NVS Tutorial Electrochemistry Suraj Sir-9883219693

Application of Electrochemical series/Activity Series

To predict whether a metal reacts with acid to give hydrogen gas. In order that a
metal M (assuming it to be monovalent) may react with an acid to give H2 gas, following
reaction should take place :
1
M + H+  M+ + 2 H2

which can be split into two half reaction as : M  M+ + e– (Oxidation half

reaction)
1
and H+ + e  2 H2 (Reduction half reaction)
Thus, the metal should have the tendency to lose electrons, i.e., undergo
oxidation, with respect to hydrogen. In other words, the metal should have a negative
reduction potential. Thus, all metals lying above hydrogen in the electrochemical
series react with the acid to give hydrogen gas. Further, evidently, lower the reduction
potential (i.e., more negative the reduction potential) higher is the reactivity.
.
To predict the spontaneity of a redox reaction. To see whether a given redox
reaction is feasible or not, the EMF of the cell based upon the given redox reaction is
calculated. For a redox reaction to be spontaneous, the EMF of the cell must be
positive. If the EMF comes out to be negative, the direct reaction, as given, cannot
take place; the reverse reaction may take place. This is illustrated by the numerical
problems given below.

Problem 1 : Predict whether zinc and silver react with 1M sulphuric acid to give
out hydrogen gas or not. Given that the standard reduction potentials of zinc
and silver are – 0.76 volt and 0.80 volt respectively.
Solution. (a) To predict reaction of zinc with sulphuric acid : If it reacts, the following
reaction should take place :
Zn + H2SO4  ZnSO4 + H2, i.e., Zn + 2H+  Zn2+ + H2
By convention, the cell will be represented as : Zn | Zn2+ || H+ | H2
Std. EMF of the cell (Ecell) = [Std. redn. pot. of R.H.S. electrode] – [Std. redn.
pot. of [L.H.S.electrode] = 0 – (– 0.76) = + 0.76 volt.
Thus, the EMF of the cell comes out to be positive. Hence, the reaction takes
place.
(b) To predict the reaction of silver with sulphuric acid : If it reacts, the following
reaction should take place :
2 Ag + H2SO4  Ag2SO4 + H2, i.e., 2 Ag + 2H+  2 Ag+ + H2
By convention, the cell may be represented as : Ag | Ag+ || H+ | H2
E°cell = E°𝐻 +,𝐻2 − E°𝐴𝑔+,𝐴𝑔 = 0 – 0.80 = – 0.80 volt.

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Thus, EMF of the supposed cell comes out to be negative. Hence, this reaction
does not take place.

Problem 2 : Can a solution of 1 M copper sulphate be stored in a vessel made of

nickel metal ? Given that 𝐄°𝑵𝒊,𝑵𝒊𝟐+ = 0.25 volt, 𝐄°𝑪𝒖,𝑪𝒖𝟐+ = – 0.34 volt.
Or
Can a nickel spatula be used to stir a solution of copper sulphate ? Support your
answer with a reason.
𝐄°𝑵𝒊𝟐+/𝑵𝒊 = – 0.25 V, 𝐄°𝑪𝒖𝟐+/𝑪𝒖 = + 0.34 V
Solution. In this problem, we want to see whether the following reaction takes
place or not : Ni + CuSO4  NiSO4 + Cu, i.e., Ni + Cu2+  Ni2+ + Cu
By convention, the cell may be represented as : Ni | Ni2+ || Cu2+ | Cu
E°𝑁𝑖,𝑁𝑖 2+ = + 0.25 volt and E°𝐶𝑢,𝐶𝑢2+ = – 0.34 volt.
Hence, the reduction potentials will be
E°𝑁𝑖 2+,𝑁𝑖 = −E°𝑁𝑖,𝑁𝑖 2+ = – 0.25 volt and E°𝐶𝑢2+,𝐶𝑢 = −E°𝐶𝑢,𝐶𝑢2+ = + 0.34 volt
E°cell = E°R.H.S. electrode – E°L.H.S. electrode = + 0.34 – (– 0.25) = + 0.59 volt
Thus, EMF comes out to be positive. This implies that CuSO 4 reacts with nickel.
Hence, CuSO4 cannot be stored in nickel vessel.

