Module:1 Electrochemistry and Battery Technology

Electrochemistry

INTRODUCTION: Important class of chemical reactions is oxidation-reduction reactions.

In oxidation: a species loses one or more electrons resulting in an increase in its oxidation number.
M Mn+ + ne-

In reduction: the species gains one or more electrons; there is a decrease in oxidation number.

Mn+ + ne- M

A reduction process necessarily accompanies an oxidation process since electrons can be lost by a
species only when there is a counterpart to receive them. Redox reaction forms the basis of
electrochemical cells. An electrochemical cell consists of two electrodes which when connected by a
metallic wire an electric current flow as a result of a spontaneous redox reaction.

Each electrode usually consists of a metal in contact with a solution of its own ion. Since a cell is a
combination of two electrodes, each electrode is referred to as a single electrode or half- cell. A
potential called the electrode potential arises at the electrode in contact with its ionic solution. The
difference between the potentials of the two half- cells constitutes the electromotive force (emf) of
the cell.

Emf: The potential difference between the two electrodes of a galvanic cell which causes the flow of
current from one electrode (higher potential) to the other (lower potential) is called the electromotive
force of the cell or the cell potential.

Electrochemical cell: Definition: Electrochemical cell is a device in which chemical energy is

converted into electrical energy or electrical energy into chemical energy by oxidation-reduction
reaction. Thus, there can be two types of Electrochemical cells.
1. Galvanic cell or voltaic cell: the one, which converts chemical energy into electrical energy.
2. Electrolytic cell: the one, which converts electrical energy into chemical energy.

GALVANIC CELL ELECTROLYTIC CELL

1) It is a device, in which electricity is produced It is a device, which converts electrical energy into
by using chemical reaction. chemical energy.
2) The redox reactions occurring at the electrodes The redox reactions occurring at the electrodes are
are spontaneous. non-spontaneous and are takes place only when
electrical energy is supplied.
3) Each electrode is dipped in its own ionic Both the electrodes are dipped the same electrolyte
solution and both have separate compartments. solution.
4) The electrodes are of dissimilar metals. The electrodes used may be dissimilar or of the
same metal.

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5) Two electrodes are connected by salt bridge. No salt bridge is needed.

6)Cathode is + ve and anode is -ve Cathode is ve and anode is + ve.

Galvanic cell:
A typical egs of galvanic cell is Daniel cell, which is illustrated in the fig.

construction and working: It consists of two beakers one of which contains zinc rod immersed in
zinc sulphate solution and the other one contains copper rod in copper sulphate solution. A salt
bridge connects the solutions of two beakers. The zinc and copper rods are connected externally
through voltmeter by using a wire. On completing the circuit the following changes are observed
1. zinc rod starts dissolving.
2. copper gets deposited on copper rod
3. zinc sulphate solution becomes more concentrated with respect to Zn2+ ions
4. copper sulphate solution becomes more dilute with respect to Cu2+
5. Migration of ions takes place in solution.

The above observations are explained by the following oxidation-reduction reactions taking place at
anode and cathode respectively.

At the anode: Zn Zn2+ + 2e- oxidation half- cell

At the cathode: Cu2+ +2e- Cu reduction half- cell

Net cell reaction Zn + Cu2+ Zn2+ + Cu cell reaction

By convention, the electrode at which oxidation occurs is anode and the electrode where reduction
occurs is cathode. In a galvanic cell anode is negative and cathode is positive. The flow of electrons
is from zinc electrode to copper electrode. Hence the flow of conventional current is from copper
electrode to zinc electrode.

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The net redox reaction, called electrochemical reaction, is the cause for production of electricity. The
net reaction is the sum of two electrode reactions and is called cell reaction. Each electrode reaction
is called as half-cell reaction.

Salt bridge: It is easy to construct. A thin paste of agar-agar in water is added to boiling water
containing a little of an electrolyte like KCl or KNO 3. It is then drawn preferably into U- tube and
cooled.

Function: The salt bridge not only connects the two half-cells internally. It maintains the electrical
neutrallity of both the half cells. And is used to complet the circuit.
Note: 1. When one of the solutions contains soluble silver, mercurous or thallous salt, the KCl salt
bridge cannot be employed.
2. KCl or KNO3 is used because the ions have almost same migration velocities.

Cell notation and sign conventions:

The following notation is used to represent the Daniel cell.

i.e. Zn/Zn2+(1M)//Cu2+(1M)/Cu

Single vertical line / a phase boundary between metal and its solution.

Double vertical line // salt bridge

Arrow indicates direction of flow of electrons

Concentration of the solutions must write in parentheses.

