0.4.

Consider the following reaction:

Cu (s) + 2Agt (ag) 2Ag (s) + Cu* (aq)
i) Depict the galvaniccell in which the given reaction takes palce.
(i) Give the direction of flow of current.
[Delhi 2018 (C)]
(iii) Write the half-cell reactions taking place at the cathode and anode.
Ans. () The cellmay be depicted as under
Cu (s) |Cu² (aq) || Ag* (aq) |Ag (s)
(ii) Current willflow from silver to copper electrode in the external circuit.
(iii) At cathode : 2Ag* (aq) + 2e 2Ag (s)
At anode:Cu (s)Cu?t (ag) + 2e
If the resistance
Q.5. Resistance of a conductivity cellfilled with 0.1 mol L-1 KClsolution is 100ohms.
conductivity and
of the same cell filled with 0.02 mol L-' KCI solution is 520 ohms, calculate the
solution is
molar conductivity of 0.02 mol L-l KCl solution. The conductivity of 0.1 mol L KCl
1.29 x 10* S cm-1, [A.I. 2018 (C)]
Ans. Cell constant, G* = Conductivity x Resistance
= 1.29 x 10- S cm' x 100 ohm
= 1.29 cm
-1
1.29 cmn
Conductivity of 0.02 mol L- KCI = = 0.00248 Scm-!
Resistance 520ohm
KX 1000 2.48 x 10-3 X1000
=124 S cm² moll
concentration 0.02
:
Q.6. Write the Nernst equation and calculate emf of the following cell at 298 K
Mg (s) | Mg* (0.1 M) | Cu* (0.01 M) | Cu(s)
[A.I. 2018 (C)]
Given Ebell
= 2.71 V.
Ans. Nernst equation for the cell may be written as
0.0591 (MgM
Ecell = Ecell log [Cu²*]
Substituting the values in the above equation,we have
0.0591 [0.1] = 2.71 V-0.0295 × 1 =2.68 V
Ecell = 2.71 V log [0.01]
2

0.7. (a) Calculate the mass of Ag deposited at cathode when a current of 2 amperes was passed
throughasolution of AgNO, for 15 minutes.
[Given: Molar mass of Ag =108 g mol;1F=96500 Cmol]
[Delhi 2017]
(b) Define fuel cell.
Ans. (a) Here, t= 15 x 60 = 900 seconds, current = 2amperes
.:.Charge = Current xTime
= 2 x 900= 1800 C

Electrochemistry95
Ag+ ’ A g (s)
We require 1F or 96500C to deposit one mol or 108 g of Ag
108
Mass deposited with 1800 C= -x 1800 g= 2.0145 g
96500
() Fuelcell :Galvanic cells that are designed to convert the energy of combustion offuels l
hydrogen, methane, methanol, etc.,directly into electrical energy are called fuel cells.
Q.8. (a) Thecell in which the following reaction occurs :
2Fe (aq) + 21 (aq) ’ 2Fe?* (aq) + I, (s)
has E°ell = 0.236 V at 298 K. Calculate the standard Gibbs energy of the cell reaction
[Given : 1F = 96,500 C moll
(b) How many electrons flow through a metallic wire if a current of 0.5 A is passed for
2 hours ? [Given :1F=96,500 mol[AI. 20171
Ans. (a) AG =- nFEcell
AG'= -2 x 96500 C mol x 0.236 V = 45548 Tmoll
= 45.548 kJ mol-l
(b) Given, I =0.5 A, t= 2 hours = 2 x 60x 60 = 7200 s
Quantity of electricity = Ixt=0.5x 7200 = 3600 C
96500C electricity is given by = 6.02 x 10 electrons
6.02 x 1023
3600 C electricity is given by = -x 3600 = 0.2245 x 10 electrons
96500
= 2.245 × 10 electrons
Q.9. The electrical resistance of a column of 0.05 M KOH solution of diameter 1 cm and length
45.5 cm is 4.55 x 10 ohm. Calculate its molar conductivity. [Foreign 2017]
Ans. Given diameter of column=lcm
Length of the column () = 45.5 cm
Area of cross-section of the column =TX = 3.14 x (0.5) = 0.785 cm?
We have the relation :

