ElECTROCHEMICAL ENERGY SYSTEMS

Electrochemistry: It is a branch of chemistry which deals with the study of transformation of

chemical energy into electrical energy and vice versa”

Electrochemical cells: “An electrochemical cell is a device which converts chemical energy into
electrical energy or electrical energy into chemical energy”

Galvanic Cell: It is an electrochemical cell which converts chemical energy into electrical
energy spontaneously.
Example: Dry cell, Lead-acid cell, Ni-Cd cell etc.

Electrolytic Cell: It is an electrochemical cell which converts electrical energy into chemical
energy.

Galvanic cells: The Daniel cell is an example of a galvanic cell. It consists of a zinc rod dipped
in a 1M ZnSO4.This forms one half cell. A copper rod dipped in a 1M CuSO4 constitutes the
other half cell. These two electrodes are connected internally by salt bridge and externally
connected through a voltmeter. The Daniel cell is based on the redox reaction.
e-

Salt bridge

+
- Copper
Zinc
_ Cathode
Anode

ZnSO4 CuSO4
Solution Solutio
n

Zn(s) + Cu2+(aq) Zn2+(aq) + Cu(s)

At the zinc electrode zinc goes into the solution as Zn2+ ions liberating electrons i.e. at zinc
electrode oxidation takes place
Zn Zn2+ + 2e-

At copper electrode reduction of Cu2+ ions takes place with the deposition of metallic copper on
copper rod by gaining electrons, i.e. at copper electrode reduction takes place
Cu2+ + 2e- Cu

By IUPAC convention the electrode at which oxidation takes place is anode and the electrode
where the reduction occurs is cathode.
In Daniel cell, zinc electrode is anode and copper electrode is cathode

1
Classification of galvanic cells:

1. Primary galvanic cell- In which the cell reaction is not completely reversible i.e. irreversible.
Example: Dry cell
2. Secondary galvanic cell- In which the cell reaction is reversible i.e. they are rechargeable.
Example:-Lead-acid battery, Ni-Cd battery etc.
3. Concentration cells:“A concentration cell is an electrochemical cell in which electrode
materials and electrolytes of two half cells are composed of same material but the concentration
of either of them is different.”
Example: Cu/Cu2+ (M1) || Cu2+ (M2)/Cu

SINGLE ELECTRODE POTENTIAL (E):

It can be defined as “the potential developed at the interface between the metal and solution,
when it is in contact with a solution of its own ions”
OR
“Single electrode potential is a measure of tendency of a given half-cell reaction to occur as
reduction, when it is in equilibrium with the other half cell”

Origin of single electrode potential:

M M

+ - - +
+ - - +
+ - - +
+ - - +
- +

Electrical double layer or Helmohltz double layer

When a metal rod is in contact with a solution of its ions, two types of reactions are possible. The
metal shows the tendency to go into the solution as metal ion by losing electrons
M Mn+ +ne-
Simultaneously, ions from the solution tend to deposited as metal atoms.
Mn+ +ne- M
These two opposite tendencies will result in an equilibrium represented by the equation.
Mn+ +ne- M

At equilibrium there is a charge separation leading to electrode potential. The metal atoms go
into the solution as positive ions leaving behind a layer of electrons on the electrode surface. The
positive ions collect around the electrode surface forming a layer of positive charges. Thus a
double layer is formed around the junction of electrode and the solution. This electrical double
layer is called Helmholts double layer (HDL. Additionally, some ions spread into the solution
and forming layers called Guoy Chapman Layer (GCL). Formation of HDL and GCL gives rise

2
to a potential difference across the layer. This potential difference between the metal and the
solution at the interface is the single electrode potential

Standard reduction potential (Eo):

Standard electrode potential is the electrode potential when the electrode is in contact with a
solution of unit concentration at 298K. If the electrode involves a gas then the gas at one
atmosphere pressure.
Sign Convention of Cell Potential:

