pressure of urea solution is 500 mm. The solution is diluted
and the temperature is raised to 25°C, when the osmotic pressure is found to be 105.3
mm. Determine extent of dilution.

27. When cells of the skeletal vacuole of a frog were placed in a series of NaCl
solutions of different concentration at 25°C, it was observed microscopically that they
remained unchanged in 0.7% NaCl solution, shrank in more cocentrated solutions,
and swelled in more dilute solutions. Water freezes from the 0.7% salt solution at –
0.406°C. What is the osmotic pressure of the cell cytoplasm at 25°C ?Kf = 1.86 kg mol–
1 K.

28. A 0.1 M solution of potassium ferrocyanide is 46% dissociated at 18°C. What will be
its osmotic pressure?

29. At 100°C, benzene & toluene have vapour pressure of 1375 & 558 Torr respectively.
Assuming these two form an ideal binary solution that boils at 1 atm & 100°C. What is
the composition of vapour issuing at these conditions?

30. An ideal solution of two volatile liquid A and B has a vapour pressure of 402.5
mmHg, the mole fraction of A in vapour & liquid state being 0.35 & 0.65 respectively.
What are the vapour pressure of the two liquid at this temperature.

31. Dry air was drawn through bulbs containing a solution of 40 grams of urea in 300
grams of water, then through bulbs containing pure water at the same temperature
and finally through a tube in which pumice moistened with strong H2SO4 was kept.
The water bulbs lost 0.0870 grams and the sulphuric acid tube gained 2.036 grams.
Calculate the molecular weight of urea.

Chapter ------Electrochemistry

1. The resistance of a N/10 KCl solution is 245 ohms. Calculate the specific
conductance and the equivalent conductance of the solution if the electrodes in the
cell are 4 cm apart and each having an area of 7.0 sq. cm.

2. The resistance of a solution 'A' is 50 ohms and that of solution 'B' is 100 ohms, both
solutions being taken in the same conductivity cell. If equal volumes of solution A and
B are mixed , what will be the resistance of the mixture using the same cell. (Assume
that there is no increase in the degree of dissociation of A and B on mixing.)

3. In a conductivity cell the two platinum electrodes, each of area 10 sq. cm. are fixed
1.5 cm apart. The cell contained 0.05 N solution of a salt. If the two electrodes are just
half dipped into the solution which has a resistance of 50 ohms, find equivalent
conductance of the salt solution.

4. A big irregular shaped vessel contained water, the sp. conductance of which was
2.56 × 10–5 mho cm–1. 500g of NaCl was then added to the water and the specific
conductance after the addition of NaCl, was found to be 3.10 × 10–5 mho cm–1. Find
the capacity of the vessel if it is fulfilled with water.

(Molar conductivity at infinte dilution NaCl = 149.9)

5. The equivalent conductance of 0.10 N solution of MgCl2 is 97.1 mho cm2 eq–1. A cell
with electrodes that

are 1.50 cm2 in surface are and 0.50 cm apart is filled with 0.1N MgCl2 solution. How
much current will flow when the potential difference between the electrodes is 5
volts?

6. At 18°C the mobilities of NH4+ and ClO4– ions are 6.6 × 10–4 and 5.7 × 10–4 cm2
volt–1 sec–1 at infinite dilution. Calculate equivalent conductance of ammonium
chlorate solution.

7. For H+ and Na+ the values of molar conductivity at infinite dilution are 349.8 and
50.11. Calculate the mobilities of these ions and their velocities if they are in a cell in
which the electrodes are 5 cm apart and to which a potential of 2 volts is applied.

8. The equivalent conductance of an infinitely dilute solution NH4Cl is 150 and the
ionic conductances of OH– and Cl– ions are 198 and 76 respectively. What will be the
equivalent conductance of the solution of NH4OH at infinite dilution. If the equivalent
conductance of a 0.01 N solution NH4OH is 9.6, what will be its degree of
dissociation?

9. Calculate the dissociation constant of water at 25°C from the following data.
Specific conductance of H2O = 5.8 × 10–8 mho cm–1. Molar conductivity at infinite
dilution for H+ = 350.0 and OH– = 198.0 mho cm2

10. Calculate Ka of acetic acid if its 0.05 N solution has equivalent conductance of
7.36 mho cm2 at 25°C. Molar conductivity of CH3COOH = 390.70)

11. The sp. cond. of a saturated solution of AgCl at 25°C after substracting the sp.
conductance of conductivity of water is 2.28 × 10–6 mho cm–1. Find the solubility
product of AgCl at 25°C. (Molar conductivity at infinite dilution for AgCl = 138.3 mho
cm2).

