(Physical Chemistry) ELECTROCHEMISTRY

1. INTRODUCTION
Chemical reactions can be used to produce electrical energy, conversely, electrical energy can
be used to carry out chemical reactions that do not proceed spontaneously.
Electrochemistry is the study of production of electricity from energy released during
spontaneous chemical reactions and the use of electrical energy to bring about non-
spontaneous chemical transformations. The subject is of importance both for theoretical and
practical considerations. A large number of metals, sodium hydroxide, chlorine, fluorine and
many other chemicals are produced by electrochemical methods. Batteries and fuel cells
convert chemical energy into electrical energy and are used on a large scale in various
instruments and devices. The reactions carried out electrochemically can be energy efficient
and less polluting. Therefore, study of electrochemistry is important for creating new
technologies that are eco friendly. The transmission of sensory signals through cells to brain
and vice versa and communication between the cells are known to have electrochemical origin.
Electrochemistry, is therefore, a very vast and interdisciplinary subject. In this Unit, we will
cover only some of its important elementary aspects.
ELECTROCHEMICAL CELL:
If a metal electrode is immersed in an aqueous solution containing cations of that metal, an
equilibrium that leads to negative charge formation on the electrode is established. This
configuration of electrode and solution is called a half-cell. Two half-cells can be combined to
form an electrochemical cell. The equilibrium condition in an electrochemical cell is that the
electrochemical potential, rather than the chemical potential, of a species is the same in all
parts of the cell. The electrochemical potential can be changed through the application of an
electrical potential external to the cell. This allows the direction of spontaneous change in the
cell reaction to be reversed. Electrochemical cells can be used to determine the equilibrium
constant for the cell reaction. Electrochemical cells can also be used to provide power, in which
case they are called batteries. Electrochemical cells in which the reactants can be supplied
continuously are called fuel cells.

Thus the two types of cells are reverse of each other.

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2. GALVANIC CELL OR VOLTAIC CELL:
A galvanic cell is an electrochemical cell that converts the chemical energy of a spontaneous
redox reaction into electrical energy. In this device the Gibbs energy of the spontaneous redox
reaction is converted into electrical work which may be used for running a motor or other
electrical gadgets like heater, fan, geyser, etc.
2.1 Constriction of galvanic cell:
Anode: Some metals (which are reactive) are found to have tendency to go into the solution
phase when these are placed in contact with their ions or their salt solutions. For example: Zn
rod is placed in ZnSO4 solution.

If a Zn electrode is partially immersed in an aqueous solution of ZnSO4 , an equilibrium is

established between Zn(𝑠) and Zn2+ (𝑎𝑞) as a small amount of the Zn goes into solution as
Zn2+ (𝑎𝑞) ions as depicted in above figure. Zn(s) ⇄ Zn2+ + 2e−
However, the electrons remain on the Zn electrode. Therefore, a negative charge builds up on
the Zn electrode, and a corresponding positive charge builds up in the surrounding solution.
This charging leads to a difference in the electrical potential between the electrode and the
solution, which we call the half-cell potential or electrode potential. This particular electrode is
known as anode.
On anode oxidation will take place. (release of electrons).
To act as source of electrons.
It is of negative polarity.
The electrode potential is represented by EZn(s)/Zn 2+(aq.)
Cathode:
Some metals (Cu, Ag, Au etc.,) are found to have the opposite tendency i.e., when placed in
contact with their aqueous ions, the ions from the solution will get deposited on the metal rod.

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The following equilibrium will be established: Cu2+ + 2e− ⇄ Cu(s).
So rod will have deficiency of electron (positive charge). Extra negative charge will surround
this positively charged rod and form double layer. An electrical double layer is developed in the
system and hence a potential difference is created between the rod and the solution which is
known as half cell potential or electrode potential. This will be known as cathode.
At cathode reduction will take place. (gain of electrons will take place)
To act as sink of electron.
Positive polarity will be developed.
Their electrode potential can be represented by : ECu2+ (aq. )/Cu(s)
Is where oxidation occurs Is where reduction occurs
Anode: { Is where electrons are produced Cathode: { Is where electrons are consumed
Has a negative sign Has a positive sign
Half-cell potentials cannot be measured directly. They are measured relative to one another
rather than absolutely. To understand how this is done, it is useful to consider an
electrochemical cell, which consists of two half-cells, such as the one shown figure. This
particular cell is known as the Daniell cell, after its inventor. On the left, a Zn electrode is
immersed in a solution of ZnSO4 (𝑎𝑞). The solute is completely dissociated of CuSO4, which is
completely dissociated to form Cu2+ (𝑎𝑞) and SO2−
4 (𝑎𝑞). The two half-cells are connected by an

ionic conductor known as a salt bridge. The salt bridge consists of an electrolyte such as KCl
suspended in a gel. A salt bridge allows current to flow between the half-cells while preventing
the mixing of the solutions. A metal wire fastened to each electrode allows the electron current
to flow through the external part of the circuit.