1) Negative sign, then it indicates that the electrode acts as anode by releasing metal
ions into the solution and leaving behind the on the metal rod. Therefore, metal/anode
acquire negative charge.
2) Positive sign, then it indicates that the electrode acts as cathode. It accepts the
electrons from the metal rod and undergo reduction to give metal atoms. Metal rod
becomes electron deficient and acquire a positive charge.
Cell Notation/Representation:
Galvanic cells are represented as
Anod/Electrolyte in which anode is placed//electrolyte in which cathode is placed/cathode
i.e anode is always written on the left hand side while the cathode is written on the right hand
side. Single vertical line indicates the boundary between metal and solution. Double vertical line
indicates the salt bridge. Arrow represents the direction of electron flow.

Example: Zn/ZnSO4 (C1)//CuSO4 (C2)/Cu or Zn/ZnSO4 (C1)//CuSO4 (C2)/Cu

Derivation of Nernst equation:

Nernst equation gives a relationship between single electrode potential and change in free energy
and concentration of metal ions.
The decrease in free energy (-ΔG) represents the maximum amount of work that can be obtained
from a chemical cell reaction.
-ΔG = Wmax
Wmax = n F E
Where, n is Number of electrons, E is Electrode potential & F is Faraday constant
At standard condition; -ΔGo= n F Eo
Where, -ΔGo is Decrease in free energy under standard condition, Eo is
Standard electrode
potential
Consider a reversible electrode reaction,
Mn+ + ne M
The decrease in free energy (ΔG) and its equilibrium constant (K) are interrelated by van’t Hoff
isotherm equation as
G  G 0  RT ln K c
Where, Kc= Equilibrium constants = [products]/[reactants]

Substitute the value of Kc, we have

3
 G  G 0  RT ln
M 
M  n

Substitute the value of ΔG & ΔGo

nFE  nFE 0  RT . ln
M 
M  n

Divide the above equation by nF

E  E0 
RT M 
nF
. ln
M n 
For a solid metal concentration is unity, so that [M] =1
RT 1
Then, we have E  E 
 
0
. ln
nF M n
E  E0 
RT
nF

. ln M n  
Converting natural logarithm to the base 10 and the equation becomes as

E  E0 
2.303RT
nF
log M n   …….. (1)
Substitute the value of R=8.314J/K/mol, T=298K, F=96500C/mol to the equation (1)

E  E0 
2.303 X 8.314 X 298
nX 96500
. log M n  
E= E 
0 0.0591
n
log M n  

This is the expression for Nernst equation for single electrode at 298 k.

EMF of a cell: “EMF is the potential difference between the two electrodes of a galvanic cell,
which causes the flow of current from one electrode to other”
Nernst equation for emf of cells:
0.0591  Species .at.Cathode 
Ecell  E 0 cell  . log  
n  Species .at. Anode 

Reference electrode: “Reference electrode is an electrode whose potential is known and with
reference to that, the electrode potential of any electrode can be measured”.
There are two types of reference electrodes. They are primary and secondary reference
electrodes.
Primary Reference Electrode: It is an electrode, whose potential is arbitrarily taken as zero at
all temperatures.
Example: Standard Hydrogen Electrode (SHE)

4
Secondary Reference Electrode: It is an electrode, whose potential is known with respect to
Standard Hydrogen Electrode (SHE). They have several advantages over SHE and it is
commonly used for determining the electrode potential of various electrodes.
Example: Calomel electrode and silver- silver chloride electrode.

Calomel electrode:
Construction:
A small amount of pure mercury is placed
at the bottom of the glass tube and covered
by a calomel paste (obtained by grinding
together Hg, Hg2Cl2). A solution of
saturated KCl with Hg2Cl2 is placed over
the solid mixture. Platinum wire is dipped
into the mercury layer to make the electrical
connection. The porous disc in the above
figure is used as a salt bridge to connect
other half cell.