R= P or
A
or K=
RA
Substituting the values, we have
45.5 cn
Conductivity, K = X
0.785 cm2
= 0.0127 S cm-1
4.55 × 10 ohm
1000
Molar conductivity, A,n =KX C
1000
= 0.0127 S cm-l x cm-3=254 S cm² mo-1
0.05 moles
0.10. Calculate emf of the following cell at 298 K:
2Cr (s) + 3Fe+ (0.1 M) ’ 2C* (0.01 M) + 3Fe (s)
Given : Ecc) =-0.74 V, E° Fe2*Fe) =- 0.44 V. [Delhi 2016]
Ans. Standard emf of the Cr - Fe cell is calculated as under:
Ecell = Ecathode - Eanode
=-0.44-(-0.74) = 0.30 V
0.059
Ecell =cell- log
(Fe2
96 U-LIKE Chemistry-XI|
Substituting the values, we have
0.059 [0.01|2
Ecell = 0.30 - log =0.30 -(-0.059/6)= 0.3098 V
[0.1j°6

Q.11. Calculate emf of the following cell at 25°C:

Fe|Fe²* (0.001 M) | H* (0.01 M)| H, (g) (1 bar) | Pt (s)
E°(FeFe) =-0.44 V, E°(H*H) =0.00V |Delhi 2015]
Ans. The cell reaction is Fe (s) + 2H (ag) ’ Fe (ag) + H,
Eell =0.00 -( 0.44) = 0.44 volt

Eçell = Ecell
0.059
log
[Fe*]
2 [H?
0.059
Ecell = 0.44 -log [0.001]
2 [0.01]'
0.001 0.0295 = 0.4105 volt
= 0.44 - 0.0295 log = 0.44 - 0.0295 × 1= 0.44
0.01 x 0.01
0.12. Calculate the emf of the following cell at 25 °C:
Zn | Zn2* (0.001 M) || H (0.01 M) | H, () (1 bar) | Pt (s)
EzntIZn) = - 0.76 V, EH/H,) = 0.00 V (Foreign 2015]
Ans. The cell reaction is
Zn (s) + 2H* (aq) Zn²* (aq) + H,; Thus n =2
E°= 0.00-(-0.76) = 0.76 volt

log [Zn]
0.059
E= E°
2 [H?
[0.001]
=0.760.0295 log = 0.76-0.0295 log 10
[0.01
= (0.760.0295) volt = 0.7305 volt
0.13. Conductivity of 2.5 x10Mmethanoic acid is 5.25 x105S cm. Calculate its molar conductivity
and degree of dissociation.
Given : A°(H) =349.5 Scm² mol and 2°(HCO0) = 50.5 S cm² mol [A.I. 2015]
Ans. AHCOOH = +2coor-349.5 + 50.5 =400S cm² mol1
AHcoOH =Kx 1000 cm° L- molarityl
5.25 x 10S cmx1000 cm L1
= 210 S cm² mol1
2.5x 10 mol L-l
Am 210
Degree of dissociation () = 400
=0.525 or 52.5%
A
Q.14. (a) Calculate A,G° for the reaction
Mg (s) + Cuz+ (aq) ’ Mg (ag) + Cu (s)
Given: E +2.71 V, 1 F= 96500 C mol-1
electrical
(b) Name the type of cell which was used in Apollo space programme for providing[A.I. 2014]
power.
Ans. (a) Apply the relation
A,G°=- nFEOcell
Here, n = 2, F = 96500 C mol and Ell = 2.71 V

