1
1
1
cm
-1
. The same cell filled
with 0.001M AgNO
3
gives a resistance of 6529 ohms. Calculate the molar
conductivity of 0.001M AgNO
3
solution at 25
o
C.
2. A conductivity cell filled with 0.1M KCl gives at 25
o
C a resistance of 85.5 ohms.
The conductivity of 0.1M KCl at 25
o
C is 0.01286
cm
-1
. The same cell filled with
0.005M HCl gives a resistance of 529 ohms. What is the molar conductivity of HCl
solution at 25
o
C?
3. The molar conductivity of 0.05M BaCl
2
solution at 25
o
C is 223
cm
2
mol
-1
.
What i9s its conductivity?
4. The conductivity of 0.02M AgNO
3
at 25
o
C is 2.428 x 10
-3
cm
-1
. What is its
molar conductivity?
5. A conductivity cell filled with 0.02M H
2
SO
4
gives at 25
o
C a resistance of 122
ohms. If the molar conductivity of 0.02M H
2
SO
4
is 618
cm
2
mol
-1
, what is the
cell constant?
6. A conductivity cell filled with 0.02M AgNO
3
gives at 25
o
C a resistance of 947
ohms. If the cell constant is 2.3cm
-1
what is the molar conductivity of with 0.02M
AgNO
3
at 25
o
C?
7. The molar conductivities at zero concentrations of NH
4
Cl, NaOH and NaCl are
respectively 149.7
cm
2
mol
-1
, 248.1
cm
2
mol
-1
and 126.5
cm
2
mol
-1
. What
is the molar conductivity of NH
4
OH at zero concentration?
8. What is the molar conductivity of AgI at zero concentration if the
values of
NaI, AgNO
3
and Na NO
3
are respectively 126.9
cm
2
mol
-1
, 133.4
cm
2
mol
-1
and 121.5
cm
2
mol
-1
?
9. Estimate the mass of copper metal produced during the passage of 5A current
through CuSO
4
solution for 100 minutes. The molar mass of Cu is 63.5gmol
-1
.
10. How long will it take to produce 2.415g of Ag metal from its salt solution by
passing a current of 3A? How many moles of electrons are required? Molar mass
of Ag is 107.9gmol
-1
.
11. What current strength in ampere will be required to produce 2.369 10
-3
kg
of Cu from CuSO
4
solution in one hour? How many moles of electrons are
required? Molar mass of Cu is 63.5gmol
-1
.
12. A current of 6 amperes is passed through AlCl
3
solution for 15 minutes using
Pt electrode, when 0.504g of Al is produced. What is the molar mass of Al?
13. How many moles of electrons are required for the reduction of
i. 3 moles of Zn
2+
to Zn
ii. 1 mole of Cr
3+
to Cr.
How many faradays of electricity will be required in each of case?
14. In the electrolysis of AgNO
3
solution 0.7g of Ag is deposited after a certain
period of time. Calculate the quantity of electricity required in coulomb. Molar
mass of Ag is 107.9gmol
-1
.
15. Calculate the amounts of Na and chlorine gas produced during the electrolysis
of fused NaCl by the passage of 1 ampere current for 25minutes. Molar masses of
Na and chlorine gas are 23gmol
-1
and 719gmol
-1
respectively.
16. Calculate the mass of Mg and volume of chlorine gas at STP produced during
electrolysis of molten MgCl
2
by the passage of 2 amperes of current for 1 hour.
Molar mass of Mg and Cl
2
are respectively 249gmol
-1
and 719gmol
-1
.
17. In a certain electrolysis experiment 0.561g of Zn is deposited in one cell
containing ZnSO
4
solution. Calculate the mass of Cu deposited in another cell
containing CnSO
4
solution in series with ZnSO
4
cell. Molar masses of Zn and Cu are
65.4gmol
-1
and 63.5gmol
-1
.