Calomel electrode can be represented as,

Hg(l)| Hg2Cl2|KCl(sat)
Working:
Reactions: The electrode behaves both as anode and cathode depending upon the other electrode
When it behaves as anode: Oxidation reaction takes place
2Hg + 2Cl- → Hg2Cl2 + 2e
When it behaves as cathode: Reduction reaction takes place
Hg2Cl2 + 2e→2Hg + 2Cl-
Net cell reaction is represented as follows Hg2Cl2 + 2e- 2Hg + 2Cl-
The electrode potential for the half cell is gven as
E = E0 – 2.303RT log [Hg]2[Cl-]2
nF [Hg2Cl2]
The concentration of Hg and Hg2Cl2 is unity. The number of moles of electrons involved 2 and
therefore, n = 2.
By substituting all these in the above equation,
E = E0 – 2.303RT log [Cl-]2
2F
By substituting R, F and at Standard condition, the above equation becomes
E = E0 – 0.0591/2 log[Cl2 at 298 K (Nernst equation for calomel electrode)
Hence, the electrode potential of Calomel electrode is dependent on the concentration of
chloride ions and it is reversible with respect to chloride ions.

Concentration of KCl 0.1N 1.0N Saturated

Potential of Calomel Electrode 0.334 V 0.280 V 0.241 V

5
Advantages:
● It is very simple to construct
● The cell potential is constant over a long period
● The potential does not vary with temperature
Silver- Silver Chloride electrode:
Construction: It is prepared by coating of Ag on Pt wire through electrolysis of an
argantocyanide solution. The coated silver is partially converted into AgCl
by making it an anode in KCl solution and passing a current of low density
for 30 minutes. The resulting Ag and AgCl coated Pt is dipped in KCl
solution. A drop of AgNO3 is added to the electrode to avoid the stripping of
AgCl from the electrode.

Ag/AgCl Electrode can be cell represented as, Ag(s)/AgCl/KCl(sat)

Net half cell reaction is

AgCl + e- Ag + Cl-
0.0591
Electrode Potential E  E O  log[ M n ]
n
0.0591
E  E0  log[ Cl  ] Where n  1
n
E  E  0.0591 log[ Cl  ] At 298 K
O

( Nernst Equatation for Ag / AgCl electrode )

Hence, the electrode potential is dependent on the concentration of chloride ions and it is
reversible with respect to chloride ions.

Concentration of KCl 0.1 N 1.0 N Saturated

Potential of Ag/AgCl 0.290 0.244V 0.199V
Electrode At 298 K

Advantages:
 It is easy to construct.
 The potential of the electrode remains constant as long as chloride ion concentration
remains constant.
 It is inexpensive
Measurement of electrode potential using reference electrode (Calomel or Ag-AgCl
electrode):
The electrode potential of a single electrode can be measured by using some reference electrode
whose electrode potential is known. Commonly used reference electrodes are Calomel electrode
& Ag-AgCl electrode. In order to measure the electrode potential of given electrode, it is coupled
with reference electrode internally through salt bridge and externally through electronic
voltmeter. Then the valve of emf of cell, E cell is measured using electronic voltmeter. i.e. the
metal is dipped is in a solution containing its own ions and connected to the reference electrode
through a salt bridge internally and by electronic voltmeter externally. Emf of the cell is obtained
from electronic voltmeter.

6
For example to determine the standard electrode potential of Zn, the Zn electrode is immersed in
1 M ZnSO4 solution and coupled with saturated calomel electrode as shown below.

Then the EMF of cell is given by

Ecell = Ecathode ̶ Eanode
Then, Ecell = ECalomel ̶ E Zn2+/ Zn
E Zn2+/ Zn = ECalomel ̶ Ecell

Here Zn electrode acts as anode and Calomel electrode act as cathode

Anodic reaction: Zn Zn2+ + 2e

Cathodic reaction: Hg2Cl2 + 2e 2Hg + 2Cl-

Net cell reaction: Zn + Hg2Cl2 Zn2+ + 2Hg

Note: (i) Similarly the electrode potential of Cu electrode can be determined, where Cu electrode
acts as cathode and saturated calomel electrode acts as anode.
(ii) In the same way you silver-silver chloride electrode can be used to determine the
electrode potential.
Ion selective electrodes: These are the electrodes that are selectively sensitive to certain
ions and develop a potential proportional to the concentration of the ions.
Example: Glass electrode

