References:

1. Engg.Chemistry by Jain and Jain

2. Engg.Chemistry by Dr. R.V.Gadag and Dr.
A.Nithyananda Shetty
3. Principles of Physical Chemistry by Puri and
Sharma

 Electrochemistry is a branch of chemistry which

deals with the properties and behavior of
electrolytes in solution and inter-conversion of
chemical and electrical energies.

 An electrochemical cell can be defined as a

single arrangement of two electrodes in one
or two electrolytes which converts chemical
energy into electrical energy or electrical
energy into chemical energy.
It can be classified into two types:
Galvanic Cells.
Electrolytic Cells.

Galvanic Cells:
A galvanic cell is an electrochemical cell that
produces electricity as a result of the
spontaneous reaction occurring inside it.
Galvanic cell generally consists of two
electrodes dipped in two electrolyte solutions
which are separated by a porous diaphragm or
connected through a salt bridge. To illustrate a
typical galvanic cell, we can take the example
of Daniel cell.

Daniel Cell.

At the anode:

Zn Zn 2+ + 2e-

At the cathode: Cu 2+ + 2e- Cu

Net reaction: Zn(s)+Cu 2+ (aq) Zn 2+ (aq)+ Cu(s)

 ELECTROLYTIC CELL
An electrolytic cell is an electro chemical cell in
which a non- spontaneous reaction is driven by
an external source of current although the
cathode is still the site of reduction, it is now the
negative electrode whereas the anode, the site
of oxidation is positive.

Representation of galvanic cell.

Anode Representation:
ZnZn2+ or Zn ; Zn2+
Zn ZnSO4 (1M) or Zn ; ZnSO4 (1M)
Cathode Representation:

Cu2+/Cu or Cu2+ ;Cu

Cu2+ (1M) ; Cu or CuSO4(1M)/Cu
Cell Representation:
Zn ZnSO4 (1M) CuSO4(1M)/Cu

Liquid Junction Potential.

Difference between the electric potentials
developed in the two solutions across their
interface .
Ej = soln, R - soln,L
Eg: *Contact between two different
electrolytes (ZnSO4/ CuSO4).
*Contact between same electrolyte of
different concentrations(0.1M HCl /
1.0 M HCl).

Salt Bridge.
The liquid junction potential can be
reduced (to about 1 to 2 mV) by joining the
electrolyte compartments through a salt
bridge.

Function Of Salt Bridge.

It provides electrolytic contact between the
two electrolyte solutions of a cell.
It avoids or at least reduces junction
potential in galvanic cells containing two
electrolyte solutions in contact.

Emf of a cell.
The difference of potential, which causes a
current to flow from the electrode of higher
potential to one of lower potential.
Ecell = Ecathode- Eanode
The E Cell depends on:
the nature of the electrodes.
temperature.
concentration of the electrolyte
solutions.

 Standard emf of a cell(Eo cell) is defined as the

emf of a cell when the reactants & products of
the cell reaction are at unit concentration or unit
activity, at 298 K and at 1 atmospheric pressure.

The emf cannot be measured accurately using a

voltmeter :
As a part of the cell current is drawn,thereby
causing a change in the emf.
As a part of the emf is used to overcome the
internal resistance of the cell.

Standard Cell.
It is one which is capable of giving constant and
reproducible emf.
It has a negligible temperature coefficient of the emf.
The cell reaction should be reversible.
It should have no liquid junction potential.
Eg: Weston Cadmium Cell. The emf of the cell is
1.0183 V at 293 K and 1.0181 V at 298 K.

 Weston Cadmium Cell

Sealed wax

Cork
CdSO4.8/3H2O
crystals

Cd-Hg
12-14%
Cd

Soturated solution of
CdSO4.8/3H2O

Paste of Hg2SO4
Mercury, Hg

 Cell representation:

Cd-Hg/Cd2+// Hg2SO4/Hg
At the anode:
Cd (s) Cd2+ + 2eAt the cathode:
Hg2SO4(s) + 2e- 2 Hg (l)+ SO42-(aq)
Cell reaction:
Cd + Hg22+ Cd2+ + 2Hg

Origin of single electrode potential.