12. The specific conductance of a N/10 KCl solution at 18°C is 1.12 × 10–2 mho cm–1.
The resistance of the solution contained in the cell is found to be 65 ohms. Calculate
the cell constant.

13. When a solution of conductance 1.342 mho m–1 was placed in a conductivity cell
with parallel electrodes, the resistance was found to be 170.5 ohm. The area of the
electrodes is 1.86 × 10–4 sq.meter. Calculate the distance between the two electrodes
in meter.
14. The resistance of two electrolytes X and Y were found to be 45 and 100 respectively
when equal volumes of both the solutions were taken in the same cell in two different
experiments. If equal volumes of these solutions are mixed in the same cell, what will
be the conductance of the mixture?

15. The resistance of an aqueous solution containing 0.624 g of CuSO4. 5H2O per 100
cm3 of the solution in a conductance cell of cell constant 153.7 per meter is 520 ohms
at 298 K. Calculate the molar conductivity. (CuSO4 . 5H2O = 249.5)

16. Given the equivalent conductance of sodium butyrate, sodium chloride and
hydrogen chloride as 83, 127 and 426 mho cm2 at 25°C respectively. Calculate the
equivalent conductance of butyric acid at infinite dilution.

17. For 0.0128 N solution of acetic acid at 25°C, equivalent conductance of the
solution is 1.4 mho cm3eq–1 and molar cond. At infinite dilution = 391 mho cm2 eq–1.
Calculate dissociation constant (Ka) of acetic acid.

18. The specific conductance at 25°C of a saturated solution of SrSO4 is 1.482 × 10–4
ohm–1 cm–1 while that of water used is 1.5 × 10–6 mho cm–1. Determine at 25°C the
solubility in g per litre of SrSO4 in water. Molar

ionic conductance of Sr2+ and SO42– ions at infinite dilution are 59.46 and 79.8 ohm–1
cm2 mole–1 respectively.[Sr = 87.6, S = 32, O = 16]

19. Specific conductance of pure water at 25°C is 0.58 × 10–7 mho cm–1. Calculate
ionic product of water (KW) if ionic conductances of H+ and OH– ions at infinite
dilution are 350 and 198 mho cm2 respectively at 25°C.

20. How long a current of 3A has to be passed through a solution of AgNO3, to coat a
metal surface of 80 cm2 with 5µm thick layer? Density of silver = 10.8 g/cm3.

21. 3A current was passed through an aqueous solution of an unknown salt of Pd for 1
hr. 2.977 g of Pd+n was

deposited at cathode. Find n. 22. 50 mL of 0.1 M CuSO4 solution is electrolysed with a

current of 0.965 A for a period of 200 sec. The reactionsat electrodes are :

Cathode : Cu2+ + 2e– -Cu(s) Anode : 2H2O =O2 + 4H + 4e.Assuming no change in

volume during electrolysis, calculate the molar concentration of Cu2+, H+ and SO42–
at the end of electrolysis.

23. A metal is known to form fluoride MF2 . When 10 A of electricity is passed through a
molten salt for 330 sec., 1.95 g of metal is deposited. Find the atomic weight of M.
What will be the quantity electricity required to deposit the same mass of Cu form
CuSO4?

24. An electric current is passed through electrolytic cells in series one containing
Ag(NO3) (aq.) and other H2SO4 (aq.) What volume of O2 measured at 25°C and 750 mm
Hg pressure would be liberated from H2SO4 if

(a) one mole of Ag+ is deposited from AgNO3 solution

(b) 8 × 1022 ions of Ag+ are deposited from AgNO3 solution.

25. Cd amalgam is prepared by electrolysis of a solution CdCl2 using a mercury

cathode. How long should a current of 5A be passed in order to prepare 12 % Cd-Hg
amalgam on a cathode of 2g, Hg (atomic weight of Cd = 112.4)

26. After electrolysis of NaCl solution with inert electrodes for a certain period of time,
600 mL of the solution was left. Which was found to be 1N in NaOH. During the same
time, 31.75 g of Cu deposited in the copper voltameter in series with the electrolytic
cell. Calculate the percentage yield of NaOH obtained.