Construction of Glass electrode: The glass electrode consists

of a long glass bulb made up of special type of glass with
composition Na2O-22%, CaO-6% and SiO2-72%. The glass
bulb is filled with a solution of known H+ ion concentration
(Generally, 0.1 M HCl). An Ag-AgCl electrode is place in the
solution and connected by a Pt wire for electrical contact.
0.1 M Hcl
Here, Ag-AgCl electrode serve as internal reference electrode

The glass electrode is represented as

Ag-AgCl electrode
Ag/AgCl(s)/0.1 M HCl/Glass
H+ Ion Solution
7
Glass electrode
Principle:
When a thin glass membrane is placed between two solutions
of different pH values, a potential difference arises across the
membrane, called as boundary potential Eb. The potential is
due to the difference in the potential of developed across the
gel layer of the glass membrane between the two solutions.
H+ Ion
Solution (C1) Working of Glass electrode:
Gel layer of When the glass electrode is immersed in the test solution, the
the glass Na+ ions of the glass membrane are exchanged for H+ ions of
memebrane the test solution.
Glass bulb
H+ + Na+Gl- Na+ + H +Gl-
H+ Ion Solution
(C2)
Let us consider the glass electrode is filled with HCl solution
E1 E2
of concentration C1, and dipped in a test solution of
concentration C2.
Then the boundary potential arising across the membrane and is given by
Eb = E2- E1

Where E2 and E1 are the potentials outside and inside the membrane respectively.

According to Nernst,
Eb = 2.303RT log C2
nF C1

Eb = 2.303RTlogC2 - 2.303RTlog C1
nF nF

constant
Since the concentration or the HCl present inside the bulb is known (0.1M HCl) and n is 1, the
above equation at cab be written as
Eb = 0.059logC2+ constant
Since C2 is the concentration of H+ ions outside the membrane and hence C2= [H+]
Eb = 0.059log [H+] + constant {since, pH = -log [H+]}
Eb = constant-0.059pH …….Boundary potential for glass electrode

The glass electrode potential (EG) depends upon boundary potential(Eb), Ag-AgCl electrode and
Asymmetry potential (Eassy).
EG = Eb + EAg-AgCl + EAsy ………………. (1)
Theoretically, Eb = 0 when C1=C2. However, it has been observed that even when C1=C2, small
potential is developed this potential is called Asymmetry potential (Eassy). This arises due to the
strain involved in the inner and outer surface of the glass membrane.

8
By substituting the Eb in the equation (1), we obtain
EG = constant + EAg-AgCl + EAsy -0.059pH

Constant = EοG
Since EAg-AgCl is known and EAsy is constant for a particular concentration, the above equation
becomes

EG = EοG-0.059pH
Determination of pH using glass electrode:

PotentioMeter

To determine the pH of the given solution the

Glass glass electrode is dipped into the solution. It is
Calomel electrode
electrode
combined with a reference electrode such as a
calomel electrode through a salt bridge
internally and by electronic voltmeter or
potentiometer externally.
Solution of
unknown pH

The cell assembly is represented as,

Hg|Hg2Cl2|KCl||Solution of unknown pH|glass|0.1M HCl|Ag+|AgCl
The emf of the cell is given by

E cell=Ecathode-Eanode
Here, glass electrode act as cathode
E cell =Eglass- Ecalomel(SCE)
E cell = EοG- 0.0591 pH - ESCE [since, EG=EGo- 0.0591 pH]
0.0591 pH = EοG - Ecell – ESCE
pH = EοG - E cell – ESCE
0.0591
pH = EοG - E cell –0.244
0.0591

9
Solution for Problems
1.Calculate the potential of Daniel cell at 250 C, given the electrode potentials of Cu and Zn are 0.34V and
–0.76V respectively.