Consider Zn(s)/ ZnSO4

Anodic process: Zn(s) Zn2+(aq)

Cathodic process: Zn2+(aq) Zn(s)
At equilibrium: Zn(s) Zn2+(aq)

Metal has net negative charge and solution has

equal positive charge leading to the formation
of an Helmholtz electrical layer.

Single electrode potential.

Electric layer on the metal has a potential
(M).
Electric layer on the solution has a
potential (aq)
Electric potential difference between the
electric double layer existing across the
electrode /electrolyte interface of a single
electrode or half cell.

De-electronation

Electronation

Helmholtz double layer

MEASUREMENT OF ELECTRODE
POTENTIAL.
It is not possible to determine experimentally the
potential of a single electrode.
It is only the difference of potentials between two
electrodes that we can measure by combining
them to give a complete cell.
By arbitrarily fixing the potential of reversible
hydrogen electrode as zero it is possible to
assign numerical values to potentials of the
various other electrodes.

Sign Of Electrode Potential.

The electrode potential of an electrode:
Is positive: If the electrode reaction is reduction
when coupled with the standard hydrogen
electrode
Is negative: If the electrode reaction is oxidation
when coupled with standard hydrogen electrode.
According to latest accepted conventions, all
single electrode potential values represent
reduction tendency of electrodes.

 when copper electrode is combined with SHE, copper

electrode acts as cathode and undergoes reduction
hydrogen electrode acts as anode.
H2(g) 2H+ +2e- (oxidation)
Cu2+ +2e- Cu (reduction)
Hence electrode potential of copper is assigned a
positive sign. Its standard electrode potential is 0.34 V.

 When zinc is coupled with S.H.E. zinc electrode

acts as anode and hydrogen electrode acts as

cathode.
Zn Zn2+ +2e2H+ + 2e- H2.
Hence, electrode potential of zinc is negative.
The standard electrode potential of zinc
electrode is -0.74 V.

Nernst Equation.
It is a quantitative relationship between electrode
potential and concentration of the electrolyte
species.
Consider a general redox reaction:
Mn+(aq) + ne- M(s) ----(1)
We know that, G =-nFE ----- (2)
Go=-nFEo-----(3)
G =Go +RT ln K

G =Go +RT ln K
G =Go +RT ln[M]/[Mn+]-----(4)
-nFE= -nFEo + RT ln [M]/[Mn+]----(5)
E= Eo RT/nF ln 1/[Mn+]------(6)
E=Eo- 2.303 RT/nF log 1/[Mn+]---(7)
At 298K,
E= Eo-0.0592/n log 1/[Mn+]-------(8)

1. A galvanic cell consists of copper plate

immersed in 10 M solution of CuSO4 and iron
plate immersed in 1M FeSO4 at 298K. If
E0cell=0.78 V, write the cell reaction and calculate
E.M.F. of the cell.

Solution:
Cell reaction:
Fe + Cu2+

Fe2+ + Cu

ECell= E0Cell-0.0592/2 log [Fe2+ ]/[Cu2+]

ECell= 0.78 + 0.0296 log 10/1
=0.8096V

Calculate E.M.F. of the zinc silver cell at 25C

when [Zn2+ ] = 1.0 M and [Ag+] = 10 M
(E0cell=1.56V at 25C). Write the cell

representation and cell reaction

Solution:
Cell representation
Zn/ Zn2+((1M)//Ag+(10M) /Ag
Cell reaction:
Zn + 2Ag+

Zn2+ + 2Ag
ECell= E0Cell-0.0592/2 log [Zn2+ ]/[Ag+]2
ECell= 1.56 + 0.0592 log 10/1.0
=1.6192 V

The emf of the cell

Mg Mg 2+ (0.01M) Cu 2+ /Cu is measured to
be 2.78 V at 298K. The standard eletrode
potential of magnesium electrode is -2.37
V. Calculate the electrode potential of
copper electrode