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2.2 Salt bridge:
A salt bridge is a U-shaped inverted tube that contains a gel permeated with an inert
electrolyte. Generally tube is filled with a paste of agar-agar powder with a natural
electrolyte/generally not common to anodic/cathodic compartment with porous plugs at each
mouth of tube. The ions of the inert electrolyte do not react with other ion in the solution and
the ions are not oxidised or reduced at the electrodes.
The electrolyte in salt bridge should be such that speed of it's cation equals speed of it's anion
in electrical field. For that charge and sign of the ions should be almost equal i.e. Mobility of
cation = Mobility of anion
KCl is generally preferred but KNO3 or NH4 NO3 can also be used.
If Ag + , Hg 2 2+ , Pb2+ , Tl+ ions are present in a cell then in salt bridge KCl is not used because there
can be formation of precipitate of AgCl, Hg 2 Cl2 , PbCl2 or TlCl at mouth of tube which will prevent
the migration of ions and its functioning will stop.
Functions of Salt Bridge:
(i) It connects the solution of two half cell to complete the circuit.
(ii) It minimize the liquid junction potential. The potential difference between the junction of
two liquids. (Liquid-Liquid Junction Potential: The potential difference which arises between
two solutions (during the progress of reaction) when in contact with each other.)
(iii) It maintains the electrical neutrality of the solution in order to give continuous flow or
generation of current.
"The simultaneous electrical neutrality of the anodic oxidation chamber and cathodic reduction
chamber is due to same mobility or velocity of K + and NO3 − ions taken into salt bridge.
(iv) If the salt bridge is removed then voltage drops to zero.
(v) It prevents mechanical mixing of two electrolytic solution.
2.3 Shorthand Notation for Galvanic Cells
We require two half cells to produce an electrochemical cell, which can be represented by
following few rules;
The anode half-cell is always written on the left followed on the right by cathode half cell.
The separation of two phases (state of matter) is shown by a vertical line.
The various materials present in the same phase are shown together using commas.
The salt bridge is represented by a double slash (∥).
The significant features of the substance viz. pressure of a gas, concentration of ions etc. are
indicated in brackets immediately after writing the substance.
For a gas electrode, the gas is indicated after the electrode for anode and before the
electrode in case of cathode. (i.e PtH2 /H + or H + /H2 Pt )

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Ex.1 Write short hand notation for the following reaction,
Sn2+ (aq) + 2Ag + (aq) ⟶ Sn4+ (aq) + 2Ag(s)
Sol. The cell consists of a platinum wire anode dipping into an Sn+2 solution and a silver cathode
dipping into an Ag + solution therefore
Pt (s)|Sn2+ (aq), Sn4+ (aq) ∥ Ag + (aq)|Ag(s).
Ex.2 Write the electrode reaction and the net cell reaction for the following cells. Which electrode
would be the positive terminal in each cell ?
(a) Zn|Zn2+ ∥ Br − , Br2 |Pt (b) Cr|Cr 3+ ∥ I − , I2 |Pt
(c) Pt|H2 , H + ∥ Cu2+ |Cu (d) Cd|Cd2+ ∥ Cl− , AgCl|Ag
Sol. (a) Oxidation half cell reaction, Zn ⟶ Zn2+ + 2e−
reduction half cell reaction, Br2 + 2e− ⟶ 2Br −
Net cell reaction Zn + Br2 ⟶ Zn2+ + 2Br −
(Positive terminal: cathode Pt)
(b) Oxidation half reaction, [Cr ⟶ Cr 3+ + 3e− ] × 2
reduction half reaction, [I2 + 2e− ⟶ 2I − ] × 3
Net cell reaction 2Cr + 3I2 2Cr 3+ + 6I −
(Positive terminal: cathode Pt )
(c) Oxidation half reaction, H2 ⟶ 2H + + 2e−
reduction half reaction, Cu2+ + 2e− ⟶ Cu
Net cell reaction H2 + Cu2+ ⟶ Cu + 2H +
(Positive terminal: cathode Cu )
(d) Oxidation half reaction, Cd ⟶ Cd2+ + 2e−
reduction half reaction, [AgCl + e− Ag + Cl− ] × 2
Net cell reaction Cd + 2AgClCd2+ + 2Ag + 2Cl−
(Positive terminal: cathode Ag)
2.4 Half cell potential/ Electrode Potential:
The potential difference developed between metal electrode and its ions in solution in known
as electrode potential.
The potential difference developed between metal electrodes and the solution in
standard conditions (i.e. 1M concentration of its ions at 1 bar pressure and at a particular
temperature) is known as standard electrode potential. According to IUPAC convention,
standard reduction potentials are now called standard electrode potentials Two types of
oxidation potentials:

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Standard Oxidation Potential(SOP) : Reduction Potential (R.P.)
The electrode potential for oxidation half The electrode potential for half reduction half
reaction reaction
Greater is the SOP, greater will be tendency Greater is the R.P. greater will be tendency to
to get oxidized in standard conditions. get reduced in standard conditions.

Type of Electrode Half reaction Representation

Metal electrode 0
EZn 2+ /Zn(s) (SRP)
Reduction : Zn2+ + 2e− → Zn(s)
1. (Zn electrode, Cu 0
Oxidation : Zn(s) → Zn2+ + 2e− EZn(s/Zn (SOP)
electrode etc.) 2+

0
Hydrogen peroxide Reduction : 2e− + 2H + + H2 O2 → 2H2 O EH 2 O2 /H2 O
(SRP)
2
electrode Oxidation : H2 O2 → O2 + 2H + + 2e− 0
EH (SOP)
2 O2 /O2

Reduction : MnO− + −
4 + 8H + 5e → Mn
2+
+ 0
3. Redox electrode EMnO − /Mn2+ (SRP)
4H2 O 4