Problem 3 : Iodine (I2) and bromine (Br2) are added to a solution containing
iodide (I–) and bromide (Br–) ions. What reaction would occur if the
concentration of each species is 1 M ? The electrode potentials for the reactions
are : 𝐄°𝑰𝟐/𝑰− = 0.54 V, 𝐄°𝑩𝒓𝟐 /𝑩𝒓− = 1.08 V
Solution. The reaction can be either Br2 + 2 I–  2Br– + I2 or I2 + 2Br–  2I– +
Br2
For 1st reaction, E.M.F. = E°𝐵𝑟2 /𝐵𝑟 − − E°𝐼2/𝐼− = 1.08 – 0.54 = 0.54 V
For 2nd reaction, E.M.F. = E°𝐼2/𝐼− − E°𝐵𝑟2 /𝐵𝑟 − = 0.54 – 1.08 = –0.54 V
As E.M.F. is positive for the 1st reaction, hence the cell reaction is Br 2 + 2 I– 
–
2 Br + I2.

PROBLEMS FOR PRACTICE

1. Predict reaction of 1N sulphuric acid with : (i) Copper (ii) lead (iii) iron.
Given, E°𝐶𝑢2+,𝐶𝑢 = 0.34 volt : E°𝑃𝑏2+,𝑃𝑏 = –0.13 volt, and E°𝐹𝑒 2+ ,𝐹𝑒 = –0.44 volt
2. Can we store : (a) Copper sulphate solution in zinc vessel ?
(b) Copper sulphate solution in silver vessel ?
(c) Copper sulphate solution in iron vessel ?

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

Give suitable explanation.

E°𝐶𝑢2+/𝐶𝑢 = 0.34 V, E°𝑍𝑛2+/𝑍𝑛 = –0.76 V, E°𝐴𝑔+/𝐴𝑔 = 0.80 V, E°𝐹𝑒 2+/𝐹𝑒 = – 0.44 V.
3. A copper wire is dipped in AgNO3 solution kept in beaker A and a silver wire is
dipped in a solution of copper sulphate kept in beaker B. If standard electrode
potential for
Cu2+ + 2e–  Cu is + 0.34 V and for Ag+ + e–  Ag is + 0.80 V,
predict in which beaker the ions present will get reduced ?
4. Why blue colour of copper sulphate solution gets discharged when zinc rod is
dipped in it ? Given
E°𝐶𝑢2+/𝐶𝑢 = + 0.34 V, E°𝑍𝑛/𝑍𝑛2+ = + 0.76V
5. Can chlorine gas be stored in a copper cylinder ? Given E°𝐶𝑢2+/𝐶𝑢 = 0.34 V and
E°𝐶𝐼2,𝐶𝐼 = 1.36 V.
6. Using standard electrode potentials, predict the reaction, if any, that occurs
between Fe3+ (aq) and I– (aq) E°𝐹𝑒 3+(𝑎𝑞)/𝐹𝑒 2+(𝑎𝑞) = 0.77 V ; E°𝐼2/2𝐼−(𝑎𝑞) = 0.54V
7. Predict whether the following reaction (s) is (are) feasible or not
(i) Fe + Zn2+  Fe2+ + Zn, Ezn = – 0.76 V, E°Fe = – 0.44 V
(ii) Zn + 2 Ag+  Zn2+ + 2 Ag, EZn = – 0.76 V, E°Ag = – 0.80 V
8. Can a nickel spoon be used to stir a solution of silver nitrate ? Support your
answer with reason.
(E°𝑁𝑖 2+ ,𝑁𝑖 = −0.25 𝑉, E°𝐴𝑔+,𝐴𝑔 = +0.80 𝑉)

ANSWERS
1. (i) No (ii) Yes (iii) Yes
2. (a) No (b) Yes (c) No
3. In beaker A, Ag+ ions will be reduced
4. Ecell = 1.10 V, i.e., +ve. Reaction takes place changing blue CuSO 4 to
colourless ZnSO4
5. No
6. 2 Fe3+ + 2 I–  2 Fe2+ + I2
7. (i) No (ii) Yes
8. No

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NUMERICAL PROBLEMS BASED ON Nernst Equation

FORMULAS AND UNIT USED
(i) For electrode potential, write electrode reaction as i.e., Mn+ + ne–  M
0.0591 1
Then by Nernst equation, at 298 K, ERed = ERed − log [𝑀𝑛+]
𝑛

(ii) For EMF of a cell, write cell reaction, e.g., in general,

aA + bB = xX + yY
Then by Nernst equation at 298 K,
0.0591 [𝑋]𝑥 [𝑌]𝑦
ECell = E°Cell − log [𝐴]𝑎 [𝐵]𝑏
𝑛

where n is no. of electrons involved in cell reaction.