Electrochemistry 97
Substituting the válues in the equation, we have
A,G°= -2 x 96500 C mol x 2.71 V
523030 J mol-1
= -523.03 k] mnol!
(0) H 0 , fuel cell was used in Apollo space programme for providing electrical power.
Q.15. State Kohlrausch law of independent migration of ions. Why does the conductivity of a
decrease with dilution ? [A.solJ. u2014|
tion
Ans. Kohlrausch law of independent migration of ions states that limiting molar conductivity of an
electrolyte can be represented as the sum of the individual contributions of anion and cation of u
electrolyte. If 2t and Aer are the limiting molar conductivities for sodium and chloride i
respectively, then limiting molar conductivity for sodium chloride is given by the equation:
Am (NaCl) = a +
Conductivity of a solution decreases with dilution because the number of ions per unit volumest
the solution decreases.
Q.16. Calculate the emf of the following cell at 25 °C:
Ag (s) | Ag* (103 M) | Cu* (10 M) |Cu (s)
Given EPell = + 0.46 V and log 10" = 1. [A.I. 2013)
Ans. The cell reaction is
Cu + 2Ag* ’ Cu' + 2Ag
EMF of the cell can be obtained by using the Nernst equation :
0.059 [Cu2t]
Ecell =Ecel 2 -log [Agtj?
Substituting the values, we have
0.059 [10-]
Ecell = 0.46 V - -log
2 [10
= 0.46 - 0.0295 log 10
= 0.46 - 0.0295 x 5 x log 10
= 0.46 -0.1475
or Ecell = 0.3125 V
0.17. The electrical resistance of a column of 0.05 M NaOH
solution of diamneter 1 cm and lengtn
50 cm is 5.55 x 10 ohm. Calculate its resistivity,
and conductivity molar conductivity.
Ans. R= p RA
or p =
A
Given that R = 5.55 × 10 ohmn, A = r = ¬x 22
0.5 = 7 x0.25 = 0.7857 cm². 1= 50 cm
7
Substituting the values in equation (), we have
1.
5.55 x 10°ohm x 0.7857 cm²
p=
50 cm =87.213 ohm cm
2. 1_ ohm cm
K=
p 87.213 =0.01147 S cm-1
K 0.01147 S cm-1 0.01147S cm
3.
C 0.05 mol L-1 0.05 mol (1000 cm)
0.01147S cm-1
x 1000 cm = 229.4 S cm² mol1
0.05 mol
98 U-LIKE Chemistry-Xl
018. Calculate the equilibrium constant K for the reaction at 298 K
Zn (s) + Cu²+ (ag) Zn?* (ag) + Cu(s)
0.34 V] IA.I. 2011 (CJ
TGveniEzn2+/Zn =-0.76 V, E..2+, = +
Ans. AG° =-nFEO
n = 2, F= 96487 C mol-, E =1.1 V
Therefore AGO = - 2x 96487 x 1.1 = - 21227 J mol
Equilibrium constant K can be obtained from the relation
AGO = - RT ln K
Or - 21227 =-8.314 × 298 x ln K
21227
Or In K = =8.5677
8.314 x 298

or K= 3.696 × 108
0.19. For the cell
Zn (s) |Zn2+ (2 M) ||Cu2+ (0.5 M) | Cu (s)
(a) Write the equation for each half-reaction.
(b) Calculate the cell potential at 25 °C.
[Given : Ezn2+Zn =-0.76 V, Ec2+1C =+ 0.34 C] [Dellhi 2011 (C)J
Ans. E = 0.34 -(-0.76) =1.1V
0.0591 Zn2+ 0.0591 2
Egell = Ecell
2 -log Cu2+
= 1.1 -
2 log 0.5
= 1.1 - 0.0295 log 4 = 1.1 0.0295 x 0.6021 = 1.1 - 0.0177 = 1.0823 V
of water to oxygen?
Q.20. (a) Calculate the charge in coulombs required for oxidation of 2 moles
[Given 1F=96,500 C mol]
watches. The following reactions
(b) Zinc/Silver oxide cell is used in hearing aids and electric
OcCur:
Zn (s) ’ Zn* (ag) + 2e E Zn2+/Zn =-0.76 V
E° Agt/Ag = 0.344 V
Ag,0 + H,0+ 2e ’ 2Ag + 20H
Gibbs energy.
Calculate (i) standard potential of the cell, (ii) standard [CBSE Sample Question Paper)

Ans. (a) 2H,O ()’0, (g) + 4H* (ag) + 4e

oxidation to oxygen or4 Faradays of electricity is
2 molecules of water release 4 electrons for
water to oxygen.
required for the oxidation of 2 moles of coulombs = 386000 coulombs
process = 4 x 96500
Charge in coulombs required for the electrode is the cathode
anode while silver
(b) (i) Zn electrOde is the
EPel = Ecathode - Ear
anode
1.104 V
= 0.344V- (-0.76) V =
AGO = - nFE°cell
(ii)
n=2
cathode reactions)
electrons each are involved in the anode and
(Because 2 F=96500 coulombs