Given: E0Zn = -0.76V; E0Cu= 0.34V

w.k.t Ecell = Ecathode -Eanode
Ecell = 0.34-(-0.76)
Ecell = 1.1 V

2. Calculate the voltage of the cell Mg(s)Mg+2(1M) Cd+2(7x10-11M) Cd(s), where E0cell=1.97V.
Given:E0cell = 1.97V
[Mg+2] =1M
[Cd+2] = 7x10-11M
0.0591 [Cd 2 ]
Ecell  E o
cell  log
n [ Mg  2 ]
0.0591
Ecell  1.97  log 7 X 10 11  1.6699V
2
3. Write the half cell and net cell reactions for the cell
Cd(s)Cd+2(0.01M)Cu+2(0.5M) Cu(s)
The standard reduction potentials of Cd and Cu are –0.4V and 0.34V respectively. Calculate the emf of
the cell.
Given: E0Cd = -0.4V; E0Cu= 0.34V; [Cd+2] =0.01M; [Cu+2] = 0.5M

At anode: Cd Cd2+ +2e-

At cathode Cu2+ + 2e- Cu

Net cell reaction Cd + Cu2+ Cd2+ + Cu

E o Cell  ECathode  E Anode  0.34  (0.40)  0.74 V

0.0591 [Cu 2 ]
E cell  E 0 Cell  
n
log

Cd  2 
0.0591 0.5
Ecell  0.74  log  0.7902V
2 0.01

10
 4. A cell is constructed by coupling Zn electrode dipped in 0.5 M ZnSO4 and Ni electrode dipped in
0.05M NiSO4. Write the cell representation, cell reaction & calculate emf of the cell, given SRPs of
Zn and Ni as -0.76 & -0.25 v respectively. [July/Aug 02]
Zn(s)Zn+2(0.5M)Ni+2(0.05M) Ni(s)

At anode: Zn Zn2+ +2e-

At cathode Ni2+ + 2e- Ni

Net cell reaction Zn + Ni2+ Zn2+ + Ni

E o Cell  ECathode  E Anode   0.25  (0.76)  0.51V
0.0591 [ Ni 2 ]
E cell  E o Cell 
n
log

Zn  2 
0.0591 0.05
Ecell  0.51  log  0.4804 V
2 0.5
5. What voltage will be generated by a cell that consists of an iron rod immersed in 1.0M FeSO 4
solutionand a manganese rod immersed in 0.1M MnSO4solution at 298K? Given E0Fe2+/Fe = -0.44V;
E0Mn2+/Mn = -1.18V [March 01]
Mn(s)Mn+2(0.1M)Fe+2(1.0M) Fe(s)

E o Cell  ECathode  E Anode  0.44  (1.18)  0.74 V

0.0591 [ Fe 2 ]
 E Cell 
 
0
E cell log
n Mn  2
0.0591 1
Ecell  0.74  log  0.7696V
2 0.1
6. Calculate the potential of Ag-Zn cell at 298 K, if the concentration of Ag+ and Zn +2 are 5.2x10-6M
and 1.3x10-3M respectively. E0 of the cell at 298K is 1.5V given: T=298K; E0cell = 1.5V.
[Ag+] =5.2x10-6M[Zn+2] = 1.3x10-3M

0.0591 [ Ag  ] 2
Ecell  E 0 Cell 
n
log

Zn  2 
6 2
0.0591 (5.2 x10 )
Ecell  1.5  log  1.27 V
2 1.3x10 3

7. An electrochemical cell consists of iron electrode dipped in 0.1M FeSO4 and silver electrode in 0.05M
AgNO3. Write the cell representation, cell reaction and calculate the emf of the cell at 298K.
(The standard reduction potentials of iron and silver are –0.44V and 0.8V respectively).
Given: T=298K; E0Fe = -0.44V; E0Ag= 0.8V
[Fe+2] =0.1M
[Ag+] = 0.05M
cell representation: Fe(s) FeSO4(0.1M)  AgNO3(0.05M)  Ag(s)