For pure solid, pure liquid and any gas at 1 atm pressure, conc. = 1.

Problem 1 : Calculate the electrode potential of a copper wire dipped in 0.1 M

CuSO4 solution at 25°C. The standard electrode potential of copper is 0.34 volt.
Solution. The electrode reaction written as reduction reaction is
Cu2+ + 2 e–  Cu so that n = 2
0.0591 1
Applying Nemst eqn. we get E = E − log [𝐶𝑢2+ ] {... [Cu] = 1}
2
0.0591 1
= 0.34 − log 0.1 = 0.34 – 0.02955 = 0.31045 volt.
2

Problem 2 : A zinc rod is dipped in 04 M solution of ZnSO 4. The salt is 95%

dissociated at this dilution at 298K. Calculate the electrode potential
(𝐄𝒁𝒏𝟐+/𝒁𝒏 = −𝟎. 𝟕𝟔 𝑽)
Solution. The electrode reaction written as reduction reaction is :
Zn2+ + 2 e–  Zn (n = 2)
0.0591 1
Applying Nernst equation, we get 𝐸𝑍𝑛2+/𝑍𝑛 = E°𝑍𝑛2+/𝑍𝑛 − log [𝑍𝑛2+]
2

As 0.1 M ZnSO4 solution is 95% dissociated, this means that in the solution,
95
[Zn2+] = 100 x 0.1 M = 0.095 M
0.0591 1
 𝐸𝑍𝑛2+/𝑍𝑛 = −0.76 − log 0.095 = −0.76 − 0.02955 (log 1000 – log 95)
2

= 0.76 – 0.02955 (3 – 1.9777) = – 0.76 – 0.03021 = – 0.79021 volt

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

Problem 3 : Represent the cell in which the following reaction takes place :
Mg (s) + 2 Ag+ (0.0001 M)  Mg2+ (0.130 M) + 2 Ag (s)
Calculate its Ecell. Given that 𝑬𝑴𝒈𝟐+,𝑴𝒈 = – 2.37 V and 𝑬𝑨𝒈+,𝑨𝒈 = 0.80 V
Solution. Here, we are given reduction potentials as 𝐸𝑀𝑔2+/𝑀𝑔
= – 2.37 V, 𝐸𝐴𝑔+/𝐴𝑔 = 0.80 V
As the emf of the cell must be positive, this can be so only if oxidation takes
place at the magnesium electrode. Hence, the electrode reactions will be
Mg  Mg2+ + 2 e– (At anode)
2 Ag+ + 2 e–  2 Ag (At cathode)
Thus, the cell may be represented as : Mg | Mg2+ (0.130 M) || Ag+ (0.0001 M) | Ag
Standard emf of the cell will be :
Ecell = Std. Red. Pot. of R.H.S. electrode – Std. Red. Pot. of L.H.S. electrode = 0.80
– (–2.37) = 3.17 V
The overall reaction is : Mg + 2 Ag+ = Mg2+ + 2 Ag (n
= 2)
Applying Nernst eqn., we get
0.0591 [𝑀𝑔2+ ]
Ecell = E°cell – log [𝐴𝑔+ ]2
𝑛
0.0591 0.130 0.0591 0.130
Ecell = Ecell – log (10−4 )2 = E°cell – log
2 2 10−8

= 3.17 – 0.02955 log (1.30 x 107) = 3.17 – 0.02955 x (7.1139 )

= 3.17 – 0.21 = 2.96 volt.
Alternatively, this problem may be solved by first calculating the electrode
potentials of the two electrodes separately and then calculating the emf from the
electrode potentials.