2.3 Free energy changes for cell reaction:

The free energy change ΔG (a thermochemical quantity) and the cell potential E (an
electrochemical quantity) both measure the driving force of a chemical reaction.
The values of ΔG and E are directly proportional and are related by the equation, ΔG = −nFE
where n = Number of moles of electron transferred in the reaction.
F = Faraday constant = 96485C/mole−
2.4 Cell potential:
The cell potential is the difference between the electrode potentials (reduction potentials) of
the cathode and anode. It is called the cell electromotive force (emf) of the cell when no current
is drawn through the cell.
The emf of the cell or cell potential can be calculated from the values of electrode potential of
the two half cell constituting the cell. The following three method are in use:
(i) When oxidation potential of anode and reduction potential of cathode are taken into account:
Ecell = oxidation potential of anode + reduction potential of cathode
= 𝐸ox ( anode ) + 𝐸red (cathode )
In standard conditions
0
Ecell = SOP of anode + SRP of cathode
0 0
Ecell 0
= Eox (anode) + Ered (cathode)
(ii) When reduction potential of both electrodes are taken into account:
Ecell = Reduction potential of cathode − Reduction potential of anode
= Ered (cathode ) − Ered (anode )
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In standard conditions
0
Ecell = SRP of cathode + SRP of anode
0 0 0
Ecell = Ered (cathode) − Ered (anode)
∘ ∘
Ecell is intensive property so on multiplying/Dividing cell reaction by any number, the Ecell
value would not change.
2.4.1 Measurement of Electrode Potential:
The potential of individual half-cell cannot be measured. We can measure only the difference
between the two half-cell potentials that gives the emf of the cell. If we arbitrarily choose the
potential of one electrode (half-cell) then that of the other can be determined with respect to
this. According to convention, a half-cell called standard hydrogen electrode (Reference
electrode) is assigned a zero potential at all temperatures corresponding to the reaction
0
2H + (aq, 1M) + 2e− ⟶ H2 ( g, 1 bar ) EH + /H = 0 V
2

0
H2 ( g, 1 bar ) ⟶ 2H + (aq, 1M) + 2e− EH 2 /H
+ = 0V

Δf G0 [H + (aq.) ] = 0
The standard hydrogen electrode consists of a platinum electrode coated with platinum black.
To achieve equilibrium on a short timescale, this reaction 2H + + 2e− ⟶ H2 is carried out over
a platinum black catalyst electrode.

The electrode is dipped in an acidic solution and pure hydrogen gas is bubbled through it. The
concentration of both the reduced and oxidised forms of hydrogen is maintained at unity. This
implies that the pressure of hydrogen gas is one bar and the concentration of hydrogen ion in the
solution is one molar.
At 298 K the emf of the cell, standard hydrogen electrode with second half-cell constructed by
taking standard hydrogen electrode as anode (reference half-cell) and the other half-cell as
cathode, gives the reduction potential of the other half-cell. If the concentrations of the oxidised
and the reduced forms of the species in the right hand half-cell are unity, then the cell potential
is equal to standard electrode potential,
0 0 0
Ecell = (Eox )SHE + (Ered )Elactrode
0 0 0
Ecell = 0 + (Ered )Electrode = (Ered )Electrode
The measured emf of the cell:

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Pt (s) ∣ H2 (g, 1 bar) ∣ H + (aq, 1M) ∥ Cu2+ (aq, 1M) ∣ Cu
is 0.34 V and it is also the value for the standard electrode potential of the half - cell
corresponding to the reaction:
Cu2+ ( aq, 1M) + 2e− → Cu(s)
Similarly, the measured emf of the cell:
Pt(s) ∣ H2 ( g, 1 bar) ∣ H + (aq, 1M) ∥ Zn2+ (aq, 1M) ∣ Zn
is −0.76 V corresponding to the standard electrode potential of the half-cell reaction:
Zn2+ ( aq, 1M) + 2e− → Zn(s)
The positive value of the standard electrode potential in the first case indicates that Cu2+ ions
get reduced more easily than H + ions. The reverse process cannot occur, that is, hydrogen ions
cannot oxidize Cu (or alternatively we can say that hydrogen gas can reduce copper ion) under
the standard conditions described above. Thus, Cu does not dissolve in HCl. In nitric acid it is
oxidised by nitrate ion and not by hydrogen ion. The negative value of the standard electrode
potential in the second case indicates that hydrogen ions can oxidise zinc (or zinc can reduce
hydrogen ions).
In view of this convention, the half reaction for the Daniell cell in Fig. 3.1 can be written as:
Left electrode : Zn(s) → Zn2+ (aq, 1M) + 2e−
Right electrode : Cu2+ ( aq, 1M) + 2e− → Cu(s)
The overall reaction of the cell is the sum of above two reactions and we obtain the equation:
Zn(s) + Cu2+ (aq) → Zn2+ (aq) + Cu(s)
0
emf of the cell = Ecell = ER0 − EL0
= 0.34 V − (−0.76)V = 1.10 V
Sometimes metals like platinum or gold are used as inert electrodes. They do not participate in
the reaction but provide their surface for oxidation or reduction reactions and for the conduction
of electrons.
For example, Pt is used in the following half - cells:
Hydrogen electrode: Pt(s)|H2 ( g)|H + (aq)
1
With half-cell reaction: H + (aq) + e− → 2 H2 ( g)

Bromine electrode: Pt(s)|Br2 (aq)|Br − (aq)