Cell reaction:
Mg + Cu2+

Mg2+ + Cu

E= Eo-0.0592/n log 1/[Mn+]

EMg= EoMg-0.0592/2 log 1/[Mg2+]
=-2.4291V
Ecell=ECu-EMg
2.78 = ECu-[-2.429]
ECu =2.78-2.429
=0.3509 V

The emf of the cell

Cu Cu 2+ (0.02M) Ag+ /Ag is measured to
be 0.46 V at 298K. The standard eletrode
potential of copper electrode is 0.34 V.
Calculate the electrode potential of silver.
electrode

Energetics of Cell Reactions.

Net electrical work performed by the cell reaction
of a galvanic cell:
W= QE ------(1)
Charge on 1mol electrons is
F(96,500)Coulombs.
When n electrons are involved in the cell
reaction,
the charge on n mole of electrons = nF

Q = nF
Substituting for Q in eqn (1)
W = nFE ----------(2)
The cell does net work at the expense of
- G accompanying. G = -nFE
- G = nFE

From Gibbs Helmholtz equation.

G = H + T [(G)/ T]P ------- (2)
-nFE = H nFT ( E/ T)P
H = nFT ( E/ T)P nFE
H = nF[T( E/ T)P E]
We know that,

[ (G)/ T]P = - S

S = nF (E/ T)P

Problem: Emf of Weston Cadmium cell is

1.0183 V at 293 K and 1.0l81 V at 298 K.
Calculate G, H and S of the cell
reaction at 298 K.
Solution:- G: G = - n FE
n = 2 for the cell reaction; F = 96,500 C
E= 1.0181 V at 298 K
G = -2 x 96,500 x 1.0181 J = -196.5 KJ

 H: H = nF [ T (E /T)P E]
(E/T)p = 1.0181 1.0183 / 298-293 =
-0.0002 / 5

= -0.00004VK-1
T = 298 K
H = 2 x 96,500 { 298 x (-0.00004)
1.0181)

= -198. 8 KJ
S:
S = nF (E / T) P

= 2 x 96,500 x (0-00004) = -7.72JK-1

Classification of Electrodes.
Gas electrode ( Hydrogen electrode).
Metal-metal insoluble salt (Calomel
electrode).
Ion selective electrode.(Glass electrode).

Gas electrode.
It consists of gas bubbling over an inert
metal wire or foil immersed in a solution
containing ions of the gas.
Standard hydrogen electrode is the
primary reference electrode, whose
electrode potential at all temperature is
taken as zero arbitrarily.

Construction.

 Representation: Pt,H2(g)/ H+
Electrode reaction: H+ + e- 1/2 H2(g)
The electrode reaction is reversible as it can
undergo either oxidation or reduction depending
on the other half cell.
If the concentration of the H+ ions is 1M,
pressure of H2 is 1atm at 298K it is called as
standard hydrogen electrode (SHE).

Applications.
To determine electrode potential of other
unknown electrodes.
To determine the pH of a solution.
E=Eo- 2.303 RT/nF log [H2]1/2/[H+]
= 0 -0.0591 log 1/[H+]
= -0.0591pH.
Cell Scheme: Pt,H2,H+(x)// SHE

 The emf of the cell is determined.

E (cell) = E (c) E(A)

= 0 (- 0.0592 pH)
E (cell) = 0.0592 pH
pH = E(cell)/ 0.0592

Limitations.
Constuction and working is difficult.
Pt is susceptible for poisoning.
Cannot be used in the presence of
oxidising agents.

Metal metal salt ion electrode.

These electrodes consist of a metal and a
sparingly soluble salt of the same metal
dipping in a solution of a soluble salt
having the same anion.
Eg: Calomel electrode.
Ag/AgCl electrode.

Construction.