27. During the discharge of a lead storage battery, the density of sulphuric acid fell
from 1.294 to 1.139 g.mL–1. H2SO4 of density 1.294 gmL–1 is 39% and that of density
1.139 g.mL–1 is 20% by weight. The battery holds 3.5 L of acid and the volume
practically remains constant during discharge. Calculate the number of ampere hours
for which the battery must have been used. The discharging and charging
reactionsare.

Pb + SO42– ==PbSO4 + 2e–(charging). PbO2 + 4H+ + SO42– + 2e– = PbSO4

+ 2H2O(discharging)

28. The e.m.f. of the cell obtained by combining Zn and Cu electrode of a Daniel cell
with N calomel electrode in two different arrangements are 1.083 V and 0.018 V
respectively at 25°C. If the standard reduction potential of N calomel electrode is 0.28
V find the emf of Daniel cell.

29. Same quantity of electricity is being used to liberate iodine (at anode) and a metal
x (at cathode). The mass of x liberated is 0.617 g and the iodine liberated is completely
reduced by 46.3 cc of 0.124 M sodium thiosulphate. Find the equivalent mass of metal
x.

30. 100 mL CuSO4 (aq) was electrolyzed using inert electrodes by passing 0.965 A till
the pH of the resulting solution was 1. The solution after electrolysis was neutralized,
treated with excess KI and titrated with 0.04 M Na2S2O3 . Volume of Na2S2O3 required
was 35 mL. Assuming no volume change during electrolysis,

calculate :

(a) duration of electrolysis if current efficiency is 80 %

(b) initial concentration (M) of CuSO4.

31. A current of 3.7 A is passed for 6 hrs between Pt electrodes in 0.5 L of 2M solution
of Ni(NO3)2. What will be the molarity of solution at the end of electrolysis?

32. Calculate the EMF of a Daniel cell when the concentration of ZnSO4 and CuSO4 are
0.001 M and 0.1 M respectively. The standard potential of the cell is 1.1V.

33. EMF of the cell Zn|ZnSO4(a = 0.2)||ZnSO4(a2)|Zn is –0.0088 V at 25°C. Calculate the
value of a2.

34. The EMF of the cell M|Mn+ (0.02 M)||H+ (1 M)|H2 (g) (1 atm), Pt at 25°C is 0.81 V.
Calculate the valency of the metal if the standard oxidation potential of the metal is
0.76 V.

35. Equinormal solution of two weak acids, HA (pKa = 3) and HB (pKa = 5) are each
placed in contact with standard hydrogen electrode at 25°C. When a cell is
constructed by interconnecting them through a salt bridge find the e.m.f. of the cell.

36. In two vessels each containing 500 mL water, 0.5 m mol of aniline (Kb = 10–9) and
25 m mol of HCl are added separately. Two hydrogen electrodes are constructed using
these solutions. Calculate the emf of cell made by connecting them appropriately.

37. The emf of the cell Ag|AgI|KI (0.05 M)||AgNO3

(0.05 M)|Ag is 0.788 V. Calculate the solubility product of AgI.

38. The cell Pt, H2 (1 atm)|H+ (pH = x)|| Normal calomel Electrode has an EMF of 0.67 V
at 25°C.Calculate the pH of the solution. The oxidation potential of the calomel
electrode on hydrogen scale is –0.28 V.

39. Estimate the cell potential of a Daniel cell having 1.0 M Zn++ and originally having
1.0 M Cu++ after sufficient NH3 has been added to the cathode compartment to make
NH3 concentration 2.0 M. Given Kf for [Cu(NH3)4] 2+ = 1 × 1012, E° for the reaction, Zn +
Cu2+. = Zn2+ + Cu is 1.1 V.
40. Consider the cell Ag|AgBr(s)|Br–||AgCl(s)|Cl–|Ag at 25°C. The solubility product
constants of AgBr & AgCl are respectively 5 × 10–13 & 1 × 10–10. For what ratio of the
concentration of Br– & Cl– ions would the em.f. of the cell be zero?

41. The pKsp of AgI is 16.07. If the E° value for Ag+/Ag is 0.7991 V, find the E° for the half
cell reaction

AgI (s) + e– =Ag + I–.