1
With half-cell reaction: 2 Br2 (aq) + e− → Br − (aq)

The standard electrode potentials are very important and we can extract a lot of useful
information from them. The values of standard electrode potentials for some selected half-cell
reduction reactions are given in Table. If the standard electrode potential of an electrode is
greater than zero then its reduced form is more stable compared to hydrogen gas. Similarly, if
the standard electrode potential is negative then hydrogen gas is more stable than the reduced
form of the species. It can be seen that the standard electrode potential for fluorine is the
highest in the Table indicating that fluorine gas (F2 ) has the maximum tendency to get reduced
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to fluoride ions (F) and therefore fluorine gas is the strongest oxidising agent and fluoride ion
is the weakest reducing agent. Lithium has the lowest electrode potential indicating that
lithium ion is the weakest oxidising agent while lithium metal is the most powerful reducing
agent in an aqueous solution. It may be seen that as we go from top to bottom in Table the
standard electrode potential decreases and with this, decreases the oxidizing power of the
species on the left and increases the reducing power of the species on the right hand side of the
reaction. Electrochemical cells are extensively used for determining the pH of solutions,
solubility product, equilibrium constant and other thermodynamic properties and for
potentiometric titrations.
Electrode Reaction SRP (at 298 K)
* Li Li+ + e− → Li(s) – 3.05 V
K K + + e− → K(s) – 2.93 V
Ba
Ca Ca+2 + 2e− → Ca(s) – 2.87 V
Na Na+ + e− → Na(s) – 2.71 V
Mg Mg +2 + 2e− → Mg(s) – 2.71 V
Al
*Electrolytes (H2O) H2 O(l) + e− → H2 + OH − – 0.828 V
Zn Zn+2 + 2e− → Zn(s) – 0.76 V
Cr Cr +3 + 3e− → Cr(s) – 0.74 V
*Fe Fe2+ + 2e− → Fe – 0.44 V
Cd Cd+2 + 2e− → Cd(s) – 0.41 V
Co
Ni Ni+2 + 2e− → Ni(s) – 0.24V
Sn Sn+2 + 2e− → Sn(s) – 0.14 V
Pb Pb+2 + 2e− → Pb(s) – 0.13 V
*H2 2H + + 2e− → H2 ( g) – 0.00 V
Cu Cu2+ + 2e− → Cu(s) – 0.34 V
I2
Fe Fe3+ + e− → Fe – 0.77V
Hg Hg 2+ −
2 + 2e → Hg(l) – 0.79 V
Ag Ag + + e− → Ag – 0.80 V
Hg Hg 2+ → Hg(l) – 0.85 V
Br2 Br2 + 2e− → 2Br − – 1.06 V

Electrochemical Series :
∗ Electrolytes O2 + 2H + + 2e− → H2 O(ℓ) 1.23 V
∗ Cr2 O2− + −
7 + 14H + 6e → 2Cr
+3
+ 7H2 O 1.33 V
− −
∗ Cl2 Cl2 + 2e → 2Cl 1.36 V
∗ MnO− + −
4 + 8H + 5e → Mn
2+
+ 4H2 O 1.51 V
− −
∗ F2 + 2e → 2 F 2.87 V

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0
Ex.3 Calculate Ecell of (at 298 K), Zn(s)/ZnSO4 (aq) ∥ CuSO4 (aq)/Cu(s) given that
0 0
EZn/Zn2 (aq) = 0.76 V, ECu(s)/Cu0 2 (aq) = −0.34 V

0
Sol. Ecell = (S. R. P)cathode − (S. R. P)anode
= 0.34 − (−0.76) = 1.1 V
Ex.4 Given the cell AgAgCl(s)|NaCl(0.05M) ∥ AgNO3 (0.30M)|Ag
(a) Write half reaction occurring at the anode.
(b) Write half reaction occurring at the cathode.
(c) Write the net ionic equation of the reaction.
∘
(d) calculate Ecell at 25∘ C.
(e) Does the cell reaction go spontaneous as written ?
∘ 0
(Given EAgCl,Cl = +0.22 volt) ; EAg+ /Ag = +0.80 volt)

Sol. (a) LHS electrode is anode and half reaction is oxidation.

Ag + + Cl− ⟶ AgCl(s) + e− .....(i)
(b) RHS electrode is cathode and half reaction is reduction.
Ag + e ⟶ Ag(s) .....(ii)
(c) From equation (i) and (ii) cell reaction is : Cl− (0.05M) + Ag + (0.30M) ⟶ AgCl(s)
∘ ∘ ∘
(d) Ecell = Eright − Eleft = (0.80 − 0.22 volt = 0.58 volt
(e) Yes, the e.m.f. value is positive, the reaction will be spontaneous as written in the cell eaction.
2.4.2 Calculation of Electrode Potential of unknown electrode with the help of given (two)
electrode.
(i) Obtain the reaction of the 3rd electrode with the help of some algebraic operations on
reactions of the given electrodes.
(ii) Then calculate ΔG∘ of the 3rd reaction with the help of some algebaric operations of ΔG0 of
1st and 2nd reactions.
0 0
Ecell is intensive property so if we multiply/divide electrode reaction by any number the Ecell
value would not changed
i.e. Zn2+ + 2e− → Zn(s) E ∘ = −0.76 V
Multiply by 2
2Zn2+ + 4e− → 2Zn(s) E ∘ = −0.76 V (remain same)

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0 2+ 0 0
Ex.5 Given that ECu /Cu = 0.337 V and ECu +/Cu2+ = −0.153 V. Then calculate ECu+ /Cu .

Sol. (i) Cu2+ + 2e− Cu ΔG1

(ii) Cu+ Cu2+ + e− ΔG2

after adding Cu+ + e− ⟶ Cu

ΔG1 + ΔG2 = ΔG3

−2FE10 − FE20 = −FE30

E3 = 2E10 + E20

= 2 × 0.337 − 0.153

= 0.674 − 0.153 = 0.521 V

0
Ex. 6 EMn 2+ /MnO− = −1.51 V
4

0
EMnO2 /Mn
+2 = +1.23 V

0
EMnO − /MnO =?
4 2
(All in acidic medium)
Sol. 4H2 O + Mn2+ → MnO− +
4 + 8H + 5e ΔG1
−

(i) MnO− + −
4 + 8H + 5e → 4H2 O + Mn
2+
−ΔG1

2e− + MnO2 + 4H + → Mn2+ + 2H2 O ΔG2

(ii) 2H2 O + Mn2+ → MnO2 + 4H + + 2e− −ΔG2

(iii) 4H + + MnO− −
4 + 3e → MnO2 + 2H2 O ΔG3

(i) + ( ii) = ( iii)

ΔG3 = −ΔG1 − ΔG2

−3E3 F = 5E10 F + 2E20 F

−[5E1 +2E2 ] −[5(−1.51)+2(1.23)] −[−7.55+2.46] +5.09
E= = = = = 1.69 V
3 3 3 3

Ex.7 Will Fe2+ disproportionate or not

Sol. This is known as Latimer diagram.

