Electrochemistry - Workbook Solution

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Solutions to Workbook-4 [Chemistry] | Electrochemistry

Daily Tutorial Sheet Level - 0
1. Representation of the galvanic cell for the given reaction is:

2 2
Zn| Zn(aq ) ||Cu(aq ) |Cu
Anode Salt Cathode
bridge
2. Kohlrausch’s law of independent migration of ions: It states that limiting molar conductivity of an
electrolyte can be represented as the sum of the individual contributions of the anion and cation of the
electrolyte.
If  and  are limiting molar conductivities of the sodium and chloride ions respectively then the
Na  Cl 
limiting molar conductivity for sodium chloride is given by  m(NaCl )    

Na  Cl
Kohlrausch’s helps in the calculation of degree of dissociation of weak electrolyte like acetic acid.

The degree of dissociation  is given by   m
m
Where,  m is the molar conductivity and  m is the limiting molar conductivity.

3. The species that get reduced at cathode is that one having higher value of standard reduction potential.
 
Hence, the reaction that will occur at cathode is Ag (aq )  e  Ag (s).
4. The species that get reduced at cathode is the one which have higher value of standard reduction
2 
potential. Hence, the reaction that will occur at cathode is Cu(aq )  2e  Cu(s)
5. Mercury cell is generally used in transistors.

At cathode : HgO  H2O  2e  Hg  2OH 
At anode : Zn(Hg)  2OH   ZnO  H2O  2e

6. Lead storage battery is a secondary cell.
Cell reactions during operation
2 
At anode : Pb(s)  SO4(aq )  PbSO 4(s)  2e
At cathode : PbO2(s)  SO24(aq

  
)  4H(aq )  2e  PbSO 4(s)  2H 2O(l )
2
Overall reaction: Pb(s)  PbO2(s)  2H2SO4(aq)  2PbSO 4(s)  2H 2O(l )
7. Mercury Cell : It is a miniature cell which finds a frequent use these days to supply energy for watches,
video cameras, hearing aids and other compact devices. In mercury cell the anode is zinc-mercury
amalgam, and the cathode is a paste of mercury (II) oxide and carbon, electrolyte is a moist paste of
KOH – ZnO.
The cell reactions are as follows:
 
Anode: Zn(Hg)  2OH  ZnO(s)  H2O(l )  2e
(Amalgam)
Cathode: HgO(s)  H2O(l )  2e   Hg(l )  2OH
Net reaction: Zn(Hg)  HgO(s)  ZnO(s)  Hg (l )

The cell potential remains constant during its life as the overall reaction does not involve any ion in
solution whose concentration can change during its use.
8. Metals of lower electrode potential value when connected with iron protect it form oxidation and prevent
corrosion. Hence, coating of metal A having lower electrode potential will be better than B which has
higher E   0.14 V.
(B2  /B)
Chemistry | Electrochemistry 280 Workbook-4 | Solutions

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2 4 
9. At anode: Sn(aq )  Sn(aq )  2e ]  5
   2
At cathode: MnO4(aq)  8H(aq )  5e  Mn (aq )  4H2O(l ) ]  2
2 2 4
Net cell reaction: 2MnO4(aq )  5Sn(aq 
)  16H(aq)  2Mn (aq )  5Sn (aq )  8H 2O(l )
Ecell  Ecathode  Eanode  1.51 V  0.15 V  1.36 V

Since, cell potential is positive therefore the reaction is product favoured.
 2
10. Ni(s)  2Ag (aq )  Ni(aq )  2Ag (s) , E  1.05 V Here, n = 2
nEcell
Using formula, log K c 
0.059
2  1.05
or log K c   35.5932
0.059
K c = antilog 35.5932 or K c  3.92  1035
Again, G  nFE cell

G  2  96500  1.05  202650 J  G  202.65 kJ
11. The reciprocal of resistivity is known as specific conductance or simply conductivity. It is denoted by
1 l
 (kappa).  or   G 
 a
Hence, conductivity of a solution is defined as the conductance of a conductor of 1 cm length and having
1 sq. cm as the area of cross section. Alternatively, it may be defined as conductance of one centimtre
cube of the solution of the electrolyte. Molar conductivity of a solution at a dilution V is the conductance
of all the ions produced from 1 mole of the electrolyte dissolved in V cm 3 of the solution. It is
represented by  m .
 m  V
Variation of conductivity and molar conductivity with concentration: Conductivity always decreases
with decrease in concentration, for both weak and strong electrolytes. Because the number of ions per
unit volume that carry the current in a solution decrease on dilution.
Molar conductivity vs C1/2 for acetic acid (weak electrolyte) and potassium
Chloride (strong electrolyte) in aqueous solutions
Molar conductivity increases with decrease in concentration. Because that total volume, V, of solution
containing one mole of electrolyte also increases. It has been found that decrease in  on dilution of a
solution is more than compensated by increase in its volume.
1 1
12. Conductivity  G   1  5  10 3 1 cm 1
R 200
  1000 5  10 3  1000
Molar conductivity (  m )    500 1 cm 2 mol 1
M 0.01
  1000 cm  M 138.9  1.5

13.  cm      0.20835 S cm 1
M 1000 1000
14. Given: Current I = 5 A; t = 20 × 60 s, w = ?
Q = I × t = 5 × 20 × 60 = 6000 C

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Reaction for deposition of Ni,

Ni 2   2e   Ni
2 mol 1 mol
2  96500 C 58.7 g
Thus, 2 × 96500 C of electricity produces 58.7 g Ni
58.7  6000
 6000 C of electricity would produce   1.825 g
2  96500
15. The given reaction is Cr2O72   14H  6e   2Cr 3   7H 2O
One mole Cr2O72  requires 6 mol of electrons for reduction. Hence, quantity of electricity required
 6 mol  96500 C mol 1  5.79  105 Coulomb

16. Those galvanic cells which give us direct electrical energy by the combustion of fuels like hydrogen,
methane, methanol etc. are called fuel cell.
The reactions taking place in hydrogen – oxygen fuel cell:
At cathode : O2( g)  2H2O(l )  4e  4OH(aq

)

At anode : 2H2(g)  4OH(aq )  4H 2O(l )  4e
Net reaction : 2H2(g )  O2(g )  2H2O(l )

17. According to electrochemical theory of rusting the impure iron surface behaves like small electrochemical
cell. In this any point of iron acts as anode and other iron surface acts as cathode. Moisture having
dissolved CO2 or O2 acts as an electrolyte. The reactions are given below.
At anode : Fe  Fe2   2e ; E  0.44 V

Fe2  /Fe
1
At cathode : 2H   O  2e  H2O ; E    1.23 V
2 2 H /O2 /H2O
1 
Overall reaction : Fe  2H  O  Fe2   H2O ; E cell  1.67 V
2 2
The Fe2 ions are further oxidized by atmospheric oxygen to Fe3 ions, which form hydrated ferric oxide
(rust).
1
2Fe2   O 2  2H2 O  Fe2O3  4H   Fe2O3  xH2O  Fe2O3  xH2O (Rust)
2
2 
18. (i) The cell reactions are: Zn(s)  Zn(aq )  2e (Anode) ; Cu  2e  Cu(s) (Cathode)
2 2
Net reaction: Zn(s)  Cu(aq)  Zn(aq )  Cu(s)
(ii) Ecell  E right  E left


 0.34 V  ( 0.76 V)  1.10 V
(iii) Copper electrode will be positive on which reduction takes place.
 2
19. The reaction is Zn(s)  2Ag (aq )  Zn (aq)  2Ag (s)
2 
Cell can be represented as Zn|Zn(aq ) ||Ag (aq ) | Ag

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(i) The zinc electrode is negatively charged (anode) as it pushes the electrons into the external
circuit.
(ii) Ions are the current carries within the cell.
(iii) The reactions occurring at two electrodes are:
2 
At zinc electrode (anode): Zn(s)  Zn(aq )  2e
 
At silver electrode (cathode) : Ag (aq )  e  Ag (s)
20. G  nFC cell

G 43600
Ecell    0.226 V
nF 2  96500
2AgCl(s)  H2(g )(1 atm)  2Ag (s)  2H  (0.1 M)  2Cl  (0.1 M)
0.0591 [Product]
Ecell  Ecell  log
n [Reactant]
0.0591 (0.1)2 0.0591 0.0591
 0.226  log  0.226  log(10 2 )  0.226  ( 2)  0.226  0.0591  0.2851 V
2 (1) 2 2
21. Given cell, 2Al(s)  3Cu 2  (0.01 M)  2Al3  (0.01 M)  3Cu(s) Ecell  1.98 V, Ecell ?
Using Nernst equation at 298 K
0.0591 [Al3  ]2
Ecell  Ecell  log
6 [Cu2  ]3
0.0591 [10 2 ]2
1.98 V  E cell  log
6 [10 2 ]3
0.0591
1.98 V  E cell  log10 2
6
0.0591 0.0591
1.98 V  E cell  2  Ecell  1.98   1.99 V
6 6
22. At anode : Ni  Ni2   2e
At cathode : [Ag   e   Ag]  2
Cell reaction: Ni  2Ag   Ni 2   2Ag
Ecell  Ecathode  Eanode  E   E  0.80 V  ( 0.25)
Ag  /Ag Ni2 /Ni
0.0591 Ecell  n 1.05  2

Ecell  log K c  log K c  
n 0.0591 0.0591
log K c  35.53
K c  antilog 35.53  3.38  1035

23. The cell reaction in button cell:
2 
Zn(s)  Ag 2O(s)  H2O(l )  Zn(aq)  2Ag(s)  2OH(aq )
(i) Calculation of Ecell

2 
Reactions: Zn(s)  Zn(aq )  2e
Cathode: Ag 2O(s)  H2O(l )  2e  2Ag (s)  2OH(aq)


 2e
n=2
Ecell  E cathode  Eanode  EAg  E   0.80  (  0.76) V  1.56 V
2O/Ag Zn 2  /Zn
(ii) Calculate of  rG

 rG   nFE cell

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  2  96500 C mol 1  1.56 V   301080 C V mol 1   301080 J mol 1   301 kJ mol 1

24. The given cell may be represented as
Cu(s)|Cu 2  (0.10 M)||Ag  (C)|Ag (s)
Ecell  E cathode  Eanode  0.80 V  0.34 V  0.46 V
0.0591 [Cu 2  ]
Ecell  Ecell  log
2 [Ag  ]2
0.0591 0.1
or, 0.422 V – 0.46 V – log
2 [Ag  ]2
0.1 0.1 0.038
– 0.038 V = – 0.0295 log or, log   1.288
 2  2 0.0295
[Ag ] [Ag ]
0.1 0.1
or, log  antilog 1.288 = 19.41  [Ag  ]2   5.1519  10 3
 2 19.41
[Ag ]
[Ag  ]  7.1  10 2 M
  1000
25. Using formula,  cm 
C
Given   3.905  10 5 S cm 1
3.905  10 5  1000
C = 0.001 mol L1  cm   39.05 S cm 2 mol 1
0.001
The degree of dissociation,
cm 39.05
   0.1 [ m  349.6  40.9  390.5 S cm 2 mol 1]
cm 390.5
26. Resistance of 0.1 M KCl solution R  100 

Conductivity   1.29 S m 1
Cell constant G    R  1.29  100  129 m 1
Resistance of 0.02 M KCl solution, R  520 
cell constant 129 m 1
Conductivity,     0.248 S m 1
R 520 
Concentration, C  0.02 mol L1  1000  0.02 mol m 3  20 mol m 3
 0.248 S m 1
Molar conductivity,  m    0.0124 S m 2 mol 1
C 20 mol m 3
27. Reaction for deposition of Mg from molten MgCl 2 :
MgCl 2  Mg 2   2Cl 
Mg 2   2e  Mg
24 g of Mg is deposited by 2 × 96500 C of electricity
 1.2 g of Mg will be deposited by
2  96500
 1.2  9650 C of electricity
24
Q 9650
Now, Q = It  I   2.68 A
t 60  60
28. We have
 Ni2  
0.059  (aq ) 
Ecell  E cell  log 
n Cu2  
 (aq ) 
0.059  0.01 
0.059  E cell  log   [Here n = 2]
2  0.1 

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0.059  1  0.059
0.059  Ecell  log   ; 0.059  Ecell  (  log10)
2  10  2
0.059 0.059 0.059
0.059  Ecell   Ecell  0.059   Ecell   0.0295  0.03
2 2 2
Now, Ecell  E cathode  E anode
0.03  0.34  Eanode
Eanode  0.34  0.03  0.31 V
Hence, E  0.31 V
Ni2  /Ni
Daily Tutorial Sheet 1 to 5 Level – 1 | JEE Main
1.(A) Zn  Fe2   Zn 2   Fe
Ecell  ERP cathode  E RP anode   0.44  0.76   0.32V    (  )ve  will be spontaneous
2.(B) 50% H2SO4 is very concentrated solution, so, oxidation of SO24  to S2O82  takes place.
3.(A) Ag can not reduce H  ions in acidic solution since reduction potential for silver is more than zero.
4.(B) Cell rxn Zn(s)  Cu2 (aq)  Zn 2 (aq)  Cu(s)
 Zn 2  
0.06  
Ecell  E cell  log 
2 Cu 2  
 
Ecell decreases with increase in  Zn 2  and Ecell increases with increase in Cu 2 
   
 E1  E 2  E 3
5.(B) Increasing Ered indicates increasing oxidising power. Thus A  C  B
RT pH
2
6.(D) Reduction potential, , E  E  n
nF [H ]
2.303 RT 1
 E  0.0  log  
  0.059 pH
1  96500 [H ]
HF  HCl  HBr  HI
7.(A) 

increasing order of reducing power
8.(A) More reactive metal displaces less reactive metal. 9.(A) Oxidation of Cu will take place.
10.(A) Reduction potential of Mg is lesser than reduction potential of Zn.
11.(D) Reduction potential of Ag is positive and can be reduced by H2.
12.(C) Most negative reduction potential imply most powerful reducing agent. Thus ‘D’ will displace A, B and C.
13.(D) E  0.059  pH  0.059  3  0.177 V .
14.(B) Standard hydrogen electrode has zero electrode potential (assumed to be zero).
15.(D) E  1.66 V and E  0.76 V . 16.(B) Charge on one e  Avogadro' s no  F .