11
E o Cell  ECathode  E Anode  0.8  (0.44)  0.36 V
0.0591 [ Ag  ] 2
E cell  E 0 Cell 
n
log
Fe  2 
2
0.0591 [0.05]
Ecell  0.36  log 1.19V
2 0.1
8. Calculate the emf of the cell Fe(s)FeSO4(0.01M)  AgNO3(0.1M)  Ag(s) at 298 K, if SRPs of Fe and
Ag are -0.44 Vand 0.8 V respectively (Jan/Feb 03: Dec 07/Jan 08)

E 0 Cell  ECathode  E Anode  0.8  (0.44)  0.36 V

2
0.0591 [ Ag  ]
ECell  E 
 
0
Cell log
n Fe  2
2
0.0591 [0.1]
Ecell  0.36  log 1.24V
2 0.01
9. An Electrochemical cell consists of a copper electrode dipped in 0.5 M CuSO4 and silver electrode
dipped in 0.25 M AgNO3. Write the cell scheme, half cell and net cell reactions. Also, calculate the emf.
Given, SRPs of Cu & Ag are 0.34 and 0.8V respectively.
cell representation: Cu(s) CuSO4(0.5M)  AgNO3(0.25M)  Ag(s)

At anode: Cu Cu2+ +2e-

At cathode 2Ag+ + 2e- 2Ag

Net cell reaction Cu + 2Ag+ Cu2+ + 2Ag

E 0 Cell  ECathode  E Anode  0.8  (0.34)  0.46 V

2
0.0591 [ Ag  ]
ECell  E 
 
0
Cell log
n Cu  2

Ecell  0.46 
0.0591
log
0.25  0.433 V 2

2 0.5

10.Calculate the cell potential of a cell containing Ag+/Ag & Cu/Cu2+ if the concentrations
of Ag+ and Cu2+ ions are 4.2 X 10-6 and 1.3 X 10-3 respectively. Given E0Ag+/Ag=0.8V,
E0Cu2+/Cu = 0.34V

E 0 Cell  ECathode  E Anode  0.8  (0.34)  0.46 V

2
0.0591 [ Ag  ]
ECell  E 
 
0
Cell log
n Cu  2

12
 Ecell  0.46 
0.0591
log
4.2 X 10 6   2

 0.2275V
2 1.3 X 10 3
11. Calculate single electrode potential of Zn electrode when [ Zn2+] =0.1M Given EoZn2+/Zn=-0.76V
(July/Aug05)
0.0591 [H  ]
Ecell  Ecell 
0
log
n [ Zn  2 ]
0.0591 [1]
Ecell  .076  log   0.7895V
n [0.1]
12. Calculate the electrode potential at a copper electrode dipped in a 0.1M solution of copper sulphate at
298K, assuming copper sulphate to be completely dissociated. The standard electrode potential of
Cu+2/Cu is 0.34V at 298KGiven: T=298K; E0Cu= 0.34V
[Cu+2] =0.1M
logCu 2  
0.0591
E Cu  2  E0  at 298 K
Cu n
0.0591
E Cu  2  0.34  log( 0.1)
Cu 2
E Cu  2  0.34  0.0296
Cu

E Cu  2  0.3105 V
Cu

13. Calculate the standard electrode potential of Cu2+/Cu if its electrode potential at 25oC
0.296V when [Cu2+]= 0.015M(June-July 08)

Ecell  Ecell 
0 0.0591
n
log Cu 2  
0.0591
E0  E  log 0.015
2

0.0591
E 0  0.296  log 0.015
2
E0 =0.349V
14.Write the electrode reactions and Calculate the EMF of the given cell at 298K, Ag(s)AgNO3
(0.018M) AgNO3 (1.2M)Ag(s).