18. Two electrolytic cells one containing AlCl
3
solution and the other containing
ZnSO
4
solution are connected in series. The same quantity of electricity is passed
between the cells. Calculate the amount of Zn deposited in ZnSO
4
cell if 1.2g of Al
are deposited in AlCl
3
cell. The molar masses of Al and Zn are 27 gmol
-1
and 65.4
gmol
-1
respectively.
19. Write the cell reaction and calculate the standard potential of the cell,
Ni(s)|Ni
2+
(1M) Cl
-
(1M)|Cl
2
(g, 1atm|Pt
E
0
Cl2
=-1.36V and E
0
Ni
=-0.25V(1.61V)
20. Write the cell reaction and calculate the emf of the cell,
Pb(s)|Pb
2+
(1M) KCl(sat)|Hg
2
Cl
2
(s)|Hg
E
0
anode
=-0.126V, E
0
cathode
=0.242V.
Identify anode and cathode. Name the right hand side electrode.
21. The following redox reaction occurs in a galvanic cell.
2Al(s)+3Fe
2+
(1M) 2Al
3+
(1M)+3Fe
(a)Write the cell notation.
(b)Identify anode and cathode.
(c)Calculate E
0
cell
if E
0
anode
=-1.66V and E
0
cathode
=-0.44V.
(d)Calculate G
o
for the reaction.
22. Calculate the potential of the following cell at 25
o
C.
Sn(s)|Sn
2+
(0.025M) Ag
+
(0.015M) Ag(s)
E
0
Sn
=-0.136V, E
0
Ag
=0.799V
23. Consider the following cell
Pb(s)|Pb
2+
(0.5M) Cu
2+
(0.001M)|Cu
(a)Write the cell reaction.
(b)Calculate E
cell
and E
0
cell
at 25
o
C.
(c)CalculateG and G
o
for the cell reaction.
24. Consider the following redox reaction
Mg(s)+ Sn
2+
(aq) Mg
2+
(aq)+Sn(s)
(a)Write the cell formula
(b)Calculate E
cell
for the reaction at 25
o
C if [Mg
2+
]=0.035M, [Sn
2+
]=0.025M, E
0
Mg
=-
2.37V and E
0
Sn
=-0.136V
(c)Calculate G for the reaction.
25. Write the cell reaction and calculate the emf of the cell at 25
o
C, Cr(s)|Cr
3+
(0.0065M) Co
2+
(0.012M)|Co(s)
E
0
Co
=-0.280V, E
0
Cr
=-0.74V
What is G for the reaction?
26. Construct a cell consisting of Ni
+
|Ni half cell and H
+
|H
2
(g, 1atm)|Pt half cell.
(a)Write the cell reaction.
(b)Calculate emf of the cell if [Ni
2+
]=0.1M, [H
+
]=0.05M and E
0
Ni
=-0.257
27. Calculate the equilibrium constant for the redox reaction at 25
o
C,
Sr(s)+ Mg
2+
(aq) Sr
2+
(aq)+Mg(s) that occurs in a galvanic cell, Write the cell
formula. E
0
Mg
=-2.37V and E
0
Sr
=-2.89V.
28. Using Nernst equation, calculate the potentials for the following reactions:
(a)I
2
+2e
-
2I
-
, [I
-
]=0.0M, E
0
I2
=0.535V.
(b)Fe
3+
(aq)+ e
-
Fe
2+
(aq), [Fe
2+
]=0.1M, [Fe
3+
]=0.01M, E
0
Fe2+, Fe3+
= 0.771V
29. Consider the galvanic cell that uses the half reactions.
2H
+
(aq)+ 2e
-
H
2
(g)
Mg
2+
(aq)+ 2e
-
Mg(s)
Write balanced equation for the cell reaction, Calculate E
0
cell
, E
cell
and G
o
if
concentrations are 1M each and
=10atm. E
0
Mg
=-2.37V.
30. Calculate E
0
cell
and G
o
equilibrium constant for the reaction 2Cu
+
(aq)
Cu
2+
(aq),
=-0.52V and
=0.16V
31. Calculate the potential of the following cell at 25
o
C.