Al3  /Al Zn2  /Zn
17.(B)   
Charge Q  it  9.65  16  60  40  9.65  1000  0.1F 
1
O2  O2  2e
2
0.5  22400
2F  0.5 mol O2  0.5  22400 mol O2  0.1F   0.1F  560 ml O2
2F
18.(B) Electrolysis of water is done to produce H2 /O2 gas.
19.(C) Q  Zi t  Q  Z.1  1  QZ

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Amount deposited by 1 C is equal to electrochemical equivalent.

20.(B) Q  it  1  60  60 C 21.(A) 2H   H2  2e  oxidation  Anode
 
22.(B) W  Z. Q  Z  W / Q  g / coulomb
1
23.(B) H  e  H2
2
0.5 mol H2  11200 cc H2  1F
1F
1.12cc H2   1.12  9.65 C
11200
Q  it  9.65  i  1  i  9.65 A
2 
24.(B) Cathode Cu  2e  Cu
Anode 2H2O  O2  4H   4e
Cu deposited on cathode but at anode O2 liberated on anode and simultaneously H ions are dissolved
in water. Ultimately H & SO24  ions left in the solution to from H2SO4 .
25.(B) Electrolysis of dil. NaCl produces H2 gas at cathode because reduction of water is more favourable than
reduction of Na .
2H2O  2e  H 2  2OH
1 mol H2  2 F
0.01 mol H2  2 F  0.01C  0.02 F
So, Q  it  2  96500  0.01 10  10 3  t  t  19.3  10 4 sec

1120 1
26.(C) Moles of H2 collected   mol
22400 20
1 mol H2  2 F coulomb
1 1
mol H2  2 F   0.1F coulomb
20 20
Thus 0.1F  1930  i  9650  2  965  i  i  5A
3 3 3
27.(D) 3Ag   3e  3Ag ; Cu 2    2e   Cu
2 2 2
3
Au 3   3e   Au ; Thus ratio of mol of Ag : Cu : Au  3 : :1  6 : 3 : 2
2
28.(A) Electricity passed in one hour  12  3600 C
Electricity used to deposit Ni  0.6  12  3600 C
Ni 2   2e   Ni  2  96500 C produces 1 mol or 58.7 g Ni

58.7
0.6  12  3600 C produces   0.6  12  3600  7.883 gm
2  96500
29.(A) In electrolytic purification, anode should be formed of impure metal.
30.(A) MnO4  5e   Mn 2  ; n-factor = 5
q  (n  n  factor)F  q  (0.5  5)F  2.5F
31.(C) Specific conductance decreases on dilution.
32.(C) On dilution, dissociation of weak electrolyte increases and also it increases the movability of ions in the
solution. Since conductivity measurement requires unit volume solution no. of ions decreases on
dilution, but conductivity measurement uses whole solution containing one equivalent electrolyte, causes
increase the in no. of ions.
33.(B) In solid NaCl, Na  & Cl  cannot move. 34.(D) H ion has maximum conductance.

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35.(B) Specific conductivity decreases with dilution because it is defined for per unit volume of solution.
1 
36.(B) For 0.2 M solution : R  50 , G  S ;   G  G  G   1.3  50 m 1  65 m 1
50 G
1 65
For 0.4M solution : R  260  ; G  ;   G  G   0.25 Sm 1
260 260
 0.25
 m    6.25  10 4 Sm 2 mol 1
1000C 1000  0.4
1 2 1
37.(B)   
 
 
   
eq NH 4 OH   eq NH 4 Cl   eq NaCl   eq NaOH  149.74  126.4  248.1  271.44  cm eq 
38.(D) HCl is strong electrolyte and one of its ion is H which has highest movability due to jumping
mechanism.
0.0129 1000 
39.(B)   G  G  G   1.29 1 40.(D) If  is taken in S cm 1 then  eq   10000 
0.01 N
41.(C) Unit of equivalent conductance is ohm 1 cm 2 eq 1 42.(D)  CH 
 CH   HCl  NaCl
3COOH 3COONa
43.(A) Difluoroacetic acid is strongest acid, so, highest electrical conductivity.
  1000 G G  1000 0.5  1000
44.(A)  eq  &   G  G  ;  eq    10
N R RN 50  1.0
45.(D)   G  G
1.29 1 129
For 0.1M solution G   129 m 1 For 0.2M solution   G   S m 1
G R 520
If we dilute 0.2 M solution by 10 times, its concentration becomes 0.02 M. Thus number of ions per unit
1 129
volume is th of initial one. So  for this solution is S m 1
10 520  10
129
520  10
 0.02   12.4  10 4 S m 2mol 1
1000  0.02
46.(B) For strong electrolyte, no. of ions are constant on dilution, molar conductivity depends only movability
which increases on dilution.
47.(C) K 4 Fe CN
  6   dissociates into five ions (maximum) Pt  NH3  Cl2   no ions
 2 
CO NH
 3  4 Cl2  Cl  two ions
 
Cr NH
3 6  Br3  4 ions

Fe CO 5  no ions
48.(B)  HOAC   NaOAC

 
 HCl   NaCl  91.0  426.2  149.9  367.3 S cm 2mol 1
49.(C)  ClCH  ClCH   HCl  NaCl  224  230  38.5  415.5

2COOH 2 COONa
50.(A) G net  G1  G2
G1G*  G 2G* V 1 1 1  *
 
net  V1  V2  1 V1  2 V2 ; net  ; net     G  G net G*
2V 
2  R1 R 2 
0.16
51.(B) Amount of electricity to deposit 0.16g copper from CuSO4 solution  2 F   0.005 F
64
Since 2F electricity liberates 1 mol H2 , 0.005 F electricity will liberates
1
  0.005 F mol H2  2.5  10 3 mol H 2  2.5  10 3  22400 ml H2  56 ml or 56 cm 3
2F

Vidyamandir Classes
[Fe2 ]2 [10 3 ]2 10 6
52.(D) QC     10 1
[H  ]4  PO (10 4 )  0.1 10 5
2
log QC  1
0.0591 0.0591 0.0591
E  ERxn  (log QC )  1.67  [ 1.0]  1.67    1.685V
4 4 4
1
53.(C) H  e  H2
2
0.06 pH 2
2
E  E  log  For negative E, pH  H   or p H  H  
1 H   2   2  
 
0.059 0.059
54.(A) For equilibrium E  log Keq  0.59  log Keq
n 2
or log Keq  20  Keq  1020
 x  0.06
55.(A) 
E  2.37  0.45  
log  
 0.01  2
 
0.06 x
1.92  1.92  log  log100x  0  x  0.01
2 0.01
56.(C) M3   3e   M ; G   3  0.036 F
M  M2   2e ; G   2  0.439 F  M3  e  M2  , G  3  0.036  2  0439 F

 
 
1  F  E  0.108  0.878 F   E  0.77 V
57.(A) According to oxidation tendency.
0.06 pH   M2  
58.(B) Let E 2+  x : Ecell  Ecell  log 2  
M /M 2 2
 H 
 
0.06 1  0.1
 
1.5  0  x   log   x  0.03  x   1.47V
2 12
59.(B) Zn  Cu 2 

 Zn
2
 Cu
1M 1M
0.5M 1.5M
(1.5) 3
QC  
(0.5) 1
60.(D) Consider the concentration of Ag  ions is x
1
Cell reaction is H2 (g)  Ag   H (aq)  Ag(s)
2
0.059 [H  ] 0.059 1
Ecell  Ecell  log or 0.62  0.8  log

1 [Ag ] p H 1 [Ag  ]
2
0.059
log [Ag  ]   0.18  log[Ag  ]   3  [Ag  ]  10 3
1
100
So mass of Ag in solution   10 3  108  0.0108 g
1000
0.0108  100
Percentage of Ag in Alloy   1%
1.08

Vidyamandir Classes
61.(D) Initially by adding Ba(NO3 )2 to K 2SO4 the number of ions increases is very small amount but after
completion of the reaction the number of ions enormously. Thus conductance initially remain same or
increases with negligible amount and the it will abruptly increases.
62.(C) Mg 2   2e  Mg
2F C electricity produces 1 mole Mg
1
1C electricity produces mole Mg
2F
1
9.65C electricity produces   9.65 mol of Mg  5  10 5 mole Grignard reagent (1 mole
2  96500
mg = 1 mole Grignard).
63.(C) Cathode : Cu2  2e   Cu ;
Anode : 2H2O  O2  4H   4e   Solution will be acidic
 
64.(B) Na  e  Na
23g Na is obtained by 1F C electricity
F 1
230g Na is obtained   230  10 F C ; Cl   Cl2  e
23 2
1 1
1F C produces mol Cl 2  10F C will produce  10  5 mol Cl2
2 2
65.(A) Cathode  H 2(g) : Anode  O2 (g)
66.(C) Mn 2   2e  Mn ; G  2  1.18 F
Mn 3  e  Mn 2 ; G   1.51F
Mn 3   3e   Mn ; G  2.36  1.51 F     

3 F E  2.36  1.51 F  E    0.28
67.(A) E  E
Cl2 /Cl Br2 /Br 
So reduction of Cl2 will take place and bromine Br    is oxidised.

Thus cell reaction is Cl 2  2Br   2Cl   Br2
68.(D) E  0  0.059(pH)   59 mv
69.(A) Since only Ered of Zn 2 is less then E it reduces H ions to produce H2 gas from acidic solution.
H  /H2
70.(D) Rate constant is a kinetic property while E° is a thermodynamic property and thus do not have any direct
relationship.
71.(A) see electrochemical series.
0.06 [Cu 2 ]
72.(D) Ecell  E cell  log . From above equation, Ecell increases on increasing [Ag  ] .
2 [Ag  ]2
73.(C) From given data
Cu 2   2e   Cu ; E  0.34, G    2 F  0.34
Cu   Cu2  e  ; E   0.15 ; G   1F  0.15  

Cu   e   Cu ; G   0.53 F
 1  F  E   0.53 F  E   0.53 V
Now Cu   Cu2   e ; E   0.15 V
Cu   e   Cu ; E  0.53 V
2 Cu   Cu 2   Cu ; E  0.38 V

Vidyamandir Classes
74.(D) Ag | AgI| I || Ag  | Ag
Net cell reaction for this cell is Ag   I   AgI(s)

0.059 1
Ecell  E cell  log  
 0  0.8  0.152  0.059 log K sp
1 [Ag  ][I ]
(Since at equilibrium, Ecell  0 &  Ag   I    K sp )  log K sp   16.1

   
75.(C) MnO4  8H  5e   Mn 2   4H 2O
0.06 [Mn2  ]
E  E  log
5 [MnO4 ][H  ]8
 8
0.06  [Mn 2 ] [MnO4 ]  1  
E2  E1   log  
5  [MnO4 ][10 4 ]8 [Mn 2 ] 
 
0.06 32 0.06
E2  E1   log 10    32  E2  E1   0.38
5 5
Daily Tutorial Sheet 6 to 10 Level – 2 | JEE Advanced Pattern
76.(C) E 2  /Cr 3   1.33V;E  1.23V; E  1.51V;E   1.36V

Cr2 O7 MnO2 /Mn2  MnO
4 /Mn
2 Cl 2 /Cl 
 E  /Mn 2  is highest, KMnO4 is the strongest oxidising agent.