E° = 1.104 V
have
Substituting the values, we 213072 J mol =-213.072
kI mol-!
96500 x 1.104 =- cell. Write the
AGO =-2x merit and one demerit over storage
nickeloadmium cell? State its one [A.I. 2010 (C)]
21. What is discharging of this cell.
occurs during
Overall reaction that Electrochemistry|99
Ans. Nickel-cadmium cellis a secondary cell and it is rechargeable.
Merit : It has a longer life than the storage cell.
Demerit : It is more expensive to manufacture.
The overall reaction when the discharging takes place is as under :
Cd (s) + 2Ni(OH), CdO (s) + 2Ni(OH), (s) + H,O ()
O.22. Give reason
(a) Why does an alkaline medium inhibit the rusting of iron ?
(b) Why does a drycell become dead after a long time
even if it has not been used 2
(c) Why is zinc better than tinin protecting iron from corrosion ?
[CBSESample Question Paperl
Ans. (a) Rusting of iron takes place in the presence of H*. Alkaline mediumn neutralises H+ ione
inhibits the process of rusting.
(b) Adry cell becomes dead after a long time even if it has not been used. This is because acidic
NH,CI, which is a salt of weak base and strong acid, corrodes zinc container.
(c) Zinc protects iron from corrosion because reduction potential of Zn+ is lower than that of Fel:
but that of Sn* is higher than that of Fe*.
Q.23. Consider the figure below and answer the following questions :
Salt Bridge

-Copper plate
Zinc plate Zn2*(aq) Cu2t(aq)
Cell A

(A) Electrode (B)Electrode

Cell B
Fig. 3.14
() Cell'A'has E.oll=2 V and Cell 'B' has E.alu = 1.1 Vwhich of the two cells 'A' or B' will
an electrolytic cell. Which electrode act as
reactions willoccur in this cell ?
(1) If cell'A'has Enell=0.5 V and cell 'B' has
Erell =1.1 Vthen whatwill be the
and cathode ? reactions at anode
Ans. (1) Cell 'B' willact as
electrolytic cell as it has lower emf. [NCERT Exemplarl
.:. The electrode reactions will be:
Zn + 2e ’ Zn at cathode
Cu Cu + 2e at anode
(ii) Now cell 'B' acts as galvanic cell as
it has higher emf and will
The electrode reaction will be : push electrons into cell 'A.
At anode :
Zn Zn + 2e
At cathode :
Cu?t + 2e
’Cu
Q.24. The following chemical
reaction is occurring in an
Mg (s) + 2Ag (0.0001 M) ’
Mg*
electrochemical cell:
The E° electrode values are (0.10 M) + 2Ag (s)
Mg*/Mg=- 2.36 V,
Ag*/Ag= 0.81 V
For this cell
calculate/write
(a) (1) E° value for the electrode
2Ag*/2Ag
100 U-LIKE Chemistry-X
(i) Standard cell potential Ecell
(b) Cell potential (E) cell
(c) () Symbolic representation of the above cell.
(ii) Will the above cell reaction be spontaneous ? |CBSE Sample Question Paper]
Ans. (a) () The electrode potential is not multiplied by thecoefficients of metal/metal ion (Ag ana
Ag* in this case).
Thus E°Agt/Ag = 0.81 V
(ii) Ecell =E Agt/Ag E Mg2+/Mg
= 0.81 -(-2.36) = 3.17 V

(b) Ecell = cell

0.059 Mg²] 0.059 0.1
2 log [Agt2
= 3.17
2 -\o8 10
= 3.17 -
0.059
log10 = 3.17 - 0.0295 x 7 log 10 = 3.17 - 0.2065 = 2.9635 V
2

(c) (1) Mg (s) | Mg (0.1M) | Ag* (0.0001M) | Ag (s)

(ii) Yes, because Eell is positive.
Q.25. (a) A curent of 1.50 amp was passed through an electrolytic cellcontaining AgNO, solution
with inert electrodes. The weight of Ag deposited was 1.50 g. How long did the current
flow?
(b) Write the reactions taking place at the anode and cathode in the above cell.
(c) Give reactions taking place at the two electrodes if these are made up of Ag.
[CBSE Sample Question Paper]
Ans. (a) I=1.50A, m =1.50 g
Atomic mass of Ag =108
Eq. mass of Ag = 108
108 g silver is deposited by = 96500 C
96500
1.5 g silver isdeposited by = x1.5 =1340.28 C
108
Quantity of electricityQ=Ix t
Or t=

Substituting the values, we get

1340.28
t= = 893.52 s
1.5

(b) At cathode: Agt +eAg (s)

At anode: 2H,O4H* + O, + 4e
(c) At anode: Agt +e Ag (s)
At anode: Ag ’Ag* +e
0.26. Calculate the emf and AG of cell reaction for the following cell at 25 °C:
Mg (s) | Mg* (0.001 M) || Cu* (0.0001 M) | Cu (s)
[E'Mo2+/Me =- 2.37 V, Eu2+/Cu = t 0.34 V and 1 F = 96500 C mo-y
Ans. Thefollowing reactions take placein the cell:
Mg (s) ’ Mg* (aq) + 2e