S.R.P to right of the species greater than SRP of its left species will undergo disproportionation.

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2.5 NERNST EQUATION:
Cell potentials depend on temperature and on the composition of the reaction mixtures. It
depends upon the concentration of the solute and the partial pressure of the gas, if any. The
dependence upon the concentration can be derived from thermodynamics. From
thermodynamics
ΔG = ΔG∘ + RTln Q
−nFE = −nFE ∘ + 2.303RTlog Q
2.303RT
E = E∘ − log Q
nF

Take T = 298 K, R = 8.314 J/molK, F = 96500C

0.059
Now we get, E = E ∘ − log Q
n

Where n = number of transfered electron, Q = reaction quotient

• Nernst equation can be used to calculate cell potentials for non standard conditions also.
• Nernst equations can be applied to half cell reactions also.

Applications of Nernst equation

2.5.1 Nernst Equation for Electrode Potential

M n+ (aq) + ne− ⇌ M(s)
0 RT M(s)
ERed = Ered − nF /n [ Mn+ ]
0 2.303RT M(s)
ERed = Ered − log [ Mn+ ]
nF

0 0.059 1
at 298 K, ERed = ERedn − log [Mn+]
n

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Hydrogen Electrode
H2 ( g) ⇌ 2H + (aq) + 2e−
2
0.0591 (H+ )
E = E0 − log [ ]
2 PH2

Metal-metal soluble salt electrode.

Zn2+ + 2e− → Zn(s)
0 2.303RT 1
ERed = ERedn − log (Zn+2) at 298 K
nF
0 0.059 1
ERed = Ered − log (Zn+2)
2

Gas - electrode Hydrogen electrode.

2H + + 2e− → H2 ( g)
0 0.059 PH
ERedn = ERedn − log ([H+2]2 )
2

Redox electrode
4H2 O + Mn2+ → MnO− +
4 + 8H + 5e
−

0 0.059 [MnO− + 8
4 ][H ]
EOX = Eox − log [Mn+2 ]
5

Ex.8 Calculate R.P. of hydrogen electrode at 298 K which is prepared with the help of aq. solution of
acetic acid with 0.1M concentration at 1 atm pressure Ka = 1.8 × 10−5 .
Sol. [H + ] = √Ka × c = √1.8 × 10−5 × 10−1 = √1.8 × 10−6
2H + + 2e− → H2
0 0.059 PH2 0
ERedn = Ered − log [H+ ]2
(ERedn = 0)
2
0.059 1 0.059
ERedn = − log (1.8×10−6) = − [6 − log (1.8)]
2 2
0.059
ERedn = − × 5.74 = −0.169 V
2
Ex.9 Which is stronger oxidizing agent
(i) K 2 Cr2 O7 in solution in which
7 ] = 0.1M, [Cr ] = 10 M and [H ] = 10 M
[Cr2 O2− 3+ −2 + −1

(ii) KMnO4 in a solution in which

[MnO− −1 2+ −2 + −2
4 ] = 10 M, [Mn ] = 10 M, [H ] = 10 M
0 0
ECr 2−
2 O /Cr
+3 = 1.33 VEMnO− /Mn+2 = 1.51 V
4
7

Sol. (i) 14H + + Cr2 O2−

7 2Cr
+3
+ 7H2 O + 6e−
0.059 10−4 ×10 0.059
ERedn = 1.33 − log [ ] = 1.33 − × 11
6 10−14 6
0.649
ERedn = 1.33 − = 1.330 − 0.108 = 1.222 V
6

(ii) 5e− + 8H + + MnO−

4 → Mn
2+
+ 4H2 O
0.059 10−2
ERedn = 1.51 − log [10−16 ×10−1 ] = 1.51 − 0.059 × 3 = 1.51 − 0.18 = 1.33 V
5

𝐄Redn is more so, good oxidising agent

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2.5.2 Nernst Equation for cell Potential:
aA + bB ⇌ cC + dD
0 RT
Ecell = Ecell − nF ln Q

n - no. of electrons which gets cancelled out while making cell reaction.
Equilibrium in electrochemical cell
o
ΔG0 = −𝑛nFEcell
Δ𝐆 = −𝐧𝐅Ecell
From thermodynamics
ΔG = ΔG0 + RT/nQ
at chemical equilibrium ΔG = 0
Ecell = 0 cell will be of no use
so, ΔG0 = −RT/nK eq
o
at equilibrium −nFEcell = −2.303RTlog (K eq )
nF o
log K eq = 2.303RT Ecell

at 298 K and R = 8.314 J/molK

n o
log K eq = 0.059 Ecell

Ex.10 Calculate Ecell of Pt(s)

given that EC02O2/Cr+3 = 1.33 V

7

0 −
E Cl ∣ Cl2 = −1.36 V
Sol. 6e− + 14H + + Cr2 O2−
7 → 2Cr
+3
+ 7H2 O
[2Cl− → Cl2 + 2e] × 3
14H + + 6Cl− + Cr2 O2−
7 → 3Cl2 + 2Cr
+3
+ 7H2 O
0
Ecell = 1.33 − (+1.36) = −0.03
2 3
0.059 [Cr3+ ] [PCl2 ] 0.059×23
Ecell = −0.03 − log [H+ ]14 [Cl− ]6 [Cr2 O2−
= −0.03 −
6 7 ] 6

Ecell = −0.26 V

APNI KAKSHA 14
(Physical Chemistry) ELECTROCHEMISTRY
Example problem 11.5
For the Daniell cell E ∘ = 1.10 V. calculate K for the reaction at 298.15 K
Zn(s) + Cu2+ (aq) ⇌ Zn2+ (aq) + Cu(s).
Solution.
nF 2×96485Cmol−1 ×1.10 V
In K = RT E ∘ = 8.314 J K−1 mol−1×298.15 K = 85.63

K = 1.55 × 1037
Note that the equilibrium constant calculated in Example Problem 11.5 is so large that it could
not have been measured by determining the activities of aZn2+ and aCu2+ by spectroscopic
methods. This would require a measurement technique that is accurate over more than 30 orders
of magnitude in the activity. By contrast, the equilibrium constant in an electrochemical cell can
be determined with high accuracy using only a voltmeter.
A further example of the use of electrochemical measurements to determine equilibrium
constants is the solubility constant for a weakly soluble salt. If the overall reaction corresponding
to dissolution can be generated by combining half-cell potentials, then the solubility constant
can be calculated from the potentials. For example, the following half-cell reaction can be
combined to calculate the solubility product of AgBr.