Sign conventions:

The half cell at which oxidation (Anode) occurs is always written on the left side and The half cell
at which reduction (cathode) occurs is always written on the right side

1. The concentration of solutions, pressure of gases and physical state of the solid or liquid
involved are indicated by suitable signs within brackets.
2. If the arrow is in the forward direction ie the electrons are flowing from anode to cathode the
emf of the cell is positive. If the arrow mark is in backward direction the electrons flow from
cathode to anode the emf of the cell is negative.
3. Anode to be represented as M/Mn+and cathode in the form Mn+/M.
4. The term electrode potential refers the reduction potential. It is represented as E Mn+/M
5. The potential difference between the two electrodes, called EMF (Electro Motive Force), is
stated in volts. Ex: Ecell = Ecathode -Eanode.

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Single electrode potential [E]

Single electrode potential is the potential developed at the interface between the metal and the
solution, when the metal is in contact with a solution of its own ions. (OR) It is the tendency of the
metal to lose or to gain electrons when it is in contact with a solution of its own ions.

Standard electrode potential [Eo]

The standared electrode potential is defined as the potential developed when the electrode is in
contact with a solution of unit concentration at 298K.

Calculation of standard emf of a cell:

The standard emf of the cell is calculated using the following expression

Eocell = Eocathode - Eoanode

= EoR - EoL

Eocell = EoReduction - Eooxidation

Electrochemical series: Metals are arranged in the increasing order of their standard reduction
potential with respect to hydrogen scale.

Electrode Standrd reduction

or Metal potential
Li - 3.05
K - 2.93
Ca - 2.87
Mg - 2.36
Al - 1.66
Mn - 1.18
Zn - 0.76
Fe - 0.44
Ni - 0.23
Pb - 0.18
Sn - 1.14
H 0
Cu + 0.34
Ag + 0.80
Pt + 1.2
Au + 1.69

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Nernst Equation
The equation for single electrode potential was derived by Nernst and is called Nernst Equation.
It is a thermodynamic equation, which gives the relationship between electrode potential and
concentration of the substance involved.
Consider a general red-ox reaction: Mn++ ne- M ----(1)

Free energy change for a reversible reaction ( Vant Hoff equation ) is given by
G = G0 + RT lnK ----(2)
Decrease in free energy represents the maximum work done
G = Wmax
Wmax = No moles electrons charge per mole electron potential
Wmax = n F E
. . G = - nEF and G0= - nE0F
.
----(3)
(where, G= free energy change, G = standard free energy change, E=electrode potential;
0

E0=standard reduction potential n=number of electrons involved in the reaction; F is Faraday =

96,500 Cmol-1)

Where K is the Equilibrium constant of reaction it is equal to the concentration of the products to
the concentration of reactants, i.e.
[Products] [M ]
K= ----(4)
[Reactants] [ M n ]
by substituting Eqs.(3) and (4) in Eq.(2)
[M ]
-nEF = -nE0F+ RT ln
[ M n ]
RT [M ]
E= E ln
0
Divide by nF Then,
nF [ M n ]
RT 1
E= E ln
0
(since [M]=1)
nF [ M n ]
2.303 RT
E= E
0
log M n
nF
(R is a gas constant = 8.314 J K -1 mol-1; T= temperature in absolute scale (298K); F is Faraday
= 96,500 C mol-1)
0.0591
E= E
0
log M n at 298 K
n
The cell potential may be calculated by using the above relation
ECell = Ecathode - EAnode
ECell = {Eo cathode + 0.0591 log [Mn+]cathode } - {Eo Anode + 0.0591 log [Mn+] Anode }
n n
ECell = EoCell + 0.0591 log [Mn+]cathode
n [Mn+] Anode

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2.303 RT [ M n ]cathode
Ecell = E cell
0
OR log
nF [ M n ] anode
The electrode potentials vary with temperature and the concentration of metal ions.
The term Electrode Potential (E) refers to the Reduction Potential, also depends upon the
nature of the metal.

0.0591
E= E 0
log M n at 298 K is the reduction potential
n

Types of electrodes:
Metal-metal ion electrode: This type of electrode consists of a metal in contact with a solution of its
own ions.
Egs: 1.Zinc rod in a solution of zinc sulphate.
2. Copper rod in a solution of copper sulphate.