Problem 4 : The EMF of the following cell is found to be 0.20 V at 298 K

Cd | Cd2+ (?) || Ni2+ (2.0 M) | Ni
What is the molar concentration of Cd 2+ ions in the solution ?

(𝐄°𝑪𝒅𝟐+ = −𝟎. 𝟒𝟎 𝑽, 𝐄°𝑵𝒊𝟐+ = −𝟎. 𝟐𝟓 𝑽)

𝑪𝒅 𝑵𝒊

Solution. The cell reaction is : Cd + Ni 2+  Cd2+ + Ni,

E°cell = – 0.25 – (– 0.40) = 0.15 V
0.0591 [𝐶𝑑2+ ]
Applying Nernst equation, Ecell = E°cell – log [𝑁𝑖 2+ ]
2

0.0591 [𝐶𝑑2+ ]
0.02 = 0.15 – log
2 2

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

or log [Cd2+] – log 2 = – 1.690

or log [Cd2+] = – 1.690 + 0.3021 = – 1.3879 or [Cd2+] = antilog 2.6121= 0.0409 M

Problem 5 : Calculate the potential (emf) of the cell

Cd | Cd2+ (0.10 M) || H+ (0.20 M) | Pt, H2 (0.5 atm)
(Given E° for Cd2+/Cd = – 0.403 V, R = 8.314 J K–1 mol–1, F = 96, 500 C mol–1)
Solution. The cell reaction is : Cd + 2 H+ (0.20 M)  Cd2+ (0.10 M) + H2 (0.5 atm)
E°cell = E°𝐻 +,1 𝐻 − E°𝐶𝑑2+,𝐶𝑑 = 0 – (– 0.403) = 0.403 V
2 2

Applying Nernst equation to the cell reaction,

1
2.303 𝑅𝑇 [𝐶𝑑2+ ]× 𝑃𝐻 2.303 ×8.314 ×298 0.1 ×0.5
Ecell = E°cell – log [𝐻 + ]2
2
= 0.403 – log (0.2) 2
𝑛𝐹 2 ×96500

= 0.403 – 0.003 = 0.400 V

PROBLEMS FOR PRACTICE

1. Calculate the electrode potential of the electrode Zn/Zn 2+ (conc. = 0.1 M) at
25°C
Given that E°𝑍𝑛,𝑍𝑛2+ = 0.7618 volt.
2. Calculate the emf of the cell, Cd | Cd2+ (0.001 M) || Fe2+ (0.6 M) | Fe at 25°C
The standard reduction potential of Cd/Cd2+ and Fe/Fe2+ electrodes are – 0.403
and – 0.441 volt respectively.
3. Iron and nickel are used to make an electrochemical cell by using a salt bridge
to join a half–cell containing 1.0 M solution of Fe2+ (aq) in which a strip of iron
has been immersed to a second half–cell which contains 1.0 M Ni 2+ (aq)
solution in which a strip of nickel has been immersed. A voltmeter is connected
between the two metal strips.
(i) In which cell does reduction occur ?
(ii) Write the half–cell reactions involved.
(iii) Which metal is the anode ?
(iv) In which direction are the electrons passing through the voltmeter ?
(v) What would be effect on the voltmeter reading if Fe 2+ concentration were
increased ?
(vi) What will be the voltmeter reading when the cell reaches equilibrium ?

