1.

ELECTROCHEMISTRY

Syllabus: Introduction to electrochemical cells, Galvanic cell and electrolytic cells, Representation of a
galvanic cell, Liquid junction potential and functions of a salt bridge, Calculation of E.M.F., of a galvanic
cell using electrode potential, Energetics of cell reactions, Thermodynamic deduction for G, H and S,
Determination of E.M.F., of a galvanic cell, Standard cell, Weston cadmium cell, Construction, working
and applications of Calomel electrode and Glass electrode, Application of E.M.F. Measurements,
Concentration cells.
Learning Objectives: At the end of the chapter the learner will be able to
1. Understand the terms, electrochemistry, galvanic cell, electrolytic cell, concentration cell and
standard cell.
2. Describe the major features of galvanic and electrolytic cells.
3. Know how to minimize the liquid junction potential.
4. Define standard cell and know how to measure emf.
5. Derive Nernst equation for electrode potential and solve simple Nernst equation problems.
6. Explain the basic relationship between EMF of a cell and G, H, and S.
7. Describe construction, working of and applications of glass electrode & calomel electrode.
8. Demonstrate knowledge of construction and working of concentration cell.
1.0 INTRODUCTION
Electrochemistry deals with the behavior of electrolytes in solution and interconversion of
chemical and electrical energies; that is, the study of chemical changes due to the flow of an
electric current and production of an electric current due to chemical reaction. Electrolysis,
electrometallurgy and electroplating use electrical energy to drive chemical reactions, while
chemical energy is transformed into electricity in galvanic cells, batteries and fuel cells. Substances
such as metals and alloys conduct electricity under the influence of an applied electric potential
through a flow of electrons and hence are known as electronic conductors. The flow of electricity in
electronic conductors does not cause any physical or chemical change in the conductor. On the other
hand electrolyte solutions and molten salts conduct electricity through the migration of ions and are
known as electrolytic conductors or electrolytes. When direct current is passed through an electrolyte
solution, decomposition and changes occur in the composition of the electrolyte. The practical
importance of electrochemistry include electroplating, electroextraction of metals, electro-refining
of metals, and electro-production of certain compounds.

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1.1 ELECTROCHEMICAL CELLS
Single arrangement of two electrodes in one or two electrolytes is called an electrochemical cell.
It is represented in figure 1.1
Electrochemical cells can be classified into two types:
1. Galvanic Cells Example: Daniel cell
2. Electrolytic Cells Example: Copper refining cell

Fig.1.1 A schematic diagram of Electrochemical Cell

Similarities between two types of cells:
Anodic oxidation. Cathodic reduction
Equivalent oxidation and reduction in the separate regions
Reactions occur on electrode surface only
Electrons flow from anodic part to cathodic part in the external circuit.
Differences between them:
Galvanic Cell Electrolytic Cell

1. Cell reaction is spontaneous 1. Cell reaction is non-spontaneous

2. Converts chemical energy to electrical 2. Converts electrical energy into
energy chemical energy
3. Anode is negative and cathode is 3. Anode is positive and cathode is
positive negative
4. Usually have two electrodes and two 4. Single electrolyte and two electrodes
electrolytes 5. Used for electrolysis apparatus like
5. Used as potable source of electrical electroplating and electrorefining
energy in cars, flashlights and
calculators
Example. Daniel cell Example. Electroplating of nickel

2
1.1.1 Galvanic Cells
A single arrangement of two electrodes in one or two electrolytes, which converts stored up
chemical energy in the form of active anodic and cathodic materials directly into electric energy is
called a galvanic cell. 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. Figure 1. 2
represents a Daniel cell.

Figure1.2 A schematic diagram of Daniel cell

In a Daniel cell a zinc rod is dipped in zinc sulfate solution and a copper rod dipped in copper sulfate
solution. The two electrolytes are connected by a salt bridge. On completing the circuit the following
oxidation-reduction reactions taking place at the electrodes. At the zinc electrode, zinc goes into the
solution as Zn2+ ions, liberating two electrons. In the process zinc undergoes oxidation liberating two
electrons. The positive ion flows from salt bridge to cathode and the zinc electrode becomes lighter.
Zn (s) Zn2+ (aq) + 2e (1).