42. Voltage of the cell Pt, H2 (1 atm)|HOCN (1.3 × 10–3 M)||Ag+ (0.8 M)|Ag(s) is 0.982 V.
Calculate the Ka for HOCN. Neglect [H+] because of oxidation of H2(g).

Ag+ + e– = Ag (s) = 0.8 V

43. The standard oxidation potential of Zn referred to SHE is 0.76 V and that of Cu is –
0.34 V at 25°C. When excess of Zn is added to CuSO4 , Zn displaces Cu2+ till
equilibrium is reached. What is the ratio of Zn2+ to Cu2+ ions at equilibrium?

44. The standard reduction potential values, E° (Bi3+ /Bi) and E° (Cu2+ / Cu) are 0.226 V
and 0.344 V respectively. A mixture of salts of bismuth and copper at unit
concentration each is electrolysed at 25°C. To what value can [Cu2+] be brought down
before bismuth starts to deposit, in electrolysis.

45. Calculate the potential of an indicator electrode versus the standard hydrogen
electrode, which originally contained 0.1 M MnO4 – and 0.8 M H+ and which was
treated with Fe2+ necessary to reduce 90% of the MnO4–to Mn2+. . MnO4– + 8H++ 5e
== Mn2+ + H2O, E° = 1.51 V,

46. Kd for dissociation of [Ag(NH3)2]+ into Ag+ and NH3 is 6 × 10–8. Calculate E° for the
following half reaction;

Ag (NH3)2+ + e– ==Ag + 2NH3Given Ag+ + e– ==Ag, E° = 0.799 V

47. The overall formation constant for the reaction of 6 mole of CN– with cobalt (II) is 1
× 1019. The standard reduction potential for the reaction [Co(CN)6]3– + e– ==[Co(CN)6]
4– is –0.83 V. Calculate the formation constant of [Co(CN)6]3– .

Given Co3+ + e– Co2+ ; E° = 1.82 V

48. Calculate the e.m.f. of the cell

Pt|H2|(1.0 atm)|CH3COOH (0.1 M)||NH3(aq, 0.01 M)|H2

(1.0 atm)|Pt. Ka(CH3COOH) = 1.8 × 10–5, Kb, (NH3) = 1.8 × 10–5.

49. An external current source giving a current of 5.0 A was joined with Daniel cell
arrangement opposing the normal current flow and was removed after 10 hrs. Before
passing the current the LHE and RHE contained 1L each of 1M Zn2+ and Cu2+
respectively. Find the EMF supplied by the Daniel cell after removal of the external
current source. E° of Zn2+/Zn and Cu2+/Cu at 25°C is –0.76 and +0.34 V respectively.

50. Calculate the equilibrium constant for the reaction :

3Sn (s) + 2Cr2O72– + 28 H+ ===3 Sn+4 + 4Cr3+ + 14H2O

E° for Sn/Sn2+ = 0.136 V E° for Sn2+/Sn4+ = –0.154 V

E° for Cr2O72–/Cr3+ = 1.33 V

51. Calculate the voltage E, of the cell at 25°C

Mn(s)|Mn(OH2 )(s)|Mn2+(x M), OH– (1.00 × 10–4 M)||Cu2+ (0.675 M)|Cu(s) given that Ksp=
1.9 × 10–13 for Mn(OH)2

(s) E° (Mn2+/Mn) = –1.18 V, E°(Cu+2/Cu) = +0.34 V

52. Calculate the voltage E, of the cell

Ag(s) AgIO3 (s)|Ag+ (x M), HIO3 (0.300 M)||Zn2+ (0.175 M)|Zn (s) if KSP = 3.02 × 10–8 for
AgIO3 (s) and Ka = 0.162 for HIO3 , E°(Zn+2/Zn) = –0.76 V, E° (Ag/Ag+) = –0.8 V)

53. The voltage of the cell

Pb(s)|PbSO4(s)|NaHSO4 (0.600 M)||Pb2+(2.50 ×10^5 M)|Pb (s)

is E = +0.061 V. Calculates K2 = [H+] [SO42–]/[HSO4–], the dissociation constant for

HSO4–.Given Pb(s) + SO4 2– ==PbSO4 + 2e– (E° = 0.356 V), E° (Pb2+ / Pb) = –0.126 V.