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

Given that the standard electrode potentials of Fe 2+/Fe and Ni2+/Ni electrodes
are – 044 and – 0.25 volt respectively.
4. A galvanic cell consists of a metallic zinc plate immersed in 0.1 M Zn(NO3)2
solution and metallic plate of lead in 0.02 M Pb(NO 3)2 solution. Calculate the
emf of the cell. Write the chemical equation for the electrode reactions and
represent the cell. (Given E°𝑍𝑛2+,𝑍𝑛 = –0.76 V, E°𝑃𝑏2+,𝑃𝑏 = –0.13 V)
5. Calculate the standard electrode potential of the Ni 2+/Ni electrode if the cell
potential of the cell
Ni | Ni2+ (0.01 M) || Cu2+ (0.1 M) | Cu is 0.59 V. Given E°𝐶𝑢2+/𝐶𝑢 = + 0.34V.
6. A voltaic cell is set up at 25°C with the half cells, Al3+ (0.001 M) and Ni 2+ (0.50
M)
Write an equation for the reaction that occurs when the cell generates an
electric current and determine the cell potential. (Given E°𝑁𝑖 2+ /𝑁𝑖 = – 0.25 V,
E°𝐴𝐼3+/𝐴𝐼 = –1.66 V)
7. The measured e.m.f. at 25°C for the cell reaction
Zn (s) + Cu2+ (1.0 M) = Cu (s) + Zn2+ (0.1 M) is 1.3 volt. Calculate E° for the cell
reaction.
8. Calculate the potential of the following cell reaction at 298 K
Sn4+ (1.50 M) + Zn (s)  Sn2+ (0.50 M) + Zn2+ (2.0 M)
The standard potential E° of the cell is 0.89 V. Whether the potential of the cell
will increase or decrease, if the concentration of Sn 4+ is increased in the cell ?
(R = 8.314 JK–1 mol–1 ; F = 96,500 C mol–1)
9. Calculate the potential of a zinc–zinc ion electrode in which the zinc ion activity
is 0.001 M
(E°𝑍𝑛2+/𝑍𝑛 = – 0.76 V, R = 8.314 J K–1 mol–1, F = 96,500 C mol–1)
10. (a) Calculate the electrode potential of silver electrode dipped in 0.1 M solution
of silver nitrate of 298 K assuming AgNO 3 to be completely dissociated. The
standard electrode potential of Ag+ | Ag is 0.80 V at 298 K.
(b) At what concentration of Ag+ ions will this electrode have a potential of 0.0
volt ?
11. Cu2+ + 2 e–  Cu, E° = + 0.34 V ; Ag+ + 1 e–  Ag, E° = + 0.80 V
(i) Construct a galvanic cell using the above data.
(ii) For what concentration of Ag+ ions will the emf of the cell be zero at 25°C,
if the concentration of Cu2+ is 0.01 M ? (log 3.919 = 0.593)
12. Calculate the potential for half cell containing 0.10 M K2Cr2O7 (aq), 0.20 M Cr3+
(aq) and 1.0 x 10–4 M H+ (aq). The half–cell reaction is 𝐶𝑟2 𝑂72− (aq) + 14H+ (aq)
+ 6 e–  2 Cr3+ (aq) + 7 H2O (l)
and the standard electrode potential is given as E° = 1.33 V.

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13. Calculate the emf of the following cell at 298 K

Fe(s) | Fe2+ (0.001 M) || H+ (1 M) | H2(g) (1 bar), Pt(s) (Given E°cell = + 0.44 V)
14. Calculate emf of the following cell at 25°C :
Fe | Fe2+ (0.001 M) || H+ (0.01 M) | H2(g) (1 bar), Pt(s)
E° (Fe2+/Fe) = – 0.44 V, E° (H+/H2) = 0.00 V
15. Calculate the e.m.f. of the following cell at 298 K :
2 Cr (s) + 3 Fe2+ (0.1 M)  2 Cr3+ (0.01 M) + 3 Fe (s)
Given : E°(𝐶𝑟 3+/𝐶𝑟) = – 0.74 V, E°(𝐹𝑒 2+/𝐹𝑒) = – 0.44 V
16. Write the cell reaction and calculate the e.m.f. of the following cell at 298 K
Sn (s) | Sn2+ (0.004 M) || H+ (0.020 M) | H2 (g) (1 bar) | Pt (s)
(Given : E°𝑆𝑛2+ /𝑆𝑛 = – 0.14 V)
17. Calculate the e.m.f. of the following cell at 298 K : Ni (s) | Ni2+ (0.01 M) || Cu2+
(0.1 M) | Cu (s)
[Given : E°𝑁𝑖 2+/𝑁𝑖 = – 0.25 V, E°𝐶𝑢2+/𝐶𝑢 = 0.34 V]
Write the overall cell reaction.
(CBSE Sample Paper 2018)