The value of the solubility constant is K SP = 4.88 × 10−13 .

∘
Ex.11 The Ecell for the reaction Fe + Zn2+ ⇌ Zn + Fe2+ , is -0.32 volt at 25∘ C. What will be the
equilibrium concentration of Fe2+ , when a piece of iron is placed in a 1MZn2+ solution ?
Sol. We have the Nernst equation at equilibrium at 25∘ C
0.0591
E∘ = log K .....(i)
n

Since E ∘ Cell for the given reaction is negative, therefore, the reverse reaction is feasible for
∘
which Ecell will be +0.32 V, Thus for

APNI KAKSHA 15
(Physical Chemistry) ELECTROCHEMISTRY
Work done by a cell:
(i) Let ' 𝑛 ' faraday charge be taken out of a cell of EMF 'E'; then work done by the cell will be
calculated as : work = Charge × Potential = nFE
(ii) Work done by cell = Decrease in free energy
so − ΔG = nFE
Ex.12 Calculate the maximum work that can be obtained from the Daniel cell given below -
o o
Zn(s)|Zn2+ (aq) ∥ Cu2+ (aq)|Cu(s). Given that EZn 2+ /Zn = −0.76 V and ECu2+ /Cu = +0.34 V.

Sol. Cell reaction is: Zn(s) + Cu2+ (aq) ⟶ Cu(s) + Zn2+ (aq) Here n = 2
o o o
Ecell = Ecathode − Eanode ( On the basis of reduction potential )
= +0.34 − (0.76) = 1.10 V
We know that: Wmax = ΔGo = −nFE ∘
= −(2 mol) × (96500Cmol) × (1.10 V) = −212300
C.V. = −212300 J
Or Wmax = −212300 J

2.6 CONCENTRATION CELLS :

A concentration cell consists of two electrodes of the same material, each electrode dipping in a
solution of its own ions and the solution being at different concentrations.

The two solutions are separated by a salt bridge.

e.g. Ag (s)|Ag + (a1 ) ∥ Ag + (a2 )|Ag (s) (a1 < a2 )a1 , a2 are concentrations of each half cell At LHS
electrode Anode: Ag(s) ⟶ Ag + (a1 ) + e−

At RHS electrode Cathode : Ag + (a2 ) + e− ⟶ Ag(s)

The net cell reaction is: Ag + (a2 ) ⟶ Ag + (a1 )

The nernst eq. is

0.059 a1
Ecell = − log (Here n = 1, Temp, 298 K)
n a2

• Likewise, the e.m.f. of the cell consisting of two hydrogen electrodes operating at different
pressure P1 and P2 (P1 > P2 ) and dipping into a solution HCl is:
0.059 P1
Ecell = log ( at 298 K)
2 P2

APNI KAKSHA 16
(Physical Chemistry) ELECTROCHEMISTRY
Q. If for the concentration cell.
1 n+ 1
𝑋(s) |𝑋(aq) (20 M)| |X(aq) (2 M)| X(s)

Ecell = 0.029 V at 298 K calculate n.

Sol. X(s) ⟶ X n+ (aq) + ne− anodic reaction

Xn+ −
(aq) +ne ⟶X(s)
cathodic reaction
Xn+ n+
(aq) cathod ⇌X(aq) anode

0.059 [X+n ]anode

0.029 = 0 − log [X+n ]cathode
n

1
0.059 ( )
20
∵ 0.029 = 0 − log 1
n ( )
2

0.059 1
0.029 = − log
n 10

0.059
0.029 = − log 10−1
n

0.059
0.029 = n

∴n=2

Q. A hydrogen electrode is immersed in a solution pH = 0(HCl). By how much will the reuction
potential change if an equivalent amount of NaOH is added to this solution, so that solution, so
that solution becomes neutral (PH2 = 1 atm)T = 298 K
+
Sol. 2H(aq) + 2e− ⟶ H2( g)

∘ 0.0591 (PH2 )
ERP = ESRP − log ( )
n [H+
(aq) ]

0.059 1
ERP = 0 − log (12)
1
0.059 1
ERP1 = 0 − log (12 ) = 0
1

ERP1 = 0
0.059 1 0.059
ERPfiral = 0 − log (10−7 )2
= × 14 V = 0.4137 V
2 2

Change in reduction potential [0.4137 − 0] = 0.4137

APNI KAKSHA 17
(Physical Chemistry) ELECTROCHEMISTRY
Q. Calculate Ecell of:

0.059 C1 Ka1
Prove that Ecell = − log
2 C2 Ka2

Sol. HCOOH ⇌ HCOO− + H +

C1 (1 − 𝛼1 ) c1 𝛼1 c1 𝛼1
Anode H2 ( g) ⟶ 2Ha+ + 2e−
Cathode 2HC+ (aq) + 2e− ⟶ H2 ( g)
(H2( g) )a + 2H + (aq) ⇌ 2Ha+ (aq) + (H2 ( g))c
0.059 [H+ ]2a [PH2 ]
c
∴ Ecell = 0 − log [H+ ]2C [PH2 ]
(PH2 )c = (PH2 )a = 1 atm
2
a