Zn|Zn
2+
(0.6M) H
+
(1.2M)|H
2
(g, 1atm)|Pt
=-0.763V.
32. A constant electric current flows for 4 hours through two electrolytic cells
connected in series. One contains AgNO
3
solution and second contains CuCl
2
solution. During this time 4 grams of Ag are deposited in the first cell.
(a) How many grams of Cu are deposited in the second cell?
(b) What is the current flowing in amperes?
33. The passage of 0.95A for 40 minutes deposited 0.7493g of Cu from CuSO
4
solution. Calculate the molar mass of Cu.
34. A quantity of 0.3g of Cu was deposited from CuSO
4
solution by passing 4A
through the solution for 3.8minute, calculate the value of Faraday constant.
35. In the electrolysis of water, one of the half reactions is
2 H
+
+ 2e
+
H
2
(g)
Calculate the volume of H
2
gas collected at 25
o
C and 1atm pressure by passing 2A
for 1h through the solution. R=0.08205L.atm.K
-1
mol
-1
.
36. Set up the cell consisting of H
+
(aq)|H
2
(g) and Pb
2+
(aq)|Pb(s) electrodes.
Calculate the emf of the cell if [Pb
2+
]=0.1M, [H
+
]=0.5M and hydrogen gas is at
2atm pressure.
=-0.126V.
37. Write balanced equations for the half reactions and calculate the reduction
potentials at 25 for the following half cells:
(a)Cl
-
(1.2M)|Cl
2
(g, 3.6atm) E
0
=1.36V
(b)Fe
2+
(2M)|Fe(s) E
0
=-0.44V
38. Device galvanic cell for each of the following reactions and calculate G
o
for
the reaction,
(a)Zn dissolves in HCl to produce Zn
2+
and H
2
gas.
=-0.763
(b)Cr dissolves in dilute HCl to produce Cr
3+
and H
2
gas.
=-0.74V.
39. The equilibrium constant for the following reaction at 25 is 2.9 10
9
.
Calculate standard voltage of the cell.
Cl
2
(g)+Br
-
(aq) Br
2
(l)+2Cl
-
(aq).
Chemical Kinetics:
Theory:
1.Define average rate & instantaneous rate how is instantaneous rate is evaluated?
2. Define rate law & rate constant explain rate law with two examples.
3. Explain the term order of reaction with example.
4. What is pseudo first order reaction? Give one example
5. Define integrated rate law. Derive the expression for integrated rate law for first order
reaction, Aproducts
6. Define half life of reaction. Derive the relationship between half life & rate constant for
a first order reaction.
7. Describe one method to determine rate law & order of reaction.
8. Give the units of rate of reaction & rate constant of first & zero order reaction.
9. The gas-phase reaction between NO & Br
2
is
2NO(g) + Br
2
(g) 2NOBr(g)
(a) Write the expressions for the rate of consumption of reactant and formation of
product.
(b) Write the expression for rate of overall reaction in term of rate of consumption of
reactant & formation of product.
10. The decomposition of N
2
O
5
is represented by the equation
2N
2
O
5
(g) 4NO
2
(g) + O
2
(g)
(a) how the rate of formation of NO
2
related to the rate of formation of O
2
?
(b) how the rate of formation of O
2
is related to the rate of consumption of N
2
O
5
?
11. Nitric oxide reacts with H
2
according to the reaction
2NO(g) + 2H
2
N
2
(g) + 2H
2
O(g)
What is the relationship among
d[NO]/dt, d[H
2
]/dt, d[N
2
]/dt & d[H
2
O]/dt?
12. The rate law for the gas-phase reaction
2NO(g) + 2O
2
(g) 2NO
2
(g)
is rate = k[NO
2
][O
2
]. What is the order of the reaction with respect to each of reactant &
what is the overall order of the reaction ?
13. The reaction H
2
O
2
(aq) + 3I
-
(aq) + 2H
+
(aq) 2 H
2
O
2
(l) +I
3-
(aq)
Is first order in H
2
O
2
& I
-
,zero order in H
+
.