54. The voltage of the cell

Zn(s)|Zn(CN)42– (0.450 M), CN– (2.65 × 10–3 M)||Zn2+(3.84 × 10–4 M)|Zn(s) is E = +0.099
V.. Calculate the constant Kf for Zn2+ + 4CN– ==Zn(CN)4 2–, the only Zn2+ + CN–
complex reaction of importance..

Chapter 3rd CHEMICAL KINETICS

Test 1st

1. How does the reaction rate change on increasing the

temperature?
2. Identify the order of reaction from the following rate
constant: k= 2.2 ×10^-5Lmol^-1sec^-1

3. What is activation energy?

4. 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.

5. State any one condition under which a bimolecular reaction

may be kinetically first order.

6. For the chemical decomposition of SO2Cl2

, its initial concentration is 0.8420 mol L-1

and final concentration is 0.215 mol L-1 in 2 hours. What

is the average rate of this

reaction?

7. Give one example of pseudo first order reaction.

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 the reactant

will be left after 3hours?

9. 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 the sample of
sucrose remains After 8 hours..

10. Is there any reaction for which reaction rate does not
decrease with time?

11. The decomposition reaction of ammonia gas on

platinum surface has a rate constant k= 2.5 10-4
mol L-1 s-1. What is the order of the reaction?

12. Distinguish between molecularity and order of reaction.

15. The rate of the chemical reaction doubles for an
increase of 10 K in absolute temperature from 298 K.
Calculate Activation energy.

Test 2nd

1. Give one example of photochemical reaction. [ 2000 ]

2. For the reaction 3H2(g) + N2(g) =2NH3(g), how are the rate of reaction and interrelated ? [
2000 ]

3. The rate of reaction is given by: Rate = k [N2O5]. In this equation what does k stand for ?[
2000 ]

4. Why is the instantaneous rate of a reaction does not change when a part of the reacting
solution is taken out ? [ 2000 ]

5. Under what conditions does the rate of a reaction equal its rate constant? [ 2000 ]

6. A first order reaction is 20% complete in 10 minutes. Calculate the time for 75%
completion of the reaction. [ 2000 ]

7. In general it is observed that the rate of a chemical reaction doubles with every 10º rise
in temperature. If this generalization holds for a reaction in the temperature range 295 K to
305K, what would be the value of activation energy for this reaction? (R = 8.314 JK–1 mol–1)[
2000 ]

8. Show that the time required for the completion of 3/4th reaction of first order is twice the
time required for completion of 1/2 of the reaction. [ 2000 ]

9. What is the effect of catalyst on activation energy ? Explain. OR

What aspect of the reaction is influenced by the presence of catalyst which increases the
rate or possibility of the reaction ? [ 2001 ]

10. A reactant with initial concentration ‘a’ mol lit–1 follows zero order kinetic with a rate
constant k mol lit–1 sec–1. In how much time will the reaction go to completion ? [ 2001]

11. A reaction is 50% completed in 2 hour and 75% complete in 4 hours what is the order
of. The reaction.? [ 1996, 2001 ]

12. The reaction SO2Cl2 == SO2 + Cl2 is a first order reaction with k = 2.2 × 10–5s–1 at
320ºC.

Calculate the percentage of SO2Cl2 that is decomposed on heating this gas for 30 min.[
2001 ]
13. Calculate the time required for the completion of 90% of a reaction of first order
kinetics .[ t1/2 reaction = 44.1 minutes ] [ 2001 ]

14. The decomposition of compound is found to follow a first order rate law. If it takes 15
minutes for 20 per cent of original material to react. calculate :

(i) the specific rate constant

(ii) the time at which 10 per cent of the original material remains unreacted

(iii) the time it takes for the next 20 per cent of the reactant left to react after the first 15
minutes. [ 2002 ]

15. The rate constant of reaction is 1.5 × 107 sec–1 at 50 ºC and 4.5 × 107sec–1 at 100 ºC.
Calculatethe value of activation energy, Ea for the reaction [ R = 8.314 JK–1 mol–1 ] [ 2003 ]

16. What are photochemical reactions ? Explain the mechanism of the photochemical
reaction between hydrogen and chlorine gas. [ 2003 ]