MnO4
77.(D) EO /O  2.07V; E  2.87V; E 

 /Mn 2   1.51V; ECl /Cl   1.36V
3 2 F2 /F  MnO4 2
 E is lowest, Cl 2 is the weakest oxidising agent.

Cl2 /Cl 
78.(AC) EZ is highest  strongest oxidising agent.
 EX  weakest oxidising agent

 Y will oxidise X but not Z. Also, Z will oxidise both X and Y.
79.(A) Cathode: AgBr(s)  e  Ag(s)  Br  (aq.) E  0.07 V
 
Ag(s)  Ag (aq.)  e
Anode: E   0.8 V
AgBr(s)  Ag  (aq.)  Br  (aq.)
0.059
At equilibrium: Ecell  0.07  0.8  log10 K sp
1
 log10 K sp  12.37  K sp  4  10 13
80.(B) Given cell: Cu|Cu2  (2M)||Ag  (2M)| Ag

It 1  96500
Number of faradays supplied   1
96500 96500
After cell has supplied 1.0 F electricity:
At Anode: Cu  Cu2  2e
 2 F electricity  1 mole Cu2 product
2  1  0.50
 1.0 F electricity  0.50 mole Cu2  product  [Cu 2  ]new   2.5M
1
At Cathode: Ag   e   Ag
2  1  1.0
 1F electricity  mole Ag  used  [Ag  ]new   1.0 M
1

Vidyamandir Classes
0.059 [Cu2 ]
Using: Ecell  Ccell  log10
2 [Ag  ]2
0.059 2 0.059 2.5
 (Ecell )1  E cell  log10 and (Ecell )2  Ecell  log10
2
2 2 2 12
0.059 0.059
 Change in Ecell  (E cell )2  (Ecell )1   log10 2.5  log10 2
2 2
0.059
 log10 5  0.0266V
2
81.(D) Write cell reaction: Zn(s)  2Ag  (1.25M)  Zn 2 (0.01M)  2A(g)
a 0.01
Q Zn 2    6.4  10 3
2
  (1.25)2
 a Ag  
 
82.(B) Zn(s)  Cu2  (aq.) 
 2
 Zn (aq.)  Cu(s)
 0.0591
Ecell  Ecell  log10 Q
2

At O, log10 Q  0  Ecell  Ecell  1.1V
0.0591 [Zn2  ]
When Ecell  1.1591V  1.1591  1.1  log10 Q  Q  10 2
2 [Cu2  ]
83.(D) Cu2  2e   Cu
0.059 1 RT
E  E  log10  E 2   ln[Cu 2 ]
Cu2  /Cu Cu2  Cu 2 2
[Cu ] Cu /Cu 2F
Intercept = 0.34 V  E  0.34 V

Cu 2  /Cu
0.059 0.059
 E  0.34   log10 0.1  0.31V  E  E  0.34  V
Cu 2  /Cu 2 Cu/Cu2  Cu 2  /Cu 2
84.(C) E° = 1.3 V
0.0591

EOxidation  EOxidation  log10 [H  ]2 = 1.3 + 0.059 pH = 1.3 + 0.059 × 2 = 1.42 V
2
85.(C) Higher the reduction potential, higher is the tendensy to get reduce
 Order of deposition will be Ag, Hg, Cu. And Mg will not be deposited
86.(AB) Clearly, O2 will be evolved in (A) and (B)
  Cu(s)  Cu2  (aq.)  2e E   0.34V 

 Cu/Cu2  
In (C), Cu will get oxidised.  

2H2O(l )  O2 (g)  4H (aq.)  4e
 E H O/O  1.23V 
 2 2 
  Ni(s)  Ni 2 (aq.)  2e  E  0.25V 
 Ni/Ni2  
In (D)  

 4OH (aq.)  O2 (g)  2H2O(l )  4e E  
 OH /O2 0.4V 
87.(AB) At Cathode:  Cu 2  2e   Cu E  0.34V

Cu2 /Cu
× 2H2O  2e   H2 2OH  d EH O/H  0.83V

2 2

Vidyamandir Classes
At Anode: 2Br   Br2  2e E  1.09V

Br  /Br2
× 2H2O  O2  4H   4e EH O/H  1.23V

2 2
It 2.68  1  3600
88.(AB) Number of Faradays    0.1
96500 96500
At Cathode: Cu 2 (aq)  2e   Cu(s)
 2F  1 mole Cu  0.1F  0.05 mole Cu = 0.05 × 63.5 gm Cu = 3.175 g Cu deposited
2
At Anode: Cu(s)  Cu (aq.)  2e
 2F  1 mole Cu  0.1F  0.05 mole Cu = 0.05 × 63.5 gm Cu = 3.175 gm Cu used.
4  1  3600
89.(ABC) Number of faradays   0.15
96500
Initially, moles of Fe3  0.1  1  0.1
First, Fe3 will get reduced to Fe2
Fe3  e   Fe2 
1F  1 mole Fe3 deposited  0.15 F  0.15 mole Fe3 deposited [> Fe3 available]
3
Thus, 1 mole Fe  1F
 0.1 mole Fe3  0.1F electricity is used  0.1 mole Fe2 produced
 0.15  0.1  0.05F of electricity left for the reduction of Fe2
Fe2  2e   Fe
2F  1 mole Fe2
0.05
 0.05F   0.025 mole Fe2 reduced  0.025 mole Fe deposited
2
 Fe2  left  0.1  0.025  0.075 moles

Paragraph for Questions 90 - 93
90.(B) M(s)|M  (0.05M)||M  (1M)|M(s)|E cell |  70 mV
0.059 0.05

Ecell  E cell  log10 0 (Ecell  0) ; Gcell  0
1 1
91.(C) M(s)|M  (0.0025M)||M  (1M)|M(s)
0.059  0.0025  0.059

Ecell  0  log10    log10 0.052  2  70 mV = 140 mV
1  1  1
It 0.3  15  60
92.(A) Number of Faradays    2.8  10 3 F
96500 96500
AuCl 4  Au(s)  Cl   3e
2.8 2.8
3F  1 mole Au  2.8  10 3 F   10 3 mole Au   197  10 3 gm Au  0.184 gm Au
3 3
93.(B) Volume of be covered  (0.25  10 4 cm 2 )  (2  10 3 cm)  5 cm 3
35.95
 Mass of Cr to be deposited = 5 × 7.19 gm = 35.95 gm  moles = 0.69 moles
52
E
Now, using w  It
F
WF 1 35.65  F 1
t  (hours)  t   3 hr
EI 3600 (52 / 3)[75] 3600
94.(A) E  E 2    ve 95.(B) Refer given E° values
A|A 2  B |B

Vidyamandir Classes
96.(ABD) Check Ecell . If Ecell  0 then the reaction is spontaneous.
(A) Ecell  0.8  0.34  0.46 V (2Ag   Cu  2Ag  Cu2 )
(B) Ecell  0.34  ( 2.37)  2.81 V (Cu 2  Mg  Cu  Mg 2 )
(C) Ecell  0.34  0.8  0.46 V (Cu 2  2Ag  Cu  2A  )
(D) Ecell  0.79  0.34  0.45 V (Hg 2   Cu  Cu 2  Hg)
In (A), (B) and (E), Ecell  0 which means that the respective solution in the respective vessel cannot be
stored.
97.(A) MnO4  8H   5e  Mn 2  4H2O
0.059  [Mn2  ] 
E  /Mn 2   E 2  log10  
MnO4 MnO
4 /Mn 5  [MnO ][H ]8 
 4 
8 0.059  [Mn 2 ] 
E 2   0.059 pH  log10  
MnO
4 /Mn 5 5  [MnO ] 
 4 
 If [H  ] is doubled i.e. pH is reduced by log10 2  0.3, then E 2 will be changed

MnO
4 /Mn
8
(increased) by 0.059  0.3 V  28.36 mV
5
98.(AB) Cell Reaction: Co(s)  2H (M2 )  Co2 (M1 )  H 2 (g)
0.059  [Co2  ] 
Ecell  E cell  log10   p H  Qcell 
2   2 2 
 [H ] 
(A) Increase in the volume (i.,e dilution) of COCl2 solution (i.e. decrease in [Co2  ] ) will cause Qcell
to decrease causing Ecell to increase
(B) Increasing M2 will cause a reduction in Q thus increasing Ecell
(C) Increasing p H will increase Q thus reducing Ecell

2
(D) Increasing M1 will increase Q thus reducing Ecell
99.(BC) E  0.28 V; E   0.4 V; E  0.44 V; E  0.76 V; E 0 V

Cu 2  /Co Cd2  /Cd Fe2  /Fe Zn2  /Zn H /H2
Using: Ecell  (E reduction )cathode  (Ereduction )anode
(A) Ecell  0.44  ( 0.28)  0.16 V (B) Ecell  0.4  ( 0.44)  0.04 V
(C) Ecell  0.28  ( 0.4)  0.12 V (D) Ecell  ( 0.76)  0  0.76 V
100.(CD) Aqueous Zn(NO3 )2 :
Cathode:  Zn2  (aq.)  2e   Zn(s) E  0.76 V

Zn2  /Zn
× 2H   3e   H2 (g) ( E  0V )
Anode:  2H2O(l )  O2(g)  4H  (aq.)  4e  EH O/O  1.23 V

2 2
× NO3  X
101.(A) Refer your notes on conductance. The question is related to variation of conductance using strong
acids and strong bases.

Vidyamandir Classes
102.(B) Initially neutralization of HCl will decrease conductance of the solution ; later neutralisation of
CH3COOH will increase conductance by small amount and after equivalent point it will increase
sharply.
It 2  965
103.(A) Number of faradays    0.02
96500 96500
Anode: 2H2O(l )  O2 (g)  4H  (aq.)  4e 
 4F electricity  1 mole O2  22.4L O2 at STP
0.02
 0.02F electricity  22.4   0.112 L O2 at STP
4
104.(B) Cathode (R.H.E): 2H2O(l )  2e   H2 (g)  2OH  (aq.)
Anode (L.H.E): 2H2O(l )  O2(g)  4H  (aq.)  4e 
In R.H.E., OH  will be produced which will react with NH4 (salt) to form NH4OH (base), causing pOH
to decrease or pH to increase.
In L.H.E., H will be produced which will react with NH4OH (base) to form NH4 (salt), causing pOH to
increase or pH to decrease.
105.(C) Refer to conduct metric titrations topic in Electrochemistry-III.
106.(AB) Cell reaction: Zn(s)  2H  (aq.)  Zn 2 (aq.)  H 2 (g)
0.0591
 pH  [Zn 2 ] 
Using: Ecell  E cell  log10  Qcell  2 
  
For Ecell  Ecell ,Qcell  1.0
2  [H  ]2 
 
11 1  0.01 11
(A) Qcell  1 (B) Qcell  1 (C) Qcell   100
12 (0.1)2 (0.1)2
107.(B) In the production of Al (in Hall’s process), reactions are:
Cathode: Al 3  3e  Al
Anode: 2O2   O2  4e
C  O2  CO2
108.(A) 
 r Gcell 
  ncell FEcell  12  96500  2.73  3.16  10 3 kJ mol 1
109.(AC) If E  0.44 V & E  0.33V then oxidation of M and reduction of X will be
M  /m X/X 
spontaneous.
Ecell  0.33  [0.44]  0.77V  
M  X   
 M  X is the spontaneous reaction
110.(C) Ionic mobilities of K  and NO3 are approximately same.
111.(A) For concentration cells
(a) Ecell  0, QC  1
(b) For spontaneous cationic concentration cell, their must be EXPANSION of the gas during the
reaction

H2  2H  H2  2H

A C C A
QC 
P H2
C
P H2
A

Vidyamandir Classes
2
(c) Zn aq can be reduced to Zn on using some electrodes like Fe cathode. It is due to over potential
concept.
(d) For electrolysis in an aqueous solution. Au , Pt and graphite can work as an inert electrode.
Paragraph for Questions 112 - 114
2
112.(C) X X Y 2 Y
(0.1M) (1M)
0.059 0.1 0.059
Ecell  0.59  log  0.59   0.62V
2 1 2
113.(B) 2 × 0.34 = 0.15 + ?
0.68 – 0.15 = ?
0.53 V = ?
114.(C) YI  e Y E  0.27V
  I
Y  Y
  e E  0.53V
YI  Y
  I E  0.80V
G  nf Ecell  2.303 RT log ksp
Ecell  0.059 log ksp

0.80
 log ksp –13.56 = log ksp
0.059
Ksp = antilog (–13.56)  2  10 14
115.(D) Cd(s)|CdCl2 (0.1M)| AgCl/Ag(s) is equivalent to; Cd(s)|Cd2 (0.1M)||Cl  (0.2M)/AgCl(s) / Ag(s)
 dEcell 
Use: H  nF  T   E cell 
 dT 
  0.6753  0.6915   1
H25C  2  96500 298     0.6753   167.6 kJ mol
  25  0  
 E  S
116.(A)     S  1.5  104  2  96500  28.95 J/K
 T P nF
5 3 7

117.(D) 2ClO3   
 CiO2  ClO4
The reaction includes to steps.