Metal-metal salt ion electrode: Here a metal is dipped in its insoluble salt that is in contact with a
solution containing the anion of the salt
Egs 1. Calomel electrode Hg / Hg2Cl2 (s) /Cl-
2. Silver-Silver chloride electrode Ag / AgCl (s) / Cl-

Gas electrode: Here a gas is in contact with an inert metal that is dipped in an ionic solution of the
gas molecule.
Egs: SHE, Pt / H2 (1atm) / H+ (1M)

Amalgam electrode: Amalgam electrode is similar to Metal-metal ion electrode except for the fact
that in an Amalgam electrode, Metal- Amalgam is in contact with a solution containing its own metal
ions (or)
Amalgam of a metal in contact with solution containing its own metal ions. Highly active metals are
used in the form of amalgams, since the activity of metal can be varied.
Ex. Zinc in mercury in contact with zinc sulphate solution [Zn(Hg) +/ Zn2+]
Ex. Lead Amalgam electrode (Pb(Hg) / Pb2+)

Oxidation-reduction electrode: This type of electrode consists of an inert electrode (Pt or Au)
immersed in a mixed solution containing both the oxidized and reduced forms of a molecule or ion.
Egs: Pt / Fe2+: Fe3+
Pt / Sn2+: Sn4+
Ion-selective electrode: Possesses the ability to respond only to certain specific ions, thereby
developing potential w.r.t that species only in a mixture and ignoring the other ions totally. In other
words, the potential developed by an ion-selective electrode depends only on the concentration of

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species or ions of interest. For egs. Glass electrode which responds to hydrogen ions
(Ag/AgCl/HCl/Glass).

Reference electrodes
Reference electrodes are the electrodes whose potential is known and with reference to those, the
electrode potential of any other electrode can be measured
There are 2 types of reference electrodes
1) Primary reference electrode
2) Secondary reference electrode
Primary reference electrode: Standard hydrogen electrode (SHE) is the primary reference electrode
and its electrode potential taken as zero at all temperature.
Secondary reference electrodes: These are the electrodes having constant electrode potential value
and their potential is known with respect to SHE, hence they are called as secondary reference
electrodes.
Eg 1. calomel electrode 2. Ag-AgCl electrode.

Calomel electrode: The calomel electrode consists of a glass vessel containing a layer of Hg over
which a paste of Hg, Hg 2Cl2 is placed. Above this there is a solution of KCl. A platinum wire is
dipped into the Hg layer provides external electrical connection. A salt bridge is used to couple with
other half-cell.

The half-cell is represented as

Hg/ Hg2Cl2 (salt)/ KCl (sat)
Calomel electrode can act either as anode or cathode depending on the other electrode used
When it is Anode:- 2 Hg + 2Cl - Hg2Cl2 + 2e-

When it is Cathode:- Hg2Cl2 + 2e- 2 Hg + 2Cl-

Net reaction is:- Hg2Cl2 (s) + 2e- 2 Hg + 2Cl -

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The electrode potential may be represented by the Nernst equation as

E = Eo 0.059/n log [Cl -]2
E = Eo 0.0591/2 log [Cl-]2
E = Eo 0.0591 log [Cl-] at 298 K

The potential of the calomel electrode depends on the concentration of KCl used.
The electrode potential decreases with increase in the concentration of chloride ions.
For 0.1N KCl E= 0.33V
1N KCl E= 0.28V
saturated KCl E = 0.24V

Advantages of secondary reference electrodes:

1. Easy to construct
2. Easy to maintain.
3. The cell potential is stable over a long period and does not vary with temperature
4. Oxidaizing agents can also be used.

Silver-silver chloride electrode:

It is a secondary reference electrode used in analytical instrumentation.
It consists of a silver electrode coated coated with AgCl, is immersed in saturated KCl solution

The electrode can be represented as Ag / AgCl (s)/Cl-

Ag: AgCl electrode can act either as anode or cathode depending on the other elctrode used
When it is Anode: Ag + Cl- AgCl + e-
-
When it is Cathode: AgCl + e Ag + Cl-

The Net reaction is AgCl + e- Ag + Cl-

The electrode potential may be represented by the Nernst equation as

E = E 0 0.0591logCl at 298K

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The potential of the Ag-AgCl electrode depends on the concentration of KCl used.
The electrode potential decreases with increase in the concentration of chloride ions.
For 0.1N KCl E= 0.290V
1N KCl E= 0.223V
Saturated KCl E = 0.199 V

Application:
1. As a secondary reference electrode in place of calomel electrode
2. In determining whether the potential distribution is uniform or not in ship hulls and old
pipelines protected by cathodic protection.