Electrochemistry 101
Cu (ag) + 2e’Cu (s)
Mg (s) + Cu (aq) ’ Mg (ag) + Cu (s)
Thus, n = 2
Applying Nernst equation and substituting the values, we get
0.0591 [Mg²"]
Eel = ECuz+/Cu- EMg2+/Mg 2 -log ICu]
0.0591 0.001
= 0.34 V -(-2.37 V) 2 log 0.0001
0.0591
= 2.71 V log 10 =2.71V-0.0295 V = 2.6805 V
AG can be obtained as under :
AG =-nFE =-2 x2.6805 x 96500
=-517336.5 J mol-l=-517.34 k] mol-1
Q.27. Calculate the standard cellpotential of the galvanic cell in which the following reaction takes
place:
2Cr (s) +3Cd* (ag) ’ 2Cr* (ag) +3Cd (s)
Alsocalculate the A,G° value of the reaction.
[Given: E"c=-0.74 V; Eca2*/ca =-0.40Vand F= 96500 Cmof)
Ans. The electrode reactions may be represented as under:
2Cr (s) ’ 2Cr (ag) + 6e
3Cd² (ag) + 6e’ 3Cd (s)
Thus, n = 6.
Standard cell potential may be obtained as under :
Ecell = E°,ca2+/Cd - ECr3+/Cr =- 0.40 V -(-0.74 V)
or E°l = 0.34 V
To calculate A,G°, applying the following
relation and substituting the values, we get
A,G° =- nE°F =-6 x 0.34 V x 96500 C
A,G° =- 196.86 k] mol-!
Q.28. (a) Calculate the charge in
coulombs required for the oxidation of 2 moles of
Oxygen ? water to
(b) Zinc/Silver oxide cell is used in [Given 1F-96500 C mol]
hearing aids and watches. The following
Zn (s) Zn* (aq) + 2e reactions occur:
Zn2+/Zn =-0.76 V
Ag,O + H,0 + 2e 2Ag + OH EO Ag+/Ag 0.344 V
Calculate (i) standard potential of the cell (ii)
Ans. (a) 2H,0 () ’0, (g) +4H (aq)Gibb's + 4e
free energy
Two molecules of water
of electricity is release four electrons for oxidation to oxygen. Thus
required for the oxidation of two moles of four Faradays
Charge in coulombs = 4 x 96500 water.
(b) (i) Zinc
electrode is the anode while coulombs = 386000 coulombs
silver electrode is the
Eoell =0.344 V
(-0.76 V) = 1.104 V cathode
(11) Gibbs free
energy can be calculated as
AGO =- nFEO under:
102 | U-LIKE
Chemistry-XIl
Substituting the values, we have
AG = -2x 96500 Cmolx 1.104 V
=-213072 J mol- =-213.072 k] mol
o29, Conductivity of 0.00241 Macetic acid is 7.896 x 10-5 S cm-, Calculate its molar conductivity. 1"
for acetic acid is 390.5 S cm² mol-l,what is its dissociation constant ?
Ans. K= 7.896 x 105 Scml

Molar conductivity can be obtained as under :

1000K 1000× 7.896 x 10 7.896 x 10 7896 =32.76S cm mo!
M 0.00241 241 241

32.76
=
=0.0838 =8.38%
390.5
Use the following relation to calculate dissociation constant, K,
Ca' 0.00241 x (0.084) =1.86 x105
K, =
1-a (1-0.084)
0.30. () Solutions of two electrolytes 'A' and B are diluted. The limiting molar conductivity of
'B' increases 1.5 times while that of 'A' increases 25 times. Which of the two is a strong
electrolyte? Justify your answer.
(i) The products of electrolysis of aqueous NaCl at the respective electrodes are :
Cathode : H,
Anode : Cl, and not O,. Explain. [CBSE Sample Question Paper]
Ans. () Bis a strong electrolyte.
A strong electrolyte is already dissociated into ions, but there are interionic forces of attrac
tion. COn dilution, these forces are overcome and the ions become free to move. So there is
greater increase in molar conductivity on dilution.
(ii) Water should get oxidised in preference to CI, but due to overvoltage or overpotential, CIr is
Oxidised in preference to water.