∵ [H + ]a = √c1 Ka1

[H + ]c = √c2 Ka2
0.059 c1 Ka1
∴ Ecell = − log
2 c2 Ka2

2.6 METAL -METAL INSOLUBLE - ION ELECTRODE:

In this half cell, a metal coated with its insoluble salt is in contact with a solution containing the
anion of the insoluble salt.
(i) Construction:

(ii) Half cell reaction:

(a) If it act as Anode: At anode oxidation take place.
If it is normal silver electrode than.
Ag(s) ⟶ Ag + (aq) + e− .....(i)
But solution have Cl.(aq) ion so Ag + (aq)&Cl.(aq) Form PPT of AgCl(s)
Ag + (aq) + Cl− (aq) ⟶ AgCl(s) … . . (ii)
Overall half cell reaction at anode [from eq. (i) & (ii)].
Ag(s) + Cl− (aq) ⟶ AgCl(s) + e− .....(iii)
(b) If it act as cathode: At cathode reduction take place.
If it is normal silver electrode than.

APNI KAKSHA 18
(Physical Chemistry) ELECTROCHEMISTRY
Ag + (aq) + e− ⟶ Ag(s) … . . (i)
AgCl(s) ⟶ Ag + (aq) + Cl− (aq).....(ii)
Overall half cell reaction at cathode [from eq. (i) & (ii)].
AgCl(s) + e. ⟶ Ag(s) + Cl− (aq) … ..(iii)
(iii) Cell representation:

Abode: Ag (s)|AgCl(s)|Cl− (aq) ∥ __________

E∘Ag(s)|AgCl|Cl− (aq)
Cathode: ∥ Cl− (aq)|AgCl(s)|Ag(s)
E∘Cl− (aq)|AgCl(s)|Ag(s)

∘
(iv) Relation between ECl− (aq)|AgCl(s)|Ag(s) & K sp of AgCl

If a cell is constructed using metal-metal soluble salt and metal-metal unsoluble salt electrode.
0 0
Given EAg+ ∣Ag = 0.80 V, ECl− |AgC|Ag = 0.22 V

Anode Cathode
Ag|AgCl|Cl− (aq) ∥ Ag + (aq) ∣ Ag
Anode : Ag(s) + Cl− (aq) ⟶ AgCl(s) + e− (Metal-metal insoluble salt)
Cathode: Ag + + e− ⟶ Ag (Metal-metal soluble salt)
Overall cell reaction:
Ag + (aq)c + Cl− (aq)a ⟶ AgCl(s)
At equilibrium the concentratuion of [Ag + ]a = [Ag + ]c
So that at equilibrium Ecell = 0
0 0.059 [AgCl(s)]
But Ecell = Ecell − log [Ag+ ]c [Cl− ]a
1

At equilibrium
0 0.059 1
0 = Ecell − log [Ag+ ]c [Cl− ]a
1

Now for AgCl

AgCl(s) ⟶ Ag + (aq)a + Cl− (aq)a
K sp = [Ag + ]a [Cl− ]a
Ksp (AgCl)
So, [Cl− ]a = [Ag+ ]a

0 0.059 [Ag+ ]a
0 = Ecell − log [Ag+ ]a ×Ksp
[At equilibrium the concentratuion of [Ag + ]a = [Ag + ]c ]
1

0 0.059 1
Ecell = log
1 Ksp

APNI KAKSHA 19
(Physical Chemistry) ELECTROCHEMISTRY
0 0.059 1
Ecell =− log
1 Ksp

0 0 0
Ecell = Ecathode − EAnode
0 0
= EAg + /Ag − ECl− /agCl/Ag

0 0 0.059 1
So, EAg + ∣Ag − ECl− |AgCl|Ag = log
1 Ksp

0 0 0.059
ECl− /AgCl/Ag = E
Ag+ /Ag + log K sp
1

Some other example:

Pb|PbSO4 |SO4 2− ∥ Pb2+ ∣ Pb
White ppt.
0 0 0.059
ESO 2− |PbSO |Pb = EPb2+ ∣Pb + log Ksp
4 4 2

Ex. Calculate Ksp of AgI with the help of following cell.

Ag|Agl(s)|0.05MKI(aq)||0.05MAgNO3 ∣ Ag(s)
0
Sol. First methode: If Ecell =0
Anode : Ag ⟶ Ag a+ + e−
Cathode : Ag + −
c + e ⟶ Ag
Ag + +
c ⇌ Ag a

According to nernst equation.

0 0.059 [Ag+ ]a
Ecell = Ecell − log [Ag+ ]c
1

0.059 [Ag+ ]a
0.7884 = 0 − log
1 0.05
0.7884
− = log [Ag + ]a − log (5 × 10−2 )
0.059
0.7884
log [Ag + ]a = −1.3 − 0.059

[Ag + ]a = 2.17 × 10 −15

K sp = [Ag + ]a [I − ]a
K sp = 2.17 × 10−15 × 0.05 = 1 × 10−16 .
0
Second Methode: if Ecell ≠0
0 0.059 1
Ecell = Ecell − log [Ag+ ] −
1 c [I ]a
0.059 0.059 1
Ecell = − − log K sp − log [Ag+ ] −]
1 1 c [I a
0.059 [Ag+ ]a I− ]a
𝑆𝑜 Ecell = − log [Ag+ ]c [I− ]a
1
0 0.059 [Ag+ ]a
Ecell =− log [Ag+ ]c
1

APNI KAKSHA 20
(Physical Chemistry) ELECTROCHEMISTRY
(4) Calomel Electrode:
• A calomel cell consists of a platinum electrode dipping into mercury in contact with calomel
(dimercury) (1) chloride, Hg 2 Cl2 ) and potassium chloride solution.
• Usually the solution is saturated with potassium chloride.
• The cell has an e.m.f of 0.246 V at 28∘ C

DO YOURSELF–1
1. Colour of KI solution containing starch turns blue when Cl2 water is added. Explain.