ANSWERS
1. E°𝑍𝑛2+,𝑍𝑛 = –0.7914 volt
2. 0.0441 volt
3. (i) Nickel half cell (ii) Ni2+ + 2e–  Ni
(iii) Fe is anode (iv) Iron to nickel
(v) Voltmeter reading decreases (vi) V = 0
4. 0.6094 V, Zn + Pb2+  Zn2+ + Pb ; Zn | Zn2+ (0.1 M) || Pb2+ (0.02 M) | Pb
5. – 0.2205 V 6. 1.46 V 7. 1.27045 V 8. 0.895 V, Increase
9. – 0.849 V
10. (a) 0.741 V (b) 2.9 x 10–14 M
11. 5 x 10–9 M
12. 0.76 V
13. 0.53 V
14. 0.41045 V
15. 0.31 V
16. 0.1104 V
17. 0.62 V

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

EQUILIBRIUM CONSTANT FROM NERNST EQUATION

Problem : Calculate the equilibrium constant for the reaction

Cu (s) + 2Ag+ (aq) = Cu2+ (aq) + 2Ag (s),
Given that 𝐄𝑨𝒈+/𝑨𝒈 = 0.80 V and 𝐄𝑪𝒖𝟐+/𝑪𝒖 = 0.34 V
Solution. The cell may be represented as : Cu | Cu2+ (aq) || Ag+ (aq) | Ag
E°cell = E°RHS – E°LHS = 0.80 V – (0.34 V) = 0.46 V
0.0591
E°cell = log Kc
𝑛

For the given reaction, n = 2, E°cell = 0.46 V

0.0591 0.46×2
 0.46 = log Kc or log Kc = = 15.5668
2 0.0591

 Kc = Antilog 15.5668 = 3.6 x 1015

PROBLEMS FOR PRACTICE

1. Calculate the equilibrium constant for the reaction, Zn + Cd 2+ = Zn2+ + Cd,
if 𝐄°𝑪𝒅𝟐+ /𝑪𝒅 = 0.403 V and 𝐄°𝒁𝒏𝟐+/𝒁𝒏 = – 0.763 V
2. Calculate the equilibrium constant for the reaction, Zn + Cu2+ = Cu + Zn2+.
Given : E° for Zn2+/Zn = – 0.763 V and for Cu2+/Cu = + 0.34 V ; R = 8.314 J
K–1 mol–1, F = 96500 C mol–1
3. Calculate the equilibrium constant for the reaction at 298 K.
4 Br– + O2 + 4 H+  2 Br2 + 2 H2O. Given that E°cell = 0.16 V.
4. Calculate the equilibrium constant for the reaction, 2 Fe 3+ + 3 I– = 2 Fe2+ +
𝑰−
𝟑 . The standard reduction potentials in acidic conditions are 0.77 and
0.54 V respectively for Fe3+/Fe2+ and 𝑰− −
𝟑 /𝑰 couples.

5. Calculate the equilibrium constant for the reaction at 298 K :

NiO2 + 2 Cl– + 4 H+  CI2 + Ni2+ + 2 H2O if Ecell = 0.320 V.
6. Calculate the equilibrium constant for the following reaction at 298 K :
Cu (s) + CI2 (g)  CuCI2 (aq)
R = 8.314 JK–1 mol–1, 𝐄°𝑪𝒖𝟐+/𝑪𝒖 = 0.34 V, 𝐄°𝟏𝑪𝑰 − = 1.36 V, F = 96500 C mol–
𝟐 𝟐 /𝑪𝑰
1

ANSWERS
1) 1.52 x 1012 2) 2.121 x 1037 3) 6.747 x 1010 4) 6.073 x 107 5) 6.747 x 1010
6) 3.295 x 1034