ClO3  
 clO4 [oxidation] , 
ClO3  
 ClO2 [Reduction]
E  0.36V E  0.33V
 ERxn  0.33  ( 0.36)  0.03 volt
0.0600
as ERxn  log10 Kcal
n
Here n  2 (n-factor of the reaction)
0.03  2 0.06
log10 Kcal    1  Kcal  0.1
0.0600 0.06
118.(C) NO3  4H   3e  NO  2H 2O , E  0.96V
NO3  4H   3e  NO  2H2O , E  0.96V

1M 5M – –
After 80% completion
4
0.2M 1.8M 4 bar QC 
0.2[1.8]4

Vidyamandir Classes
0.06 20
Eelectrode  0.96  log QC  0.96  0.02 log  0.96  0.02 log1.90  0.954 V
3 10.9
119.(D) Ag   e  Ag
1
2OH  H2O  O  2e  Eq. of Ag  lost = 0.1 = Eq. of O2 formed and escaped
2 2
0.1  32
 Total mass loss  0.1  108   11.6  Mass of solution = 108 – 11.6 = 96.47
4
120.(B) Ecell  EOP  ERP  0.76  0.41  0.35 V
Zn Fe
121.(D) 2e   Cu2   Cu; G1  2  0.34  F
Cu   Cu 2  e ; G2  1  ( 0.15)  F

+ + + +
e  Cu   Cu; G3  1  E3  F
G3  G1  G2


 0.68F  0.15  F  E3  0.53V
Now, for 2Cu  Cu  Cu2

E  E OP  ERP = – 0.15 + 0.53 = + 0.38 V 122.(B) Mn7   5e   Mn2 
Cu|Cu2  Cu|Cu
123.(A) [2e  Fe2  Fe]  3
[2(Fe3  )  6e   2Fe]  1 Thus, ratio of Fe3 : Fe2  is 2 : 3
0.059 [Cr 3 ]R.H.S. 0.059 1

124.(A) E log  log  0.028 V
3 [Cr 3 ] 3
L.H.S.
[0.04]
2 
Cu (aq)  2e  Cu(s)
125.(B) Cu(s)  S2 (aq)  CuS(s)  2e
Cu2  (aq)  S2 (aq)  CuS(s)

0.059 0.059
E E  log K SP  0.34  log10 35 = – 0.34 + 1.0325 = 0.963 V
Cu|CuS|S2  Cu|Cu 2  2 2
Daily Tutorial Sheet 11 Numerical Value Type for JEE Main
126.(1.63) From om   CH3COOH

 o
CH3COO
 o   349  41  390 Scm 2 mol 1
H
C( 2 ) 0.04  (0.02)2 m 7.8

and K a    1.63  10 5 (    0.02 )
(1   ) (1  0.02) om 390
 K a  105  1.63
W1 E1 1.008 1.008
127.(8.0 g) From   
W2 E2 W2 8
W2  8.0 g
128.(2) The cell will be
Al(s) | Al 3 (aq)||Cu2  (aq)|Cu(s)
E ocell  EoR  E oL  E  Eo  0.34  (1.66)  2.00 V

Cu2 |Cu Al 3 |Al
129.(24)   nFE  2.303 RT log K

 nE 
 K  anti log  
 0.059 

Vidyamandir Classes
10  0.15  25
K  anti log    2.4  10  K  10 24  2.4  1025  10 24  24
 0.059 
130.(13)  Electrolysis of NaCl gives H2 (g) at cathode and O 2 (g ) at anode, the electrolyte solution contains
NaOH after electrolysis
0.04  1000
 Number of equivalents of NaOH formed = 0.04  N  0.1
400
[HO ]  0.1M  pOH   log[HO ]  1 So pH  13
131.(1.24 V)
G0 nFE
 Efficiency  
0 H
H
2  E  96500
0.84   E  1.24 V
285  1000
132.(6) m  133.(1) H2  2H  2e
 eq   n  factor  m  6
n  factor eq
0.059 [H  ]2
2 E log
Ca 3(PO4 )2  3Ca  2PO43 2 pH
2
0.059  0.059pH
pH  1
134.(6) 135.(1)  q  ne
Cr2O72   2Cr 3
n-factor  3  2  6
 6.24  1018  1.6  10 19  1
So for 1 mol of Cr2O72, 6F required.
136.(6)  Cr  Cr 3   3e  ........ (i)
Fe2   2e   Fe(s) ........ (ii)

Cell reaction is : (i)  2  (ii)  3 we get
2Cr  3Fe2   2Cr 3   3Fe  n6
 3 
137.(6.84)  M M  2e ; E   0.25 V
  G  for above reaction is  nFE  48.25 kJ / mol
330.03
So the number of moles of M  oxidised from ( X  Y )   6.84
48.28
138.(178) oCX  oCA  oBX  oBA  120  198  140  178
139.(89.2)  K a  c2  0.01  (0.05)2  2.5  10 5
Ka m
  0.0223 ; 
c om
 m    om  0.0223  4  10 2  89.2  10 5   m  105  89.2  10 5  105  89.2

140.(0.05) Zn(s)| ZnSO 4 (C1 )||CuSO 4 (C2 )|Cu(s)
0.06 C1
E1  E  log …….(1)
2 0.5
and student II:
Zn(s)| ZnSO 4 (C1 )||CuSO 4 (C2 )|Cu(s)
0.06 C1
E2  E  log ………(ii)
2 C2
0.06  C C  0.06   0.5  

 E1  E2   log 1  log 1   0.03  log    C 2  0.05
2  C2 0.5  2   C 
  2 

Vidyamandir Classes
Daily Tutorial Sheet 1 to 2 JEE Main (Archive)
1.(D) 2H2  4OH (aq.)  4H2O(l)  4e
O2 (g)  2H2O(I)  4e  4OH (aq.)

o
2H2  O2 (g)  2H2O(l) E cell   ve
Fuel cell involves direct conversion of chemical energy to electrical energy.
2.(C) Eocell  Eo  Eo  0.14  0.77  0.91V
OPSn/Sn 2  RPFe3  /Fe2 
0059 0.059
3.(C) Eocell  log K c  0.591  log K c  K c  1  1010
1 1
4.(A)  oNaBr   oNaCl   oKBr  KCl
o
 126  152  150  128 S cm 2 mol 1
5.(C) 
Zn(s)  2H (aq)  
 Zn (aq)  H2 (g)
0.059 [Zn2  ][H2 ]
Ecell  Eocell  log
2 [H ]2
Addition of H2SO4 will increase [H ] and Ecell will also increase and the equilibrium will shift towards
right.
6.(A) Cr 2  |Cr 3   0.41 V
Mn 2 |Mn 3  1.57 V  Fe2 |Fe3  0.77 V  Co2 |Co3  1.97 V

More is the value of oxidation potential more is the tendency to get oxidised.
As Cr will have maximum oxidation potential value, therefore its oxidation will be easiest.
7.(A) For a spontaneous reaction
G   ve So, Eocell   ve as G   nFE ocell and G   RT ln K

G   RT  2.303 log K As G    ve So, K > 1
8.(C)  AcOH  
AcONa  
HCl  
NaCl
 91.0  426.2  126.5  390.7 S cm 2 mol 1

9.(D) According to Kohlrausch’s law:
 oCH  oCH  oHCl  oNaCl
3COOH 3COONa
0.059
10.(D) Eo  Eo  log K SP
I AgI/Ag Ag  /Ag 1 AgI
0.059
0.152  0.8  log K SP
1 AgI
log K SP  16.13
AgI
11.(D) C  0.1 M, R  100 ohm,

1 l l
  1.29 ohm 1m 1,        R  1.29  100 ohm,
R a a
C = 0.02 M, R = 520,
1 l 1
    129  0.248 ohm 1m 1
R a 520
 decreases with dilution.  C = 0.02 and not 0.2
1
Also,    
M(in m / L)
1 0.248  1
    12.4  10 3 S m 3 mol 1  124  10 4 S m 2 mol 1
3 3
M  10 (m / m ) 0.02  10 3

Vidyamandir Classes
0.0591
12.(C) Ecell  Eocell  log Q
n
[Zn 2 ]
Where, Q 
[Cu2 ]
For complete discharge, Ecell  0
0.0591  [Zn 2 ] 
So, Eocell  log  
2  [Cu2 ] 
 
0.0591  Zn 2    Zn 2   2  1.1  Zn 2  
Eocell  1.10V  1.10  log    log    log    37.3
2 2
 Cu   2 
 Cu  0.0591  Cu 2  
     
  Zn 2  
    37.3
   2    10
  Cu  

13.(A) From Kohlrausch’s law,
 oCH  oCH  oHCl  oNaCl
3COOH 3COONa
14.(A) As Eo  0.72V and Eo  0.42V

Cr 3  /Cr Fe2  /Fe
2Cr  3Fe2  3Fe  2Cr 3

2
0.0591 0.1 0.0591 [0.1]2
Ecell  Eocell  log   ( 0.42  0.72)  log
6  Fe2 
3 6 [0.01]3
 
0.0951 [0.1]2 0.0591
 0.30  log  0.30  log10 4  Ecell  0.2606V
6 [0.01]3 6
G 702.6
15.(D) Efficiency of fuel cell ( )    100  97%
H 1  726
16.(C) It is given that, Fe3   3e  Fe; E1o  0.036V …..(i)
Fe2   2e   Fe; Eo2  0.439V …..(ii)

We need to calculate
Fe3   e  Fe2  ;E o3  ? …..(iii)
Equation (iii) can be obtained by subtracting Eq. (ii) from (i) but E0 being an intensive property, cannot
be calculated by this way. In order to calculate Eo3 , concept of G is used.
G1o for Eq. (i) is given by
G1o  3  F  ( 0.036)  G1o  0.108 F
Go2 for Eq. (ii) is given by
Go2  2  F  ( 0.439)  G o2  0.878 F
Go3 for Eq. (iii) is given by
Go3  1  F  Go3  Go3  G1o  Go2  1  F  Eo3  0.108 F  0.878 F  Eo3  0.770 V
2 4
17.(C) Al 2O3  al  O2
3 3
2
Thus,  3(O2 )
3
i.e., 2O2   O2  4e  [ n  4]

Vidyamandir Classes
G  966 kJ mol 1  966  10 3 J mol 1  G  nFE cell

3
 966  10  4  96500  Ecell  Ecell  2.5V
18.(B) For hydrogen electrode,
1 0.0591 (p H )1/2
H (aq)  e  H2 (g)  E  E  log 2
2 n [H ]
0.0591 (p H )1/2
2
Here, n = number of electrons involved in the reaction E  E  log
1 [H ]
(PH )1/2 (PH )1/2
E  0.0591log 2
[E  0 for H  electrode]  E will be –ve when 2
is +ve.
[H  ] [H ]
i.e., (PH )1/2  [H ]
2
PH [H ] (PH )1/2 / [H  ] E red

2 2
(a) 1 atm 2.0 M 0.25 + ve

(b) 1 atm 1.0 M 1.0 0
(c) 1 atm 1.0 M 2.0 – ve
(d) 1 atm 2.0 0.50 + ve

Hence, when is 2 atm and [H ] is 1.0 M, E red is negative.
19.(D) A cell reaction is spontaneous, if G  0 .
Since, G   nFEocell
Thus, Eocell  0,Eocell  Eoox  Eored
(a) X  Ni, Y  Fe
2
Ni  Fe  X 2  Fe
E0  0.23 V
Ni/Ni2 
E0  0.44 V
Fe2  /Fe
Thus, Eocell  Eo  Eo  0.21 V  E0cell  0