Write the rate law.
14. The reaction A + B products is first order in each of the reactant.
(a) write the rate law.
(b) How does the reaction rate changes if the concentration of B decreased by a factor
3?
(c) What is the change in the rate if the concentration of each reactant is tripled?
(d) What is the change in the rate if concentration of A is doubled & that of B is halved ?
15. What is the elementary reaction ? What is the molecularity of elementary reaction ?
16. Distinguish between molecularity & order of a reaction.
17..What do u mean by a complex reaction
18. Identify the molecularity & write the rate law of each of the following elementary
reactions:
(a) NO(g) + O
3
(g) NO
3
(g) + O(g)
(b) H
2
I(g) +I(g) 2HI(g)
(c) Cl(g) + Cl(g) + N
2
(g) Cl
2
(g) + N
2
(g)
19. Explain the term rate determining step & reaction intermediate.
20. A complex reaction takes place in two steps as follows:
(i) NO(g)+O
3
(g) NO
3
(g)+O(g)
(ii) NO
3
(g)+O(g) NO(g)+O
3
(g)
(a)Write the overall reaction.
(b)Identify reaction intermediate
(c) Identify the rate determining step if the predicted rate law is rate=K[NO][O
3
]
21. What is zero order reaction? Write the differential rate law for the zero order
reaction A Products. Derive its integrated rate law. How it is represented graphically?
22. Describe the graphical representation of first order reaction.
23. What is the order of following reaction?
(a) 2NO
2
(g)+F
2
(g)
2NO
2
F(g), rate=[NO
2
][ NO
2
F]
(b) CHCl
3
(g)+ Cl
2
(g)
CCl
4
(g)+HCl(g), rate=[ CHCl
3
]
24. Write the rate law for the following reactions:
(a) A reaction that is zero order in A and second order in B
(b) A reaction that is second order in NO and first order in Br
2
.
25. Define the term activation energy. Using Arrhenius equation explain why the
rate of reaction.
(a) increases with increase in temperature.
(b) increases with decrease in activation energy.
26. Write Arrhenius equation and explain the terms involved in it.
27. Explain, with the help of potential energy barrier, how does a catalyst increase
the speed of a reaction.
28. Explain, with the help of potential energy barrier, how does increase in
temperature in increases the rate of a reaction.
29. What are the requirements for a biomolecular reaction to take place?
30. Explain briefly the collision theory of biomolecular reactions?
31. Comment on the relationship between coefficient of balanced overall
equation for a reaction and the exponents to which the concentrations term in
the rate law are raised. What do these exponents represent?
32. How does a catalyst differs from reaction intermediate?
33. Comment on the effect of catalyst on each of the following:
(a) activation energy
(b) rate of forward reaction
(c) rate of reverse reaction
34. Consider the reaction:
Tl
+
(aq)+2Ce
4+
(aq) Tl
3+
(aq)+2Ce
3+
(aq)
The rate law for the reaction is rate=K[Ce
4+
][Mn
2+
]. In the presence of Mn
2+
the
reaction occurs in the following elementary steps:
(a)Ce
4+
(aq)+ Mn
2+
(aq) Ce
3+
(aq)+ Mn
3+
(aq)
(b) Ce
4+
(aq)+ Mn
3+
(aq) Ce
3+
(aq)+ Mn
4+
(aq)
(c) Tl
+
(aq)+ Mn
4+
(aq) Tl
3+
(aq)+ Mn
2+
(aq)
Identify
(a) Catalyst
(b) intermediates
(c) Rate determining step
Problems:
1.Consider the reaction 2A+B C. Suppose that at a particular moment during the
reaction, rate of disappearance of A is 0.076M/s,
(a)What is the rate of formation of C?
(b) What is the rate of consumption of B?
(c) What is the rate of the reaction?
2. Consider the reaction
3I
-
(aq)+S
2
O
8
2-
(aq) I
3
-
(aq)+2SO
4
2-
At a particular time t,
=2.2x10
-2
M/s.
What are the values of
(a)
(b)
(c)