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ELECTROCHEMICAL CELL AND GIBBS ENERGY OF THE REACTION (RELATION

BETWEEN G° AND E°CELL)
When a cell reaction takes place, electrical energy is produced. The electrical
work thus done by the system (cell) results in the corresponding decrease in the free
energy of the system. Keeping in view the first law of thermodynamics,
Electrical work done = Decrease in free energy
for every one mole of electrons transferred in the cell reaction, the quantity of
electricity that flows through the cell is one faraday (1F = 96500 coulombs). Hence, if
n moles of electrons are transferred in any cell reaction, the quantity of electricity
flowing = nF faradays. If Ecell represents the EMF of the cell, then
Electrical work done = n FEcell
Hence, –  G = n FEcell
For comparing different cells, standard cell potentials are used which are
represented by E°cell. The corresponding free energy change is called the standard
free energy change of the reaction, represented by r G°. Hence, we can write
– r G = n FE°cell
...(i)
Also we have already learnt in Art. 3.23 that for a reaction in equilibrium,
𝑅𝑇
Ecell = 𝑛𝐹 In Kc
Substituting this value in eqn. (i), we get
𝑅𝑇
–r G = nF. In Kc or Or r G° = – RT In Kc or r G° = – 2.303 RT log Kc ...(ii)
𝑛𝐹

Hence, knowing Ecell, G° can be calculated which in turn can be used for the
calculation of the equilibrium constant Kc.
Further, as studied in thermodynamics – G = wmax. Hence, the decrease in
free energy is equal to the maximum work that can be obtained from the cell.

NUMERICAL PROBLEMS BASED ON

Calculation of G° (or Maximum Work) and Kc from E°cell

FORMULAS AND UNIT USED

– G° = nF Ecell = 2.303 RT log K = wmax
F = 96500 coulombs,
G° = Joules,
R = 8.314 JK–1 mol–1

NVS Tutorial Girish park / Dunlop Suraj Sir-9883219693

NVS Tutorial Electrochemistry Suraj Sir-9883219693

Problem 1 : (a) Calculate the standard free energy change and maximum
work obtainable for the reaction.
Zn (s) + Cu2+ (aq) = Cu (s) + Zn2+ (aq)
[Given E°𝑍𝑛2+/𝑍𝑛 = – 0.76 V, E°𝐶𝑢2+ /𝐶𝑢 = + 0.34 V, F = 96500 C mol–1]
(b) Also calculate the equilibrium constant for the reaction.
Solution. (a) The cell may be represented as :
Zn(s) | Zn2+ (1 M) || Cu2+ (1 M) | Cu(s)
E°cell = E°RHS – E°LHS = 0.34 – (– 0.76) = 1.10 volt
For the given cell reaction, n = 2
G° = –nFE°cell = – 2 x 96500 C mol–1 x 1.10 V = – 212,300 CV mol–1
= – 212, 300 J mol–1 (1 CV = 1 J) = – 212.300 kJ mol–1.
Thus, the maximum work that can be obtained from the Daniell cell = 212.3 kJ.
(b) G° = – RT ln Kc = – 2.303 RT log Kc
 – 212300 = – 2.303 x 8.314 x 298 x log Kc or log Kc
212300
= = 37.2074
2.303 × 8.314 × 298

 Kc = Antilog 37.2074 = 1.6 x 1037

Problem 2 : Estimate the minimum potential difference needed to reduce
Al2O3 at 500°C. The free energy change for the decomposition reaction
2 4
Al2O3  AI + O2 is G = + 960 kJ (F = 96500 C mol–1).
3 3
3
Solution. Al2O3 (2 Al3+ + 3 O2–)  2 Al + 2 O2, n = 6 e–
2 4
 AI2O3  3 AI + O2, n = 4 e–
3

Substituting G = + 960 kJ = + 960,000 J and n = 4 in the equation, G = – n

FE, we get
960,000 = – 4 x 96500 x E or E = – 2.487 V
 Minimum potential difference needed to reduce Al 2O3 is 2.487 V.

Problem 3: The zinc/silver oxide cell is used in hearing aids and electric
watches. The following reactions take place : Zn  Zn2+ + 2e–; E° = 0.76 V
Ag2O + H2O + 2e–  2Ag + 2OH–; E° = 0.344 V
(a) What is oxidized and reduced ?
(b) Find E° of the cell and G in joules.
Solution. (a) Zn is oxidized and Ag2O is reduced (as Ag+ ions change into Ag)
(b) Ecell = E𝐴𝑔2 𝑂/𝐴𝑔 (Red) + E𝑍𝑛/𝑍𝑛2+ (Ox) = 0.344 + 0.76 = 1.104 V