Ni/Ni2  Fe2  /Fe
i.e., reaction is non-spontaneous.
(b) X  Ni, Y  Zn
Ni  Zn 2   Ni 2   Zn
E0  0.23 V
Ni/Ni2 
E0 2   0.76 V
Zn /Zn
 Eocell  0.23  ( 0.76)  0.53 V  Eocell  0

(c) X  Fe, Y  Zn
Fe  Zn 2   Fe2   Zn

Vidyamandir Classes
Eocell  E o  Eo  0.44  0.76  0.32 V  Eocell  0

Fe/Fe2  Zn 2  /Zn
(d) X  Zn, Y  Ni
Zn  Ni 2  Zn 2  Ni
Eocell  Eo  Eo
Zn/Zn 2  Ni2  /Ni
 0.76  0.23  0.53V  Eocell  0

i.e., reaction is spontaneous.
20.(C) Higher the SRP (Standard Reduction Potential), stronger is the oxidizing agent Among the given, electrode
potentials, Eo is highest.
MnO4 /Mn 2 
Hence, MnO4 is the strongest oxidizing agent.
21.(B) Mn 2   2e   Mn; E  1.18 V ….(i)

3  2
2(Mn  e  Mn ); E  1.51 V ….(ii)
Subtracting Eq. (ii) from Eq. (i), we get
3Mn2   Mn  2Mn 3
E   1.18  ( 1.51)  2.69 V
Since, the value of E is – ve, therefore the reaction is non-spontaneous.
Alternate method :
Mn 2   2e   Mn, E  1.18 V …(i)

G  nFE [here, n = number of e involved in the reaction]
G1o  2F( 1.18)  2.36 F
2Mn 3   2e  2Mn 2  ,E  1.51 V …(ii)

Go2  2F[ 1.51]  3.02 F
Subtracting Eq. (ii) from Eq. (i), we get
Mn 2   Mn  2Mn 3  , [n  2]
Go3  G1o  Go2  5.38 F  2FE   5.38 F  E   2.69 V
22.(D) Debye–Huckel Onsager equation can be written as
c    (B) C
Where, c = Molar conductivity of the solution at certain concentration
 = Limiting molar conductivity
C=
Concentration
B=
Constant that depends on temperature, charges on the ions and dielectric constant as
well as viscosity of the solution
23.(B) For 0.2 M solution, R  50
  14 S m 1  1.4  10 2 S cm 1
The resistivity of the solution is related to specific conductance by
1 1
  m
 1.4  10 2
l
It is known that, R  
a
R l l 1
   R  50  1.4  10 2 cm
 a a 
For 0.5 M solution,

Vidyamandir Classes
R  280 
l
?   50  1.4  10 2 cm
a
The specific conductance of the solution is given by
1 1 l
  
 R a
1
  50  1.4  10 2  2.5  10 3 S cm 1
280
Now, the molar conductivity of the solution is given by
  1000 2.5  10 3  1000
m    5.5 cm 2 mol 1  5  10 4 S m 2 mol 1
M 0.5
Hence, the molar conductivity of 0.5 M solution of the electrolyte is 5  10 4 S m 2 mol 1 .
24.(B) Cu2  2e  Cu
2F i.e. 2 × 96500 C deposited Cu = 1 mol = 63.5 g
25.(D) EMF of galvanic cell = 1.1 V
If Eext  EMF , then electrons flow steadily from anode to cathode while if Eext  EMF , then electrons
flow in reverse direction and cell behaves as an electrolytic cell in which copper electrode behaves as
anode and zinc electrode behaves as cathode.
26.(C) MnO4  8H   5e  Mn 2   4H2 O
0.059 [Mn 2  ]
E  E  log
n [MnO4 ][H  ]8
Taking [Mn 2  ] and [MnO4 ] in standard state i.e., 1 M.
0.059 1 0.059 0.059
E  E  log  8
 1.51   8  pH  1.51   8  3  1.227 V
n [H ] n 5
So, MnO4 will oxidise only Br  and I  as standard reduction potential of Cl 2 / Cl  (1.36 V) is greater
than that of MnO4 / Mn 2  .
27.(C) Galvanization means applying a coating of zinc metal to prevent corrosion.
28.(A) At anode :
CH 2  COO  CH2  COO  CH2
| 2e   |   2 CO2  ||
CH 2  COO  CH  COO  CH2
 2 
2F produce 1 mole of ethene gas and 2 moles of CO2 gas. Therefore, 0.2 F produce 1 mole of H2.
Therefore, 0.2 F will produce 0.1 mole of H2 gas.
Hence, total number of moles of gases produced at anode and cathode is 0.2 + 0.1 + 0.1 = 0.4
nRT 0.4  0.0821  272
V    8.96 L
P 1
29.(C) When an impermeable barrier is formed at the surface of iron then oxygen and moisture cannot attack
the metal hence, its corrosion is prevented.
30.(C) More negative the E value of the species, more stronger is the reducing agent.
Since, E  0.74 V (most negative among the given examples), Cr is the strongest reducing
Cr 3  /Cr
agent.
31.(D) For the given reaction : Fe3   e   Fe2  ; E  0.77 V
Fe3  /Fe2 
G  nFE
G1  0.77 F . . . .(i)

Vidyamandir Classes
For the reaction

Fe2   2e   Fe; E  0.47 V ; G2  2( 0.47)F  0.47  2F . . . .(ii)
Fe2  /Fe
Overall reaction : Fe3   3e  Fe ;

G3  3FE3 . . . .(iii)
G3  G1  G 2
3FE 3  0.77 F  0.47  2F
0.17
E3    E3  0.057 V
3
0.057 [Mn 3  ]
32.(A) Ecell  Ecell  log
n [Ag  ]3
0.059 0.001
0.421  Ecell  log
3 (0.01)3
0.059
Ecell  0.421   3  0.480 V
3
Ecell  E  E
Ag  / Ag M3  / M
0.480 V  0.8 V  E  0.32 V

M3  / M
33.(C) B2 H6  3O2  B2O3  3H2O

27.66g 96g
Thus, for combustion of 27.66 g of B2H6 oxygen required is 96g. According to Faraday's law of
electrolysis,
EIt 8  100  t
w  ZIt   96 g 
96500 96500
96  96500 11580
t  11,580 s   3.2 h
8  100 3600
34.(B)
2H   2e   H2 (at cathode)

EIt
w  ZIt 
96500
112
Moles of H2 deposited =
22400
112
Mass of H2 deposited (w) = Moles  molar mass 2
22400
112 1  I  965
Thus, 2   I  1A
22400 96500
35.(D) Molar mass of p-aminophenol  6  12  7  1  14  16  109 g mol 1

Equivalent weight  I  t
109 9.65  1  60  60
W     9.81g
96500 4 96500
36.(D) 2F of electricity is used for 1 mol of PbSO 4 i.e. 303 1g of PbSO 4 .
303  1
 0.05 F of electricity is used for  0.05 g of PbSO4  7.6g
2
37.(C) G  G  RT lnQ

Vidyamandir Classes
At equilibrium
G  0 and Q  K
So, G   RT ln K
 nFE 0   RT ln K 2  96500  2   8  300 ln K
ln K  160
K  e160
38.(C) Pt (s)| H2 (1bar)| HCl(aq)||AgCl(s)| Ag(s)| Pt (s)
 
Anode Cathode
 
At A : H 2  2H  2e
At C : (AgCl  e  Ag  Cl  )  2
H2  2AgCl  2HCl  2Ag
0.92  E0cell  0.06 log (10 6 )2  0.92  E0cell  0.06 ( 12)  0.92  E0cell  0.72
E0cell  0.20  (E0c  E 0A )r  0.2   E0A  0   [E0C ]r  0.2V
39.(D) E0cell is an intensive property
E0cell  E0cathode  E 0anode
Since E0 has maximum Standard Reduction Potential, E0cell will be maximum
Au3  / Au
Zn(s) Zn 2 Au3  Au(s)  E0cell  1.40  (  0.76)  2.16 V

40.(B) G   nFE   2  9600  2   384000   384 kJ
dE
S  nF  2  96000  (  5  10 4 )   960000  10 4   96 J
dT
 TS  300  (  96)   28800   28.8 kJ  G  H  TS (at constant T and pressure)
 H   384  (  28.8)   412.8 kJ
41.(B) HA  HCl  NaA   NaCl
 425.9  100.5  126.4  400 S cm 2 mole 1
K  1000 5  10 5  1000
   50
M 0.001
 50
 
 0.125

 400
0.059
42.(D) E0 cell  log k eq
n
0.059
E0cell  log (10  1015 )  0.4736 V
2
43.(A) EZn/ Zn2  :  0.76  ECa/Ca 2  :  2.87  E :  2.36
Mg/Mg 2 
ENi/ Ni2  :  0.25 Reducing power Ca > Mg > Zn > Ni

44.(C) Conductivity  Concentration
1
Molar conductivity 
Concentration
2 2
45.(B) Cu  Zn  Zn  Cu
n2
G   n f Ecell  2  96500  2  386 kJ
46.(A) Greater is the reduction potential, stronger is the oxidizing agent.
47.(C) Oxidising power is directly proportional to SRP.
48.(D) No. of ions HCOOHaq > C6H5COOH > CH3COOHaq.

Vidyamandir Classes
(A) (C) (B)

Conductivity  no. of ions.  A>C>B
49.(B) If G   0 then K eql  1
50.(B) By passing 0.1 Faraday electricity, 0.1 gm-equivalents of Ni 2 will be discharged.

Number of gm-equivalent = (n – factor) × number of moles
 0.1 = 2 × number of moles  Number of moles  0.1/ 2  0.05
2
51.(C) Fe  Fe G10  2Fy
Fe3  Fe G02  3Fz  0

Fe 2   Fe 3  G3  1FE
0
G03  G10  G 02
 FE  2Fy  3Fz  E   2y  3z
For given cell reaction.
Fe2  aq  Ag  aq  Fe3  aq  Ag s
      
E0cell  x  2y  3z
52.(B) Molar conductivity versus c

K is less hydrated than Na  so  m for K  is more than  m of Na  .
53.(C) ( 0m )NaBr  ( 0m )NaI will be equivalent to 0m   Br 

 
0
 m
I
2 2
54.(2.15) Sn  s  |Sn  aq,1M  ||Pb  aq,1M  |Pb  s 
2 2
Overall cell reaction Sn
s   Pb aq   Sn aq   Pbs 
 Sn 2  
0.06  
E  E  log 
2  Pb2  
 
E  0.13  0.14  0.01V
At equilibrium, E  0
Sn2   Sn2   Sn 2  
    1  
0  0.01  0.03 log   0.01  0.03 log    l og 
Pb2   Pb2   3 Pb2  
     
Sn 2  
 
 101/3  2.15
Pb2  
 
55.(5.67) Ag   e   Ag 
1F charge deposits 1 mole Ag i.e. 108 gm Ag
 Quantity of electricity required = 1 F
1
H2O  O2  2H  2e
2
1
Here 2 F charge  mole O2
2
1
So, 1F charge  mole O2
4
1
n O RT  0.08314  273
VO  2
 4  5.674 litre
2 P 1
56.(–0.93) 2H2O  O2  4H  4e  Eored  1.23 V

Vidyamandir Classes
o 0.059 4
Eoxid  Eoxid  log H 
4  
0.059 0.059 0.059
Eoxid  1.23  log(10 5 )4  1.23  log10 20  1.23   ( 20)
4 4 4
 1.23  0.295
 0.935V
57.(A) Eo  0.34V Eo  0.522V
Cu2  /Cu Cu  /Cu
Cu   2e  Cu E   0.34 V -(1) Eo ?
Cu2  /Cu 
Cu   e  Cu E  0.522V -(2)
  o
Cu  e  Cu E ?
(1) - (2) 
Cu   2e  Cu E  0.34V -(3)
 o
Cu  Cu  e E   0.522V -(4)
Cu   e  Cu E  ? -(5)
G3  G4  G5  G    nFE  G3   2  F  .34 G4   1  F  522  

G4   1  F  E
 2F  .34   1   .522    1  F  E 

E   0.158V
n n
Cr 3 e
58.(60) 
2 6
1 1 It 1 2  8  60 1
 n  n     
Cr 3 3 e 3 F 3 96000 300
1 52
m   52  gm
Cr 3 300 300
m actual 0.104
% efficiency   100   100  60%
m theoretical  52 
 
 300 
59.(142)
Stopping potential  Ecell  xv  (KEe )max  x eV
H2 (g)  2H  (aq)  2e 
2AgCl(s)  2e   2Ag(s)  2Cl  (aq )
H2 (g)  2AgCl(s)  2H  (aq )  2Cl  (aq)  2Ag(s)
0.06
Ecell  (0.22  0)  log(10 1 )2  (10 1 )2
2
0.06
 Ecell  0.22   2 log10 2
2
 Ecell  0.22  0.12  0.34 V  (K.E)max  0.34 eV
 E i  (K.E e )max  (w 0 )Na  0.34  2.3  2.64 eV (where E i = Energy of incident Photon)
Now, E i  (K.E e )max  (w 0 )K  (K.Ee )max  (2.64  2.25)  0.39 eV

Vidyamandir Classes
0.06
 (Ecell )new  0.39 V  (0.22  0)  log[H ]2[Cl  ]2
2
0.06
 0.17   log[H ]4 Since [H  ]  [Cl  ]
2
0.06 0.17 17
 0.17   4pH  pH    1.42  142  10 2  142
2 0.12 12
60.(D) For strong electrolyte on increasing the temperature the mobility of ions increases but to very less extent.
For a small change in temperature, conductivity of strong electrolyte remains almost constant.
61.(A) This graph is for CH3COOH because on dilution, more CH3COOH molecules dissociate which will
increase the number of ions and also the mobility.