17. How does the value of rate constant vary with reactant concentration? [2004, 2005]

Test 3rd

1. A substance with initial concentration ‘a’ follows zero order kinetics with the rate
constant ‘k’ molL–1S–1. In how much time will the reaction go to completion? [2005, 2001]

2. The reaction A + B C has zero order. What is the rate equation? [ 2005 ]

3. Prove that the time required for the completion of 3/4th of reaction of first order is twice
the time required for the completion of half of the reaction. [ 2006 ]. 4. The
rate constant for a first order reaction is 60 s–1. How much time will it take to reduce
theconcentration of the reactant to 1/10th of its initial value? [ 2007 ]

5.. (a) Derive the general expression for half-life of a first order reaction [ 2008 ]

(b) The decomposition of NH3 on platinum surface is a zero order reaction. What would be
the rates of production of N2 and H2 if k = 2.5 × 10–4 mol–1 L s–1?

OR

(a) List the factors that determine the rate of a chemical reaction.

(b) The half-life for decay of radioactive 14C is 5730 years. An archaeological artefact
containing
wood had only 80% of the 14C activity as found in a living tree. Calculate the age of the
artefact. 6. Define the following [ 2009 ] (i) Elementary step in a
reaction (ii) Rate of a reaction

7. 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 the reactant willl be left after 3 hours?
[ 2009 ]

8.. (a) Explain the following terms [ 2010 ]

(i) Rate of reaction (ii) Activation energy of a reaction

(b) The decomposition of phosphine, PH3

, proceeds according to the following equation:

4PH3(g) = P4 (g) + 6H2(g)

It is found that the reaction follows the following rate euation:Rate = k[PH3].The half-life of
PH3 is 37.9 s at 120ºC.

(i) How much time is required for 3/4th of PH3 to dcompose?

(ii) what fraction of the original sample of PH3

remains behind after 1 minute?

OR

(a) Explain the following terms:

(i) Order of reaction (ii) Molecularity of reaction

(b) The rate of a reaction increases four times when the temperature changes from 300K to
320K. Calculate the energy of activation of the reaction, assuming that it does not change
with temperature. (R = 8.314 JK–1 mol–1)

9. Define order of a reaction [ 2011 ]

10. 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: [ 2011 ]

(i) L–1 mol s–1 (ii) L mol–1 s–1

11. The thermal decomposition of HCO2H is a first order reactoin with a rate constant of
2.4 × 10–3 s–1 at a certain temperature. Calculate how long will it take for three-fourth of
initial quantity of HCO2H to decompose (log 0.25 =0.6021) [ 2011 ]

Q.12. In Arrhenius equation for a certain reaction, the value of A and Ea (activation energy)
are 4× 1013 sec–1 and 98.6 kJ mol–1 respectively. At what temperature, the reaction will
have specific rate constant 1.1 × 10–3 sec–1 ?

Q.13.The rate constant is given by Arrhenius equation , k = Ae–Ea/RT calculate the ratio of
the catalysed and uncatalysed rate constants at 25°C if the energy of activation of a
catalysed reaction is 162 kJ and for the uncatalysed reaction the value is 350 kJ.

Q.14. At 407 K, the rate constant of a chemical reaction is 9.5 × 10–5 s–1 and at 420 K, the
rate constant is 1.9 × 10–4 s–1. Calculate the frequency factor of the reaction.

Q.15. The energy of activation for a reaction is 100 kJ mol1. Presence of a catalyst lowers
the energy of activation by 75%. What will be effect on rate of reaction at 20°C, other things
being equal.

Q.16 The gas phase decomposition , 2N2O5 =4NO2 + O2 follows the first order rate law. At
a given temperature the rate constant of the reaction is 7.5× 10–3 s–1. The initial pressure
of N2O5 is 0.1 atm.

(i) Calculate time of decomposition of N2O5 so that the total pressure becomes 0.15 atm.

(ii) What will be the total pressure after 150 seconds ?

Q.17. In hydrogenation reaction at 25°C, it is observed that hydrogen gas pressure falls
from 2 atm to 1.2 atm in 50 min. Calculate the rate of reaction in molarity per sec. R =
0.0821 litre atm degree–1mol–1.

Q.18.A drop of solution (volume 0.05 ml) contains 3 × 10–6 mol H+ ions. If the rate of
disappearance of the H+ ions is 1 × 107 mol litre–1 sec–1, how long would it take for H+ ions
in the drop to disappear ?