At anode Ag(s) Ag+ + e-

At cathode Ag+ + e- Ag(s)

0.0591  C 2 
. w.k.t E cell  log  at 298K
n  C1
 1.2 
E cell  0.0591 log  (n=1)
 0.018 

13
 Ecell = 0.1078 V.
15. Calculate the emf of Copper concentration cell at 250 C, where the copper ions ratio in the
cell is 10.
[Cu 2 ]cathode C 2
Given:   10
[Cu  2 ]anode C 1
0.0591  C 2 
w.k.t E cell  log  ; at 298 K
n  C1 
0.0591
E cell  log( 10)
2
Ecell = 0.0296 V.

16.A concentration cell was constructed by immersing two silver electrode in 0.05M and 1M
AgNO3 solution. Write the cell representation, cell reactions and calculate the EMF of the cell.
(July-06)
Cell representation: Ag(s) AgNO3(0.05M)  AgNO3(1M)  Ag(s)
At anode: Ag(0.05M) Ag+(0.05M) +e-
At cathode Ag+ (1M) + e- Ag (1M)
0.0591  C 2
 Net cell reaction Ag(0.05M) + Ag+ Ag+ (0.05M)+ Ag
E cell  log
n  C1

0.0591  1 
Ecell  log
 0.05 
 
Ecell = 0.0768V

17. A concentration cell was constructed by immersing two silver electrode in 0.01M and
10M AgNO3 solution. Write the cell representation, cell reactions and calculate the emf of
the cell. (July-Aug 05)
Cell representation: Ag(s) AgNO3(0.01M)  AgNO3(10M)  Ag(s)

At anode: Ag(0.01M) Ag+(0.01M) +e-

At cathode Ag+ (10M) + e- Ag (10M)
0.0591  C 2
 Net cell reaction Ag(0.01M) + Ag+ Ag+ (0.01M)+ Ag
E cell  log
n  C1

0.0591  10 
Ecell  log
 0.01 
 
Ecell = 0.1773V

18. The spontaneous galvanic cell Tin/Tin ion (0.024M)//Tin ion(0.064M) /Tin develop an
emf of 0.0126 V at 25OC, Calculate the Valency of Tin.(Jan-06)

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 0.0591  C 2 
E cell  log 
n  C1 

0.0591  C2 
n log 
Ecell  C1 
0.0591  0.064 
n log 
0.0126  0.024 
n =2(Valency of tin)

19. Claculate the potential of the Zn-Cu Daniel cell at 298K, if the free energy change of the cell
reaction is -212.3kJmol-1, Faraday constant, F=96.5kJV-1mol-1.

-ΔGo= nFEo
G o 212.3
Ecell    1.10 V
 nF  2 X 96.5
20. In the daniell cell
a) Calculate the cell potential if the Zn2+ and Cu2+ concentrations are 0.1 M and 1.0X10 -9M
respectively at 298K?

b) Calculate ΔG and ΔGo for the reduction of 1.0 mol of Cu2+ by Zn at 298K.
EoCell=1.10V.

0.0591 [Cu 2 ]
Ecell  Ecathode  E anode 
 
0 0
log
n Zn  2

0.0591 [1.0 X 10 9 ]
Ecell  0.34  (0.76)  log  0.8636V
2 0.1
G  nFE  2 X 96.5 X 0.8636  166.7 kJmol 1

G o  nFE o  2 X 96.5 X 1.10   212.3 kJmol 1

21. The EMF of the cell Cu/CuSO4)(0.01M) //CuSO4(XM)/Cu is 0.0295V at 25OC. Find the value
of X.

0.0591  C 2 
E cell  log 
n  C1 
0.0591  X 

0.0295  log
2  0.01 
 

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Ans: 0.09964M

22. Represent the cell formed by the coupling of two electrodes immersed in CuSO4 solution
concentration of cupric ions in one electrode system is 100 times more concentration than other.
Write the cell reaction and calculate the potential at 300K.(July 07)

Cu(s) CuSO4(1M) CuSO4(100M) Cu(s)Possibility 10/0.1=100 or 5/0.05 or 5/0.05=100

0.0591  C2  0.0591  10 
Ecell  log  Ecell  log 
n  C1  2  0.1 
ECell=0.0595V

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