62.(–6) G  nF E 0cell
G 17.37  1000

E0cell     0.06 V  6  10 2 V
nF 3  96500
63.(B) Amount of charge transfer in 15 min
 15  60  1  900 C
900
900C   10 3  9.326 m moles of e
96500
Available millimoles of Au 1 = 25 mM
Available millimoles of Ag 1 = 25 mM
As charge consumed is less than charge required to completely deposit Au 1 ions than only Au will be
deposited.
64.(96500)
0.059 [Cu 2  ]
Ecell  Ecell  log10
2 [Sn 2  ]
Ecell  Ecell  0  [Sn 2 ] = [Cu2  ]=1M  = –0.16 – 0.34 = –0.5 V

 
G   nF Ecell = –2 × 96500 × (–0.5) = 96500 J
65.(A) Zn does not dissolve at Zn electrode when E ext  1.1V

66.(144.00) Cu aq  e   Cu E  0.52V
  s 
Cu aq  Cu2aq

 e E   0.16V
   
_______________________________________
2Cu aq  Cu 2aq

 Cu E  0.52  0.16  0.36V
    s 
RT
E  ln k
nF
0.025
0.36  ln k  n  1
1
ln k  144  10 1
67.(D) Cu(s) Cu 2 (C1M) Cu 2(C2M) Cu(s)
In this concentration cell, Ecell  0,

Vidyamandir Classes
0.059 C1
So, Ecell   log
2n C2
And if G is to be negative that means Ecell should be positive and it is possible when C1  C2
WKClO 10 5
3
68.(11) n KClO   mole  mole
3 M KClO 122 61
3
5
n  n KClO  mole
ClO3 3 61
So, 1 mole of ClO3 transfers 6 moles of e
5 65
mole of ClO3 transfers  moles of e  0.492 moles of e
61 61
Q  0.492  96500  47478 C
0.6  I  t  47478
47478
t hrs  10.99 hrs  11 hrs
0.6  2  3600
Daily Tutorial Sheet 1 to 5 JEE Advanced (Archive)
1
1.(A) Reducing power 
reduction potential value
Zn is the strongest reducing agent among the given options. The substance having smaller value of the
reduction potential are better reducing agent.
9.85
2. Moles of Au deposited   0.05
197
 gram equivalent of Au deposited  0.05  3  0.15
Now, according to Faraday’s law of electrolysis, if same quantity of electricity is passed through different
cell connected in series, same number of gram equivalents of electrolytes are discharged at respectively
electrodes.
63.5
 gram equivalent of Cu deposited = 0.15  amount of Cu deposited  0.15   4.7625g
2
0.15  96500
Also, coloumbs passed = 0.15  96500  I  5  60  60  I  0.80A
5  36 00
3. For conductivity, charge carriers are required. In anhydrous state, HCl is not ionized and no charge
carrier ions are available, hence Anhydrous HCl is a bad conductor of electricity. However, in aqueous
solution, HCl is fully ionized producing H  and Cl  and thus conducts electricity.
4. (i) The cell reaction is Zn  Cu 2   Zn 2   Cu
(ii) Ecell  Ecathode


 Eanode  0.350  (  0.763) 1.113V
 Both Zn 2 and Cu2 are at unit concentrations E  E  1.113 V

(iii)  Ecell 1.113V  0
G   nEF  0
Therefore, the cell reaction is spontaneous.
W1 E1 Z it Z E
5.(C)   1  1  1
W2 E 2 Z 2 it Z2 E2
Here E1 and E2 are equivalent weights of the ions.

Vidyamandir Classes
6.(D) Charge of one mole of electrons = 96500 C

 1 gram equivalent of substance will be deposited by one mole of electrons.
7.(C) The reduction potentials (as given) of the ions are in the order :
Ag   Hg 22   Cu 2   Mg 2 
Mg 2  (aq.) will not be reduced as its reduction potential is much lower than that of water (– 0.53 V).
Hence the sequence of deposition of the metals will be Ag, Hg, Cu.
1
8.(C) H2g  AgCl(s)  H (aq)  Cl  (aq)  Ag(s)
2
There is oxidation of hydrogen and reduction of silver, therefore it occurs in the following cell :
Pt| H2g |HCl(Soln)| AgCl(s)| Ag
0.005
9. Volume of Ag coating  80 cm 2  cm  0.04 cm 3
10
 mass of Ag coating = 0.04 × 10.5g = 0.42 g
0.42 0.42
 gram equivalent of Ag  = number of Faraday’s   96500C  3  t  t 125s
108 108
10. At anode : Zn  Zn 2  2e  E  0.76V
At cathode : 2H   2e   H 2 (g) E  0.00 V
 For Zn  2H   Zn2   H2 (g) E  0.76 V

2
0.0592 [Zn ] 2(E  E) 1
E  E  log    log [log[Zn 2  ]  2 log
 2
2 [H ] 0.0592 [H  ]
1  16.2
 16.2   log(0.1)  2pH  pH   8.6
2
11. For 1.0 L H2SO4 :
39 20
Initial mass of H2SO4  1294   504.66 g ; Final mass of H2SO4 1139   227.80g
100 100
 H2SO4 consumed/litre = 504.66 – 227.80 = 276 g
969.01
 Total H2SO4 used up = 276.86 × 3.5 = 969.01 g  mol  9.888 mol
98
 1 mole of H2SO4 is associated with transfer of 1.0 mole of electrons, total of 9.888 moles of
electrons transfer has occurred. Coulomb produced = 9.888 × 96500
9.888  96500
Ampere – hour =  265 Ah
3600
10
12. 100W lamp will produce 100Js1  100J 110  C  C Coulombs
11
10
Therefore, total Coulomb passed in 10 h   10  60  60  32727.27 C
11
32727.27
Number of gram equivalent of Cd2+ deposited   0.34
96500
112.4
Weight of Cd deposited  0.34  g 19.1g
2
67.2
13. Total number of gram equivalent of H2 used  6
11.2
63.5
 6  96500  15  60  I  I  643.33 A ; Mass of Cu deposited  6  g  190.50g
2
14.  Emf = 0.118 V > 0, it is galvanic cell and anode is negative electrode :
At anode : H2 (g)  2H (106 M)  2e

Vidyamandir Classes
At cathode : 2H  (x)  2e   H2
Cell reaction : H (x)  H (10 6 M)

10 6
Emf = 0.118 V = 0 – 0.0592 log  x  10 4 M
x
1
15. 
H2O  e   H2  HO ; E   0.8277 V
2
1

H2  H2O  
 H3O  e

; E  0V
2

2H2O  
 H3O  HO

E   0.8277 V
E   0.0592 log K
0.8277
 log K   13.98  K 1.04  10 14
0.0592
16. If the salt is CuSO4
During deposition of Cu at cathode, O2(g) will evolve at anode. Gram-equivalent of Cu deposited
0.4  2
  0.0126
63.5
Volume of O2 liberated at NTP at anode = 0.0126 × 5600 mL = 70.56 mL
In the next 7 min, H2 at cathode and O2 at anode would be produced.
1.2  7  60
Faraday’s passed   5.22  10 3
96500
 Volume at H2 (at NTP)  5.22  10 3  11200 mL = 58.46 mL
Volume of O2 (at NTP) 5.22 × 10–3 × 5600 mL = 29.23 mL
Therefore, O2 (g) at NTP = 70.56 + 29.33 = 99.89 mL
H2(g) at NTP = 58.46 mL.
17. The galvanic cell is: Cu |Cu2  || Ag  | Ag , E  ( 0.337  0.799)V
 2
Cell reaction: Cu  2Ag   Cu  2Ag ; E  0.462V
0.0592 (0.01)
E  0  0.462  log
2 [Ag  ]2
 [Ag  ] 1.57  10 9 M
18. Change in oxidation number at nitrogen = 4 – (–2) = 6
123
Equivalent weight of nitrobenzene  g
6
12.3  6
 gram equivalent of nitrobenzene   0.60
123
 Theoretical requirement = 0.60 × 96500 C = 57900 C
 Actual requirement of electricity  2  57900  115800C
 V C J  Energy consumed = 115800 × 3J = 347. 40 kJ
1.7  230
19. Faraday’s passed   4.052  10 3 F
96500
Faradays used for reduction of Zn2   4.052  10 3  0.9  3.65  10 3
 Meq. of Zn2+ reduced = 3.65
Initial meq. of Zn2+ = 300 × 0.16 × 2 = 96
92.35 1
 Meq. of Zn2+ remaining = 96 – 3.65 = 92.35  Molarity of Zn 2    0.154 M
2 300

Vidyamandir Classes
20. The redox reaction is Zn  Ni 2 

 2
 Zn  Ni,    0.51 V
0.0592 0.51  2
 E  log K  log K  17.23  K 1.7  1017
2 0.0592
Such a high value of equilibrium constant indicates that the reaction is almost complete. Therefore,
concentration of Zn 2 in solution will be equal to initial concentration of Ni2+ ion, i.e. 1.0 M
2.8  10 10
21. [Ag  ] in left hand electrode chamber  1.4  10 9 M
0.2
3.3  10 13
[Ag  ] in right hand electrode chamber 
0.001
[Ag  ]anode 1.4  10 9

emf  0  0.0592 log   0.0592 log   0.037 V
[Ag  ]cathode 3.3  10 10
Therefore, the cell as written is non-spontaneous and its reverse will be spontaneous with emf = 0.037 V.
22. At anode 2Cl   Cl 2  2e
At cathode 2H2O  2e  H2  2OH 

1000
1 kg Cl2  equivalent of Cl2 = 28.17 equivalent  Therefore electricity requirement = 28.17 F
35.5
 Efficiency is only 62%
28.17  100
 Electricity requirement (experimental)  F  45.44F
62
 45.44 × 96500 = 25t (in second)]  t = 48.72 h
Also, gram equivalent of HO produced = 28.17
28.17
 Molarity of HO   1.4085 M
20
1 1
23. (i) E  0.78  0.0592 log  0.887 V (ii) E  0.78  0.0592 log   0.0488 V
82 (10 7 )2
52
24. Molar mass of Cr = 52 g Equivalent mass of Cr  g
6
24000 52
(i) Mass of Cr deposited on passing 24000 Coulombs   g  2.15 g
96500 6
1.5 9
(ii) Number of gram equivalent of Cr  6
52 52
1.5 9 9  96500
 Coulombs required for 1.5 g Cr   6  t  s  22.27 min
52 52 52  12.5
25. Given, FeO(s)/Fe(s) E    0.87 V and Ni2O3/NiO (s) E   0.40 V
Electrode at lower reduction potential act as anode and that at higher reduction potential act as cathode.
(i) Electrodes reaction:
Fe(s)  2OH  FeO(s)  H2O( ) E   0.87 V
Ni 2O3 (s)  H2O( )  2e  2NiO(s)  2OH  E  1.27 V
Net Reaction : Fe(s)  Ni2O3 (s)  2NiO(s)  FeO(s) E 1.27 V
(ii) Emf is independent of concentration of KOH.