2. E ∘ of some oxidants are given as :

I2 + 2e− ⟶ 2I − E ∘ = +0.54 V
MnO− + −
4 + 8H + 5e ⟶ Mn
2+
+ 4H2 O E ∘ = +1.52 V
3+ − 2+
Fe + e ⟶ Fe E ∘ = +0.77 V
Sn4+ + 2e− ⟶ Sn2+ E ∘ = +0.1 V
(a) Select the strongest reductant and oxidant in these.
(b) Select the weakest reductant and oxidant in these.
(c) Select the spontaneous reaction from the changes given below.
(i) Sn4+ + 2Fe2+ ⟶ Sn2+ + 2Fe3+
(ii) 2Fe2+ + I2 ⟶ 2Fe3+ + 2I−
(iii) Sn4+ + 2I − ⟶ Sn2+ + I2
(iv) Sn2+ + I2 ⟶ Sn4+ + 2I −

APNI KAKSHA 21
(Physical Chemistry) ELECTROCHEMISTRY
3. Given the standard electrode potentials;
K + /K = −2.93 V, Ag + /Ag = 0.80 V, Hg 2+ /Hg = 0.79 V, Mg 2+ /Mg = −2.37 V, Cr 3+ /Cr = −0.74 V.
Arrange these metals in their increasing order of reducing power.

4. Answer of following:
(i) In a cell, anode is represented by -ve sign and cathode by +ve sign. What is the type of the cell?
(ii) Write the reaction taking place at anode in the following cell:
Pt, H2 (1 atm) ∣ HCl(1M)Cl2 , Pt.
(iii) With the help of the following possible reactions, arrange Mg, Zn, Cu and Ag in decreasing
order of their reduction potentials.
Cu + 2Ag + ⟶ Cu2+ + 2Ag
Mg + Zn2+ ⟶ Mg 2+ + Zn
Zn + Cu2+ ⟶ Zn2+ + Cu
(iv) Cl2 can displace I2 from KI solution but I2 does not displace.
(v) The E ∘ (standard oxidation potentials) values of the elements A, B, C and D are +
0.76, −0.34, +0.25 and -0.85 volt respectively. Arrange these in decreasing order of reactivity.

5. A cell is prepared by dipping a copper rod in 1MCuSO4 solution and a nickel rod in 1M NiSO4 .
The standard reduction potentials of copper and nickel electrodes are +0.34 V and 0.25 V
respectively.
(i) Which electrode will work as anode and which as cathode?
(ii) What will be the cell reaction?
(iii) How is the cell represented?
(iv) Calculate the EMF of the cell.

6. Predict whether the following reaction can occur under standard conditions or not.
Sn2+ (aq) + Br2 (ℓ) ⟶ Sn4+ (aq) + 2Br − (aq)
∘
Given ESn4+Sn2+ ∘
= +0.15, EBr2Br− = 1.06 V.
Co3+ + e− ⟶ Co2+ E ∘ = +1.82 V
2H2 O ⟶ O2 + 4H + + 4e− ; E ∘ = −1.23 V.

7. Given that, Co3+ + e− ⟶ Co2+ E ∘ = +1.82 V

2H2 O ⟶ O2 + 4H + + 4e− ; E ∘ = −1.23 V.
Explain why Co3+ is not stable in aqueous solutions.

APNI KAKSHA 22
(Physical Chemistry) ELECTROCHEMISTRY
8. The measured e.m.f. at 25∘ C for the cell reaction,
Zn(s) + Cu2+ (1.0M) ⟶ Cu(s) + Zn2+ (0.1M)
is 1.3 volt Calculate E ∘ for the cell reaction.

9. Calculate ΔG∘ for the reaction : Cu2+ (aq) +Fe(s) ⇌ Fe2+ (aq) +Cu(s). Given that
∘ ∘
ECu+/Cu = +0.34 V, EFe∘ +2/Fe = −0.44 V

10. Calculate the equilibrium constant for the reaction at 298 K

Zn(s) + Cu2+ (aq) ⇌ Zn2+ (aq) + Cu(s)
∘ ∘
Given EZn2+ /Zn = −0.76 V and ECu2+ /Cu = +0.34 V

11. Calculate the cell e.m.f. and ΔG for the cell reaction at 298 K for the cell.
Zn(s)|Zn2+ (0.0004M) ∥ Cd2+ (0.2M)|Cd(s)
o o
Given EZn2+ /Zn = −0.763 V; ECd+2 /Cd = −0.403 V at 298 K.

F = 96500Cmol−1 .

2.6 CALCULATION OF THERMODYNAMICS FUNCTION OF CELL REACTION:

0
(1) ΔG∘ = −nFcell
ΔG∘ = −nFcell
(2) G = H − TS ( But: H = E + PV)
∴ G = (E + PV) − TS
dG = dE + PdV + VdP − TdS − SdT
(a) From 1st law of thermodynamics
dE = dq + dW
= dq − pdV
dq = dE + pdV
(b) From 2nd law of thermodynmics
dq
dS = T

dq = TdS
Using 1st law and 2nd law of thermodynamics
dG = (dE + PdV) + Vdp − TdS − SdT ⇒ dG = Vdp − SdT
If a cell reaction is taking place at constant pressure (which is generally the case).
dG = Vdp − SdT

APNI KAKSHA 23
(Physical Chemistry) ELECTROCHEMISTRY
at constant pressure
So, Vdp = 0
And dG = −SdT
dG
∴ S = − [dT] (At constant pressure)
p
d(ΔG)
ΔS = − [ ] (At constant pressure)
dT p

ΔG = −nREcell
d
ΔS = − (dT (Ecell )) (−nF)
p

APNI KAKSHA 24