Measurement of electrode potential using Calomel electrode (CE):

In order to measure the potential of given electrode using calomel electrode, a galvanic cell is
obtained by combining both the electrodes according to cell conventions.
If a given electrode undergoes oxidation w.r.t. CE, then it is taken as anode and CE is taken as
cathode.
Galvanic cell obtained in this case is represented as;
M | M+n || KCl | Hg2Cl2(s) | Hg(l)

At anode, oxidation occurs, M M+n + ne-

At cathode, reduction occurs, Hg2Cl2 + 2e- 2 Hg + 2Cl-
EMF of cell, ECell = Ecathode - EAnode
ECell = ECE EMn+/M
EMn+/M = ECE Ecell
If a given electrode undergoes reduction w.r.t. CE, then it is taken as cathode and CE is taken as
anode.
Galvanic cell obtained in this case is represented as;
Hg(l) | Hg2Cl2(s) | KCl || M+n |M

At anode, oxidation occurs, 2 Hg + 2Cl- Hg2Cl2 + 2e-

At cathode, reduction occurs, M+n + ne- M
EMF of cell, ECell = Ecathode - EAnode
ECell = EMn+/M__ ECE
EMn+/M = ECE + Ecell

Ion-selective electrode: Possesses the ability to respond only to certain specific ions, thereby
developing potential w.r.t that species only in a mixture and ignoring the other ions totally. In other
words, the potential developed by an ion-selective electrode depends only on the concentration of
species or ions of interest. For egs. Glass membrane is only H+ ions selective.

Applications: In the determination of

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1. Concentration of cations egs. H+ , Li+, Na+, K+, NH4+, Ag+, Pb2+, Cd2+, hardness (Ca2+, Mg2+) and
anions egs. Halide ions, NO3-, CN-, S2- etc.

2. PH of a solution by using H+ ion-selective glass electrode.

3. Total hardness of water

4. Testing blood electrolytes etc.

Glass electrode:

Construction: A glass electrode consists of a long glass tube with a thin walled bulb at one end,
special glass of low melting point and high electrical conductance is used for the purpose [corning
glass 22% Na2O, 6% CaO and 72% SiO2]. The bulb is filled with 0.1M HCl.
A silver-silver chloride electrode dipped in the solution provides an electrical contact. The bulb of
the glass electrode is dipped into any solution containing hydrogen ions. If the hydrogen ion
concentrations of the solution inside and outside the glass membrane are different then the potential
develops across the glass membrane. Glass electrode can be represented as

Ag / AgCl (s) / 0.1M HCl / glass

Advantages
This electrode can be used to determine PH in the range 0-9, with special type of glass even up to
12 can be calculated.
It can be used even in the case of strong oxidising agents.
The equilibrium is reached quickly.
It is simple to operate, hence extensively used in various laboratories.

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Limitations
The glass membrane though it is very thin, it offers high resistance. Therefore ordinary
potentiometers cannot be used, hence it is necessary to use electronic potentiometers.

It can be used up to 13 but becomes sensitive to Na + ions above PH 9 resulting in an alkaline

error
Working Principle of ion selective electrode or glass electrode :-
An ion selective electrode generally consists of ion selective membrane in contact with an
analyte solution on side and an internal reference solution on the other side.

The electrode is represented as

Ion selective membrane

solution to be Internal standard , Internal reference

analyzed solution electrode
n+ n+
[M ] = C1 =? [M ] = C2
The Mechanism of potential development in ion selective electrodes is different from that of the
other electrodes. Here the potiential is a kind of boundary potiential that develops across a
membrane that separates the analyte and internal std solution.
Eb = E1 E2
Eb = E0 + 0.0591/n log C1 (E0 + 0.0591/n log C2 )
Eb= 0.0591/n log C1 / C2
WhereC1 and C2 are the concentrations of analyte and internal standard solution respectively.

Theoritically Eb= 0, when C1 = C2. However a small additional potential is developed i,e Easymmetric
Since C2 is constant, then
Eb = L + 0.0591/n log C1 Where L = -0.0591/n log C2
Overall potiential of the electrode also includes, internal reference electrode potiential
.. EG= Eb + EAg/AgCl + Easymmetric

= L + 0.0591/n log C1 + EAg/AgCl + Easymmetric

EG= E0G+ 0.0591/1 log[ H+]

EG= E0G 0.0591pH.

Where EGo = L + EAg/AgCl + Easymmetric, is constant for a particular material.

Determination of a PH of a solution using a glass electrode:

PH of the solution is determined by coupling the glass electrode with saturated calomel electrode as
shown below. Conventionally, membrane electrode is treated as cathode and the refrence electrode as
the anode.