Vidyamandir Classes
(iii) Maximum amount of energy that can be obtained  G 

 G    nE F   2  1.27  96500J   245.11 kJ
i.e. 245.11 kJ is the maximum amount of obtainable energy.
26. In a saturated AgI solution : [Ag  ]  8.7  1017 M  9.32  109
1 1
 E  E  0.0592 log  0.799  0.0592 log  0.324 V
Ag  /Ag [Ag ] 
9.32  10 9

Also, for AgI  
 Ag  I

; E  0.0592 log K sp  0.95V
Ag  Ag   e E   0.799V
 
AgI  e  Ag  I E   xV
Adding : AgI  Ag   I  ;E   0.95V = x  0.799  x   0.151 V
27. For reaction, 2Hg  2Fe3 

 2
 Hg 2  2Fe
2
Initial - 10 3 M
At equilibrium - 10 3  2x x 2x
10 3  2x  5  10 5
[Fe2  ]2[Hg 2 
2 ] (9.5 10 4 )2 (4.75  10 4 )
K  
[Fe3 ]2 (5  10 5 )2
0.0592
 E  log K   0.0226 V  E (Fe3 / Fe2 )  E  (Hg 2 
2 / Hg)
2
 E (Hg2 
2 / Hg)  0.77  0.0226  0.7926V
28. pH = 14
 pOH = 0  [OH ] 1.0 M
10 19
K sp  10 19  [Cu2  ] [OH ]2  [Cu2 ]   10 19
[OH  ]2
For reaction : Cu 2  2e  Cu ; E° = 0.34 V

0.0592 1 0.0592
E  E  log  0.34  log 1019   0.222 V
2 2 2
[Cu ]
243648
29. Coulombs passed  8.46  8  60  60  243648C ; Number of Faraday’s passed   2.52
96500
63.5 80.01
Weight of Cu plated  2.52  g  80.01 g and Volume of Cu plated   7.62 cm 3
2 10.5
7.62
 Area plated out   3000 cm 2
0.00254
30. Fe2  Ce4  

 3
 Fe  Ce
3
E  E (Ce4  / Ce3  )  E(Fe3  / Fe2 )  1.44  0.68  0.76 V

E 0.76
 E° = 0.0592 log K  log K   12.83  K = 6.80 × 1012
0.0592 0.0592

Vidyamandir Classes
0.0592 [Ag  ]anode

31. E 0 log Ecell  0
1 [Ag  ]cathode
[Ag  ]anode
 0.164   0.0592 log  [Ag  ]anode 1.7  10 4 M
0.10
In saturated Ag2CrO4 solution present in anode chamber:
  2
Ag 2CrO4 (s)  2Ag  CrO4
1.7
1.7 10 4 M  10 4 M
2
 1.7  12
K sp  [Ag  ]2 [CrO24 ]  (1.7  10 4 )2  10 4   2.45  10
 2 
 
32. For 2Fe3   3I 

 2 
 2Fe  I3
E  E (Fe3 / Fe2 )  E (I3 / I  )  0.77  0.54  0.23 V

0.0592
 E  log K (n = 2)
2
2E 2  0.23
log K    7.77  K  5.89  107
0.0592 0.0592
33.(A) More negative or lower is the reduction potential, more is the reducing property. Thus the reducing power
of the corresponding metal will follow the reverse order, i.e. Y > Z > X
34.(B) (i) In a galvanic cell, oxidation occurs at anode and reduction occurs at cathode.
(ii) Oxidation occurs at electrode having higher oxidation potential and it behaves as anode and other
electrode acts as cathode.
(iii) Ecell  EC  E A
(substitute reduction potential at both places).
Fe2  Zn  Zn 2   Fe
 Zn  Zn   2e  and Fe2  2e  Fe  Zn is anode and Fe is cathode.
Ecell  EC  E A  0.41  ( 0.76)  0.35 V
35.(A) The smaller the reduction potential of a substance, the more is its reducing power and less is its
oxidizing power. The given order of reduction potential is Z > Y > X, The order of oxidizing power is Z
> Y > X. Therefore, Y will oxidize X and not Z
9.65  60  60
36. The number of Faraday’s passed   0.36 F
96500
0.36
After electrolysis : [Ag+] = 1.36 M ; [Cu2 ] 1   0.82M
2
E1 (before electrolysis) = E°
0.0592  Ag  ]2 0.0592 (1.36)2

E2 (after electrolysis) = E  log  E1  E2  log  0.01 V
2 [Cu2 ] 2 0.82
2  10 3  16  60
37. The number of Faraday’s passed  1.99  10 5
96500
 number of gram equivalent of Cu2+ deposited
1.99
 number of moles of Cu2+ deposited   10 5 10 5
2
Absorbance is directly proportional to [Cu2+]. Therefore, if ‘C’ be the initial molarity, 0.5C will be the final
molarity.
 0.5C × 0.25 = 10–5  C = 8 × 10–5 M
38.(B) That reaction is spontaneous where cathode is of higher reduction potential.

Vidyamandir Classes
For M   X   M  X,Eocell  0.44  0.33  0.11 V is positive, hence reaction is spontaneous.


39. Since, activities of all the ions are unity, Ecell  Ecell . Also left hand electrode is at lower reduction
potential, it act as anode and E  E (Ce4  ,Ce3 )  E(Fe3  ,Fe2  )  0.84

i.e. electrons will flow from left to right hand electrode and current from right hand electrode [Pt(2)] to left
[Fe3  ] [Ce3  ]
hand electrode [Pt(1)]. Also, E  E  0.0592 log
[Fe2  ] [Ce4  ]
As electrolysis proceeds, E will decrease and therefore, current will also decrease.
40.(C) The salt used to make ‘salt-bridge’ must be such that the ionic mobility of cation and anion are of
comparable order so that they can keep the anode and cathode half cells neutral at all times KNO3 is
used because velocities of K  and NO3 ions are nearly same.
41.(B) As we go down the group 1 (i.e. from Li+ to K+), the ionic radius increases, degree of solvation decreases
and hence effective size decreases resulting in increase in ionic mobility. Hence, equivalent conductance
at infinite dilution increases in the same order.
42.(A) MnO4 will oxidize Cl  ion according to equation
Mn7   5e  Mn 2 
2Cl   Cl 2  2e
Thus, Eocell  Eo  Eo
Mn 7  /m 2
n

Cl2 /Cl
 1.51  1.40  0.11 V or reaction is feasible. MnO4 will oxidise
Fe2 to Fe3
Mn7   5e  Mn 2
Fe2  Fe3  e  Eocell  Eo  Eo  1.51  0.77  0.74 V
Mn7  /Mn 2  Fe3  /FE2 
Thus, MnO4 will oxidise Fe2 to Fe3  in aqueous HCl medium as well as it will also oxidise Cl  to Cl 2 .
Suitable oxidant should not oxidise Cl  to Cl 2 and should only oxidise Fe2  to Fe3  in redox titrations.
1
43. At anode H2  H   e  ; E  0
2
At cathode AgCl(s)  e  Ag  Cl  ; E  ?
1
(i) Cell reaction : H2  AgCl(s)  Ag  H  Cl 
2
(ii) G    nEF  H  T S
At 15 C :  0.23  96500  H  288 S  . . . . (i)
At 35°C : 0.21 96500  H  308 S . . . . (ii)
Subtract (i) form (ii)
96500  0.02
 96500(0.23  0.21)   20 S  S     96.5J
20
Substituting value of S in (i)
H  288  ( 96.5)  0.23  96500   49.987 kJ
(iii) At 25°C
E  96500   49987  298( 96.5) E   0.22 V
 AgCl(s)  e  Ag  Cl  ; E  0.22V

Vidyamandir Classes
Ag  Ag   e ; E   0.80 V
Adding : AgCl(s)  Ag   Cl   E   0.58V

0.58
 E  0.0592 log K sp  log K sp    9.79  K sp 1.6  10 10
0.0592
44. (a) pH   log[H  ]
In pure water, [H+] depends on value of Kw which is
Kw = [H+] [OH–]  K w is a function of temperature, [H+] will change with temperature.
(b) Let the emf of first cell be X volt.

 emf of 2nd cell = (X + 0.03) volt
[Cu2+] in 2nd cell = 0.50 M
[Cu2+] in 1st cell = ?
2.303RT [Zn 2 ]
E1  E1  log . . . (i)
2F [Cu2 ]
2.303 RT [Zn 2  ]
E2  E1  log . . .(ii)
2F [Cu2 ]2
2.303 RT  [Cu 2 ] 
2
 Subtract (i) form (ii)  E2  E1  log 
2F  [Cu2  ] 
 1
0.50 0.50
 0.03= 0.03 log  10  [Cu 2 ]1  0.05 M
2
[Cu ]1 [Cu 2 ]1
45.(C) In an electrolytic cell, the electrons do not flow themselves. The migration of ions towards oppositely
charged electrodes indirectly constitutes the flow of electrons from cathode to anode through internal
supply.
46. Given, ln 2  e  ln  E   0.40 ....(i)
 G  0.40F
ln 3  2e   ln  E    0.42 .... (ii)

 G  0.84 F
Subtracting (i) form (ii)
ln 3  e  ln 2 ; G  0.44F   E F ;  E   0.44V
Now, for : Cu 2  ln2   Cu  ln 3   0.15  (  0.44)  0.59V

E
Also E   0.0590 log K  log K   10  K 1010
0.059
47.(B) Cell reaction is, zn  Fe2  Zn 2  Fe
0.059 10 2
Using, E  E  log
1 10 3
(n  2,[Zn 2  ]  10 2,[Fe2  ]  10 3 )
Since E = 0.2905  0.2905 = E  0.0295
or E  0.2905  0.0295  0.3200 V
0.32
0.059 0.059
Again, E  log K eq  0.32  log K eq or K eq  10 0.0295
2 2
48.(B) Applying G   nFE

Vidyamandir Classes
Fe(s)  Fe2   2e ; G1o

2H   2e   1 / 2O2  H2O(l ); G2o
1
Fe(s)  2H   O2  Fe2  H2O; G3o
2
Applying Go3  ( 2F  0.44)  ( 2F  1.23)
 (2  96500  0.44  2  96500  1.23)  322310 J  Go3  322 kJ
49. (a) G  Gf (products)  G f (reactants)   109  ( 129  77)kJ   57kJ
Cell : Ag | AgCl,Cl  || Ag  | Ag

For K sp ;reaction is AgCl(s)  
 Ag  Cl

G 57  1000
G   57kJ  G   RT ln K sp  log K sp     10
2.3 RT 2.3  8.314  298
Now, 
E of Ag   Cl   AgCl
G 57000
E     0.59 V
nF 96500
 2
(b) The cell reaction is Zn  2Ag   Zn  2Ag ; E  1.56 V
0.059 [Zn 2 ] [Zn2  ] 2E 2  1.56
 0  E  log  log    52.88
2 [Ag  ]2 [Ag  ]2 0.059 0.059
6.539  10 2
Moles of Zn added  10 3  Moles of Ag formed  2 10 3
65.39
RT
50.(B) Eocell  ln K
nF
0.0591
0.8  0.05  ln K
2  2.303
(0.8  0.05)  2  2.303
 ln K   58.45
0.0591
51.(A) On increasing concentration of NH3, the concentration of H ion decreases.
0.0591
E red  E ored  log[H  ]
n
52.(D) NH3 has no effect on the standard reduction potential.
 The potential difference developed between metal electrode and the solution of its ions of unit
molarity (1 M) at 25°C is called standard electrode potential.
 The standard reduction potential of an electrode means that reduction reaction is taking place at
the electrode.
53. The solubility of AgBr in 10 7 M AgNO3 solution is determined as

AgBr  Ag   Br 
S 107 S

AgNO3  Ag  NO 3
S  10 7 10 7
14
K sp 12 10  S (S  10 7 )
Solving for S gives: S  3  10 7 M

 [Br  ]  3  10 7 M, [ Ag  ]  4  10 7 M  [NO3 ] 10 7 M

Vidyamandir Classes
  (sp. conductance)     
Br  Ag  
NO3
 [8  10 3  3  10 7  6  10 3  4  10 7 7  10 3  10 7 ] 1000
 24  10 7  24  10 7  7  10 7  55  10 7 Sm 1 = 55(in terms of 10 7 Sm 1 )
54.(C) Reduction potential of l2 is less than Cl 2 55.(D) Reaction of Mn 3 with H2O is spontaneous.
56.(A) Prussian blue colour is due to Fe4 [Fe(CN)6 ]3
57.(D) Nacl  Na Cl 

At anode: 2Cl   Cl 2
Moles of Cl   2 in 500 ml. Therefore 1 mole of Cl 2 evolves.
58.(D) Na – Hg (amalgam) formed = 2 moles at cathode.