 Representation: Hg; Hg2Cl2 / KCl

It can act as anode or cathode depending on the
nature of the other electrode.
As anode: 2Hg + 2Cl- Hg2Cl2 + 2e As Cathode: Hg2Cl2 + 2e- 2Hg + 2 Cl-

E = Eo 2.303 RT/2F log [Cl-)2

= Eo -0.0591 log [Cl-] at 298 K
Its electrode potential depends on the concentration of
KCl.
Conc. of Cl0.1M

Electrode potential
0.3335 V

1.0 M

0.2810 V

Saturated

0.2422 V

Applications.
Since the electrode potential is a constant
it can be used as a secondary reference
electrode.
To determine electrode potential of other
unknown electrodes.
To determine the pH of a solution.
Pt,H2/H+(X) // KCl,Hg2Cl2,Hg
pH = E(cell) 0.2422/ 0.0592

Ion Selective Electrode.

It is sensitive to a specific ion present in an
electrolyte.
The potential of this depends upon the activity of
this ion in the electrolyte.
Magnitude of potential of this electrode is an
indicator of the activity of the specific ion in the
electrolyte.
*This type of electrode is called indicator
electrode.

 Glass Electrode:`

Scheme of typical pH glass electrode

1. a sensing part of electrode,

2. a bulb made from a specific glass
sometimes electrode contain small amount
of AgCl precipitate inside the glass
electrode
3 internal solution, usually 0.1M HCl for pH
electrodes
4.internal electrode, usually silver chloride
electrode or calomel electrode
5.body of electrode, made from nonconductive glass or plastics.
6.reference electrode, usually the same type
as 4
7.junction with studied solution, usually made
from ceramics or capillary with asbestos
or quartz fiber.

 The hydration of a pH sensitive glass

membrane involves an ion-exchange reaction
between singly charged cations in the
interstices of the glass lattice and protons
from the solution.
H+ +
Soln.

Na+
glass

Eg = Eog 0.0592 pH

Na+ +
soln.

H+
glass

Electrode Potential of glass

electrode.
The overall potential of the glass electrode has
three components:

The boundary potential Eb,

Internal reference electrode potential E ref.

Asymetric potential Easy.- due to the

difference in response of the inner and outer
surface of the glass bulb to changes in [H +].
Eg = Eb + Eref. + Easy.

 Eb = E1 E2
= RT/nF ln C1 RT/nF ln C2
= L + RT/nF ln C1
Eb depends upon [H+]
Eg = Eb + EAg/AgCl + Easy.
= L + RT/nF ln C1 + EAg/AgCl + Easy.
= Eog + RT/nF ln C1
= Eog + 0.0592 log [H+]
Eg = Eog 0.0592 pH.


1.

2.

3.
4.

Advantages:
It can be used without interference in solutions
containing strong oxidants, strong reductants,
proteins, viscos fluids and gases as the glass is
chemically robust.
It can be used for solutions having pH values 2 to
10. With some special glass (by incorporation of
Al2O3 or B2O3) measurements can be extended to
pH values up to 12.
It is immune to poisoning and is simple to operate
The equilibrium is reached quickly & the response
is rapid

5. It can be used for very small quantities of

the solutions. Small electrodes can be
used for pH measurement in one drop of
solution in a tooth cavity or in the sweat
of the skin (micro determinations using
microelectrodes)
6. If recently calibrated, the glass electrode
gives an accurate response.
7. The glass electrode is much more
convenient to handle than the
inconvenient hydrogen gas electrode.

Disadvantages:
The bulb of this electrode is very fragile and has
to be used with great care.
The alkaline error arises when a glass electrode is
employed to measure the pH of solutions having
pH values in the 10-12 range or greater. In the
presence of alkali ions, the glass surface becomes
responsive to both hydrogen and alkali ions. Low
pH values arise as a consequence and thus the
glass pH electrode gives erroneous results in highly
alkaline solutions.

The acid error results in highly acidic solutions

(pH less than zero)Measured pH values are
high.
Dehydration of the working surface may cause
erratic electrode performance. It is crucial that
the pH electrode be sufficiently hydrated before
being used. When not in use, the electrode
should be stored in an aqueous solution
because once it is dehydrated, several hours
are required to rehydrate it fully.