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Cell representation:-

Hg/ Hg2Cl2 /KCL// solution of unnown PH // Glass/HCl (0.01M)/AgCl/Ag

(Or)
Saturated Calomel Electrode // solution of unnown PH // Glass/HCl (0.01M)/AgCl/Ag
Emf of the cell is measured using a potentiometer.
Ecell = E cathode Eanode
Ecell = EG ESCE
Ecell = E0G 0.0591 PH ESCE

E0G ESCE Ecell

H
P =
0.0591

Classification of Galvanic cells

Primary cells: In which the cell reaction is irreversible and are not rechargeable and once
discharged have no further electrical use. Ex: Dry cell

Secondary cells: In which the cell reaction is reversible and are rechargeable cells. After
discharging it is recharged to its original condition by passing current through them and we can reuse
it again Ex: Lead acid battery, Ni-Cd cells etc

Concentration Cells:

Concentration cell is a type of galvanic cell in which electrode & electrolyte present in
both the half cells are same but only the concentration of metal or electrolyte is different.
Two types of concentration cells.

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1. Electrolyte concentration cell

2. Electrode concentration cell

Electrolyte concentration cells: It is a type of galvanic cell in which electrode & electrolyte
present in both the half cells are same but only the concentration of electrolyte is different.

Cell representation: M / M n+(C1) // M n+(C2) / M

Metal immersed in the dilute solution will have lower potential act as anode
M Mn+ (C1) + ne-
Metal immersed in the concentrated solution will have higher potential act as cathode
Mn+ (C2) + ne- M

Net cell reaction is: Mn+ (C2) Mn+ (C1)

Nernst equation for electrolyte concentration cell is

ECell = EoCell + 0.0591 log [Mn+]cathode

n [Mn+] Anode
EoCell =Eocathode - Eoanode = 0
ECell = 0.0591 log [Mn+]cathode
n [Mn+] Anode
ECell = 0.0591 log C2 at 298k
n C1
ECell is +ve and reaction is spontaneous only when C2 > C1

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Electrode concentration cells: It is a type of galvanic cell in which electrode & electrolyte
present in both the half cells are same but only the concentration of electrode is different.
Electrodes with different concentration of metal are generally obtained by dissolving different
amount of metal in liquid mercury called as amalgam electrode.

Cell representation: M n+(C1) (Hg) / M n+ / M n+(C2) (Hg) , where, C1 > C2

2+
For example : Pb(0.5 M) (Hg) Pb Pb (0.1 M) (Hg)

Electrode containing higher concentration of metal will have lower potential, acts as anode.
n+ -
M(C1) (Hg) M + ne
Electrode containing lower concentration of metal will have higher potential, acts as cathode.
n+ -
M + ne M (C2) (Hg)

Net cell reaction is : M(C1) (Hg) M(C2) (Hg)

In these cells, the potential difference is developed between two like electrodes at different
concentrations dipped in the same solution of the electrolyte.

They do not include the liquid junction potential.

Ex: 1. Cd;Hg(C1) / CdSO4 /Cd; Hg(C2)

Amalgams of the same metal Cadmium of two different concentrations are immersed in CdSO4
solution of same concentration.

2. Pt; H2(P1) //C1 /H2(P2) ;Pt

Two hydrogen electrodes at different partial pressure of hydrogen in the same solution of hydrogen
ions constitute a cell of this type.

The reactions taking place in a concentration cell is,

At Anode, M Mn+ (C1) + ne-

At Cathode, Mn+ (C2) + ne- M

Net cell reaction is, Mn+ (C2) Mn+ (C1)

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The cell reaction is spontaneous when C2> C1. As the reaction proceeds, the solution which was
originally more concentrated (C2) becomes dilute and the solution which was originally dilute (C1)
becomes more concentrated. After some times, the concentration of solution at both the half cells
becomes equal i.e., C1 = C2 and the emf of the cell becomes zero. The cell is in equilibrium. Hence in
a concentration cell, the emf depends on the ratio of concentrations of the solutions, as the ratio
changes and the ratio is 1 i.e. C2 / C1 = 1, emf is zero.

Consider a Concentration Cell,

M/Mn+ (C1 ) //Mn+ (C2 )/M

The emf of the cell is given by, Ecell = E cathode Eanode

Applying Nernst equation for single electrode potential, we get,

Ecell = { Eo Mn+ / M + 0.0591/n log C2} - { Eo Mn+ / M + 0.0591/n log C1}

Here both cathode and anode are made up of same metal.

Ecell = 0.0591/n log (C2/C1) at 250c

Case 1. When C1 = C2 , Ecell = 0, cell is in equilibrium.

Case 2. When C2 >C1 , Ecell is positive, cell reaction is spontaneous

Case 3. When the ratio , C2 /C1 changes, Ecell also changes, C2 /C1 = constant then, Ecell is also
constant , Therefore Ecell C2 /C1

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