59.(D) 2 moles of electrons (2 Faraday) are required
1 F = 96500 ; 2F = 193000
60.(B) Q  i  t ; Q  10  10 3  t
2H2O  2e  H 2  2OH 

To liberate 0.01 mole of H2,0.02 Faraday charge is required
 Q  0.02  96500  10 2  t ; t  19.30  10 4 sec

61.(ABD) The substances which have lower reduction potentials are strong reducing agents while those which
have higher reduction potentials are stronger oxidising agents.
 Eo for V, Fe and Hg are lower than that of NO3 ,so NO3 , will oxidise V, Fe and Hg.
M n |M
62.(B) The net cell reaction is
M(s)  M (aq,1M)  M(aq,0.05

M)  M(s)
According to Nernst equation,
0.059 [M  ](0.05 M) 0.059
Ecell  Eocell  log  Eocell  log(0.05)  0  0.059 log (5  10 2 )  0.059[2  log 5]
n  1
[M ](1M)
 Ecell   ve or E cell  0 and Hence G  0 as G  nFEcell
o 0.059  0.0025 
63.(C) Ecell(2)  Ecell  log  
1  1 
 
Ecell(1)  70 mV
Ecell(2) log(0.0025) 2.6
   2  Ecell(2)  70  2  140 mV
E cell(1) log(0.05) 1.3
 2
64.(D) 2Fe(s)  O2(g)  4H(aq.)  2Fe(aq.)  2H2O(l )
n = 4 (no. of electrons involved)
From Nernst equation,
0.0591 [Fe2 ]2 0.0591 (10 3 )2
Ecell  Eocell  log  1.67  log { [H  ]  10  pH }
n PO  [H  ]4 4 0.1  (10 3 )4
2
 1.67  0.103  1.57 V
65.(D) Ag(NO3 ) (aq )  KCl (aq)  AgCl   KNO3 (aq )
 Cl  ions being replaced by NO3 ions.
 (i) Till all KCl (Cl  ions) gets consumed by NO3 , Cl  will get replaced by NO3 .

Vidyamandir Classes
AgNO
K  Cl  
3
 K  NO3
(ii) When all Cl  is gone, AgNO3 will not get ppt. anymore.
AgNO
K  Cl  
3
 Ag   K  NO3
Conductance is bound to increase now.
 D is the most appropriate answer.
66.(D) M  M 2 (salt) : (Oxidation half cell)
M 2 (0.001)  M : (Reduction half cell)
Reaction is M  M (0.001)  M 2 (S : so lub ility)  M

2
0.059 S
E  E  log   E  0
n 0.001
S
2  log  S  105
10 3
K SP  4s3  4  10 15
67.(B) G   nFE  2  96500  0.059  11.4 kJ / mol
68.(D) Fe 3  e  Fe 2 E  0.77
Fe 2  2e  Fe E  0.44

___________________
Fe 3  3e  Fe E  ?
E 

0.77  1  2  0.44


 0.04 V
0.11
3 3
So, P  3 and hence Answer is (D).
69.(A) When Et3N solution is added to CH3COOH, '  ' of CH3COOH will increase, so though H+ ions ions will be
consumed by Et3N but overall no. of ions in the solution will increase and hence conductivity increases
initially.
  KI (aq) 
Ag(aq )  NO3 (aq )  AgI(s)   K (aq )  NO3 (aq )
Number of ions remain the same so, conductivity does not change much. After all Ag+ ions have been
precipitated out, then the conductivity will increase.
  CH COOH(aq ) 
)  OH (aq )  H2O( )  K (aq )  CH3COO(aq )
3
K (aq
Number of ions remains the same, but number of OH  ions decreases and hence conductivity decreases.
NaOH
H  I  H2O( )  Na (aq
 
)  I(aq )

Number of ions remains the same, but number of H decreases and hence conductivity decreases.
70.(AB) Salt bridge keeps the solutions in two half-cells electrically neutral. It prevents transference or diffusion
of the ions from one half-cell to the other.
71.(4) Given X  Y ; G   193 kJ mol 1
M   M3   2e  ; E  0.25 V
1
F  96500 C mol
Let 193 kJ is used for oxidising x moles of M  .
For 1 mole of M  , G  nFE  2  96500  ( 0.25)  48250 J mol 1  48.25 kJ mol 1
193
Thus, number of moles of M  oxidized when one mole of X is converted to Y  4
48.25
72.(D) For the given electrochemical cell, the reactions are
At anode : H2(g)  2H (aq )  2e 

Vidyamandir Classes
At cathode : M4 (aq )  2e   M2 (aq )
H2(g)  M4 (aq )  M2 (aq)  2H(aq )

0.059 [M2  ][H (aq ) ]
Ecell  Ecell  log
2 [M4  ]
0.092   E 4  2   E    0.059 log(10 x [H ]2 )

M /M H /H

 2  2
0.059
0.092  (0.151  0)  log(10  12 )
x
2
0.092  0.151  0.0295 log10 x
0.059
log10 x  2
0.0295
10 x  Antilog 2 = 10 2  x  2

73.(A) Given cell is Zn(s) | ZnSO4(aq )  CuSO4(aq) | Cu(s) ; Ecell  1.1 V
The cell reaction is
Zn  Cu 2   Zn 2   Cu
2.303RT [Zn2  ]
Ecell  Ecell  log
nF [Cu2  ]
On substituting values, we get :
2.303RT 10[Cu 2  ] 2.303RT
Ecell  1.1  log  1.1  [ log10  1]
2F [Cu 2  ] 2F
G  nFE cell
On substituting values, we get :
 2.303 RT 
G  2F 1.1    2.2F  2.303 RT or 2.303 RT  2.2F
 2F 
 7 120
74.(6)   G   5  10   6  10 S cm 1
5
a 1
  1000 6  10 5  1000
 cm    40 S cm 2 mol 1
Molarity 0.0015
pH  4   log[H ]  [H ]  10 4 M
HA 
 H  A
Internal conc. : 0.0015 0 0
Equilibrium conc. 0.0015  0.0015 0.0015 0.0015
10 4
Thus, [H ]  0.0015   104   
0.0015
4
cm 10 40
Also,   
om 0.0015 m
40  0.0015
 m   600  6  10 2 S cm 2 mol 1
10 4
On comparing it with Z  10 2 S cm 2 mol 1 , we get : Z = 6
75.(–11.62)
A (s)  A n   ne ]  2 . . . .(i)

Vidyamandir Classes
B2n   2ne   B(s)

2A (s)  B2n   2A n   B(s)
Given, H  2 G, E cell  0
G
As, G  H  TS  G  2 G  TS or G  TS or S 
T
n 2 2
RT ln K [A ] 2
Also, S   R ln  8.3  ln
T [B2n  ] 1
1 1
 S  11.62 JK mol
76.(10.00)
For the given cell,
Anodic reaction : Mg (s)  Mg 2   2e
Cathodic reaction : Cu 2   2e   Cu(s)
and balanced reaction is Mg (s)  Cu 2  (1M)  Cu(s)  Mg 2  (x M)

RT x T
Ecell  Ecell  ln  E cell  E cell  ln x
nF 1 nF
R
300 300
 2.67  2.70  ln x  0.03  ln x
2  11500 2  11500
 2.3  ln x  x  10
77.(13.32)
1
O2  2H  2e  H2O E 0  1.23 V …..(1)
2
2H   2e   H2 E0  0.00V
So, H2  2H   2e  E0  0.00V …..(2)

From (1) and (2)
1
H2  O2  H2O E0  1.23V
2
G o   nFE o
70
 2  96500  1.23  1  10 3 
100
 166.173 J
For compression of an ideal gas in a thermally insulated container work done is given as
w  nCvT
3
166.173  1  R  T
2
3
166.173  1   8.314  T
2
166.173  2
T 
3  8.314
T  13.32
3
Note : Cv for monoatomic gas  R
2

Electrochemistry - Workbook Solution

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Vidyamandir Classes

Solutions to Workbook-4 [Chemistry] | Electrochemistry

1. Representation of the galvanic cell for the given reaction is:

limiting molar conductivity for sodium chloride is given by  m(NaCl )    

Where,  m is the molar conductivity and  m is the limiting molar conductivity.

5. Mercury cell is generally used in transistors.

At anode : Zn(Hg)  2OH   ZnO  H2O  2e

At cathode : PbO2(s)  SO24(aq

Cathode: HgO(s)  H2O(l )  2e   Hg(l )  2OH

Net reaction: Zn(Hg)  HgO(s)  ZnO(s)  Hg (l )

Chemistry | Electrochemistry 280 Workbook-4 | Solutions

Ecell  Ecathode  Eanode  1.51 V  0.15 V  1.36 V

Again, G  nFE cell

  1000 cm  M 138.9  1.5

Chemistry | Electrochemistry 281 Workbook-4 | Solutions

Reaction for deposition of Ni,

 6 mol  96500 C mol 1  5.79  105 Coulomb

Net reaction : 2H2(g )  O2(g )  2H2O(l )

At anode : Fe  Fe2   2e ; E  0.44 V

(ii) Ecell  E right  E left

Chemistry | Electrochemistry 282 Workbook-4 | Solutions

20. G  nFC cell

0.0591 Ecell  n 1.05  2

K c  antilog 35.53  3.38  1035

(i) Calculation of Ecell

Cathode: Ag 2O(s)  H2O(l )  2e  2Ag (s)  2OH(aq)

Chemistry | Electrochemistry 283 Workbook-4 | Solutions

  2  96500 C mol 1  1.56 V   301080 C V mol 1   301080 J mol 1   301 kJ mol 1

Ecell  E cathode  Eanode  0.80 V  0.34 V  0.46 V

26. Resistance of 0.1 M KCl solution R  100 

Chemistry | Electrochemistry 284 Workbook-4 | Solutions

0.03  0.34  Eanode

Eanode  0.34  0.03  0.31 V

Daily Tutorial Sheet 1 to 5 Level – 1 | JEE Main

1.(A) Zn  Fe2   Zn 2   Fe

5.(B) Increasing Ered indicates increasing oxidising power. Thus A  C  B

15.(D) E  1.66 V and E  0.76 V . 16.(B) Charge on one e  Avogadro' s no  F .

Chemistry | Electrochemistry 285 Workbook-4 | Solutions

Amount deposited by 1 C is equal to electrochemical equivalent.

Anode 2H2O  O2  4H   4e

So, Q  it  2  96500  0.01 10  10 3  t  t  19.3  10 4 sec

Ni 2   2e   Ni  2  96500 C produces 1 mol or 58.7 g Ni

Chemistry | Electrochemistry 286 Workbook-4 | Solutions

48.(B)  HOAC   NaOAC

49.(C)  ClCH  ClCH   HCl  NaCl  224  230  38.5  415.5

Chemistry | Electrochemistry 287 Workbook-4 | Solutions

M  M2   2e ; G   2  0.439 F  M3  e  M2  , G  3  0.036  2  0439 F

Chemistry | Electrochemistry 288 Workbook-4 | Solutions

66.(C) Mn 2   2e  Mn ; G  2  1.18 F

Mn 3   3e   Mn ; G  2.36  1.51 F     

So reduction of Cl2 will take place and bromine Br    is oxidised.

Cu   Cu2  e  ; E   0.15 ; G   1F  0.15  

Now Cu   Cu2   e ; E   0.15 V

Chemistry | Electrochemistry 289 Workbook-4 | Solutions

Net cell reaction for this cell is Ag   I   AgI(s)

(Since at equilibrium, Ecell  0 &  Ag   I    K sp )  log K sp   16.1

75.(C) MnO4  8H  5e   Mn 2   4H 2O

Daily Tutorial Sheet 6 to 10 Level – 2 | JEE Advanced Pattern

76.(C) E 2  /Cr 3   1.33V;E  1.23V; E  1.51V;E   1.36V

 E  /Mn 2  is highest, KMnO4 is the strongest oxidising agent.

77.(D) EO /O  2.07V; E  2.87V; E 

 E is lowest, Cl 2 is the weakest oxidising agent.

78.(AC) EZ is highest  strongest oxidising agent.