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

G = – n FEcell = 2 x 96500 x 1.104 J = – 2.13 x 105 J

Problem 4: Calculate the standard free energy change taking place in

H2/O2 fuel cell in which the following reactions occur :
(i) O2 + 4H+ + 4e–  2 H2O, E° = 1.229 V
(ii) 2 H2  4H+ + 4e–, E° = 0.000 V
Solution. Ecell = E𝑂2 /𝐻2 𝑂 (Red) + E𝐻2 /𝐻 + (Ox) = 1.229 + 0 = 1.229 V
G = –n FE°cell = – 4 x 96500 x 1.229 J = – 474.4 kJ

PROBLEMS FOR PRACTICE

1. For the cell, Mg (s) | Mg2+ (aq) || Ag+ (aq) | Ag (s), calculate the equilibrium
constant of the cell reaction at 25°C and maximum work that can be
obtained by operating the cell,
𝐄𝑴𝒈𝟐+/𝑴𝒈 = – 2.37 V and 𝐄𝑨𝒈+/𝑨𝒈 = + 0.80V (R = 8.31 J mol–1 K–1)
2. For the reaction N2 (g) + 3H2 (g) = 2NH3 (g) at 298 K, enthalpy and entropy
changes are – 92.4 kJ and – 198.2 JK–1 respectively. Calculate the
equilibrium constant of the reaction (R = 8.314 JK –1 mol–1).
3. Determine the values of equilibrium constant (K) and G° for the following
reaction :
Ni (s) + 2 Ag+ (aq)  Ni2+ (aq) + 2 Ag (s), E° = 1.05 V (1 F = 96500 C mol –
1
)
4. For the equilibrium, 2 H2 (g) + O2 (g) = 2 H2O (l) at 25°C, G° is – 474.78 kJ
mol–1. Calculate log K for it (R = 8.314 J K–1 mol–1).
5. The emf (Ecell) of the cell reaction, 3 Sn4+ + 2 Cr  3 Sn2+ + 2 Cr3+ is 0.89
V.
Calculate G° for the reaction (F = 96,500 C mol–1 and VC = J).
6. Calculate the cell e.m.f. at 25°C for the cell : Mg (s) | Mg 2+ (0.01 M) || Sn2+
(0.1 M) | Sn (s)
Given 𝐄𝑴𝒈𝟐+/𝑴𝒈 = – 2.34 V, 𝐄𝑺𝒏𝟐+/𝑺𝒏 = –0.136 V, 1 F = 96,500 C mol–1
Calculate the maximum work that can be accomplished by the operation
of this cell.
7. Write the cell formulation and calculate the standard cell potential of the
galvanic cell in operation of which the reaction taking place is :
2 Cr (s) + 3 Cd2+ (aq)  2 Cr3+ (aq) + 3 Cd (s)
Calculate rG° for the above reaction
(Given : 𝐄𝑪𝒓𝟑+/𝑪𝒓 = – 0.74 V ; 𝐄𝑪𝒅𝟐+/𝑪𝒅 = –0.40 V; F = 96500 C mol–1)

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NVS Tutorial Electrochemistry Suraj Sir-9883219693

𝟕 + 14H + 6e  Cr
–
8. 𝑪𝒓𝟐 𝑶𝟐− + +++
+ 7 H2O, E° = 1.33 V ;
3 x [2 I–  I2 + 2 e–], E° = – 0.54 V
Find out the value of the equilibrium constant and Gibbs free energy
change in the reaction given above.
9. The cell in which the following reaction occurs
2 Fe3+ (aq) + 2 I– (aq)  2 Fe2+ (aq) + I2 (s)
has Ecell = 0.236 V at 298 K. Calculate the standard Gibbs energy of the
cell reaction. (Given : 1 F = 96,500 C mol–1)

ANSWERS
1. Max. work, G° = 611.81 kJ Eqm. const, K = 1.891 x 10107
2. 6.958 x 105
3. 3.41 x 1035, – 2.02 x 105 J
4. 83.2
5. – 515310 J
6. Ecell = 2.50 V, wmax = 425.372 kJ
7. + 0.34 V, – 196.86 kJ mol–1
8. K = 1.596 x 1080, G° = 457.41 kJ mol–1
9. 45.548 kJ mol–

NVS Tutorial Girish park / Dunlop Suraj Sir-9883219693