As the glass membrane has a very high

electrical resistance (50 to 500 m), the
ordinary potentiometer cannot be used for
measurement of the potential of the glass
electrode. Thus special electronic
potentiometers are used which require
practically no current for their operation.

Standardization has to be carried out frequently

because asymmetry potential changes gradually
with time. Because of an asymmetry potential,
not all glass electrodes in a particular assembly
have the same value of EoG . For this reason, it is
best to determine EoG for each electrode before
use.
The commercial verson is moderately expensive

Limitations.
The bulb is very fragile and has to be used
with great care.
In the presence of alkali ions, the glass surface
becomes responsive to both hydrogen and
alkali ions. Measured pH values are low.
In highly acidic solutions (pH less than zero)
measured pH values are high.
When not in use, the electrode should be
stored in an aqueous solution.

Applications.
Determination of pH:
Cell: SCE Test solution / GE
E cell = Eg Ecal.
E cell = Eog 0.0592 pH 0.2422
pH = Eog -Ecell Ecal. / 0.0592

Problems
The cell SCE (0.1M) HCl AgCl(s) /Ag
gave emf of 0.24 V and 0.26 V with buffer
having pH value 2.8 and unknown pH
value respectively. Calculate the pH value
of unknown buffer solution. Given ESCE=
0.2422 V

Eog= 0.0592pH +Ecell + Ecal.

= 0.0592x2.8 +0.24 + 0.2422
=0.648 V
pH = Eog -Ecell Ecal. / 0.0592
= 0.648 -0.26-0.2422/0.0592
= 2.46

CONCENTRATION CELLS.
Two electrodes of the same metal are in
contact with solutions of different
concentrations.
Emf arises due to the difference in
concentrations.
Cell Representation:
M/ Mn+[C1] Mn+/M[C2]

Construction.

 At anode: Zn Zn2+(C1) + 2e At cathode: Zn2+(C2) + 2e- Zn

Ecell = EC-EA
= E0 + (2.303RT/ nF)logC2[E0+(2.303RT/nF)logC1]
Ecell = (0.0592/n) log C2/C1
Ecell is positive only if C2 > C1

 Anode - electrode with lower electrolyte

concentration.
Cathode electrode with higher electrolyte
concentration.
Higher the ratio [C2/C1] higher is the emf.
Emf becomes zero when [C1] = [C2].

Problems
Zn/ZnSO4(0.001M)||ZnSO4(x)/Zn is 0.09V
at 25C. Find the concentration of the
unknown solution.

Ecell = 0.0592/n log C2/C1

0.09 =(0.0592/2) log ( x / 0.001)
x =1.097M

2. Calculate the valency of mercurous ions

with the help of the following cell.
Hg/ Mercurous
|| Mercurous
/Hg
nitrate (0.001N)
nitrate (0.01N)
when the emf observed at 18 C is 0.029
V
Ecell=(2.303 RT/nF) log C2/C1

Ecell=(2.303 RT/nF) log C2/C1

0.029 = 2.303RT/n) log (0.01/0.001)
0.029 =0.057 x 1/ n
n = 0.057/0.029 == 2
Valency of mercurous ions is 2, Hg2 2+

Assignment
Answer the following questions:
1.Distinguish between electrolytic and galvanic
cells.
2.Explain the origin of electrode potential. What are
the sign conventions for electrode potential?
3.Give reasons for the following.
i) The glass electrode changes its emf over a
period
of time.
ii) KCl is preferred instead of NaCl as an
electrolyte
in the preparation of salt bridge
4. What is meant by a standard cell? Give an
example

5. Quote any four limitations of glass electrode

6.Define liquid junction potential. How it can be
eliminated or minimized?
7.Derive Nernst equation for the single electrode
potential.
8.Describe potentiometric determination of emf of a
cell.
9.Writ e construction and working of Calomel
Electrode
10.What are concentration cells? Show that emf of
concentration cell becomes zero at a certain
point of its working.