At the copper electrode reduction of Cu2+ ions takes place with the deposition of metallic copper on
copper rod, by consuming two electrons. The negative ions flow from salt bridge to anode and
copper electrode becomes heavier.

Cu2+ (aq) + 2e Cu(s) (2)

Each of these reactions is known as half cell reaction. The reaction (1) in which loss of electrons
takes place is called oxidation half reaction; while the reaction 2, in which gain of electrons takes

3
place, is called reduction half reaction. The net reaction is obtained by adding reactions 1 and 2.
i.e. Zn(s)+ Cu2+ (aq) Zn2+ (aq) + Cu(s) is called redox or oxidation reduction reaction. When
the circuit is closed, the electrons flow from zinc to copper through the external wire to feed the
Cu2+ ions in the process of discharging copper and thus electrical energy or current is produced
which may be used for the purpose of external work.
As in the case of Daniel cell, by the combination of any two different electrodes materials one can
construct a galvanic cell. The electrode at which oxidation occurs is anode and the other one with
more tendency to undergo reduction acts as a cathode. In a galvanic cell anode is negative and
cathode is positive. Each galvanic cell has definite emf depending upon the nature of two half cells
which make up the cell.

1.1.3 Electrolytic cells

An electrolytic cell is a single arrangement of two elctrodes in one or two electrolytes. The
electrochemical reaction occurring in an electrolytic cell is non spontaneous.It is forcibly carried out
, by sending electric energy into the cell.
The electrolytic cell is represented in figure1.3.It finds wide applications in purification of metals &
also in electro deposition of a metal on to the surface of another metal, alloy or any conductor in
general, by the process of electrolysis.

Figure 1.3 Schematic diagram of an electrolytic cell

Electrolysis involves conversion of electrical energy into chemical energy i.e. chemical changes
are brought about by the expense of electrical energy. Since electrolysis is a non spontaneous
process, the minimum energy required to carry out such a process is equal to the free energy
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 increase accompanying the change, & this is equal but opposite in sign to the free energy
decrease accompanying the reverse spontaneous process. This is true when electrolysis is carried
out reversibly. However, in irreversible conditions, the potential to be applied for electrolysis is
higher than the reversible emf of the cell.
1.1.4 Representation of a galvanic cell
Daniel cell, may be represented as:
Zn ZnSO4 (1M) CuSO4(1M)/Cu
()Anodic (+) Cathodic
This is in accordance with IUPAC convention. Anodic half cell is shown on the L.H.S and cathodic
half-cell on the R.H.S in the cell scheme.

A single vertical line indicates a phase boundary across which electrical potential develops.

The double vertical lines in the middle indicates salt-bridge which electrolytically connect the two
electrolyte solution

The anode is represented as Metal/ metal ion and the cathode as metal ion / metal.

1.2 LIQUID JUNCTION POTENTIAL

Consider a galvanic cell containing two electrolytes separated by a diaphragm. The interface between
two miscible electrolyte solutions of a galvanic cell is called liquid-junction. Ions from each solution
diffuse into the other , across the junction. This gives rise to charge build up in the two solutions across
the junction and develops junction potential across the junction.
In a Daniel cell(Fig1.2), if the concentrations of ZnSO4 (aq) and CuSO4 (aq) are equal SO42- ions do not
diffuse across the junction and the charge cannot flow around the circuit. But Cu 2+ ions diffuse into
ZnSO4 (aq) and Zn2+ ions diffuse into CuSO4 (aq) because Cu2+ ions are slightly more mobile than Zn2+
ions. This produces a small excess positive charge on ZnSO4 (aq) side of the junction and equal
negative charge on the CuSO4 (aq) side. The liquid junction potential is the difference between the
electric potential developed in the two solutions across their interface.
soln, R soln,L soln. R
i.e. Ej = - where is the electric potential of the electrolyte solution on the
soln. L
right hand side half cell in the cell scheme. is the electric potential of the
electrolyte solution on the left hand side half-cell. Generally, LJPs are of the order of a few
millivolts.

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1.3 SALT BRIDGE
. A salt bridge is used to connect electrolytically, the two electrolyte solutions of a galvanic cell,
as shown in the Figure 1.4 below.

Figure 1.4 Schematic diagram of salt bridge used in a Daniel cell.

Saturated and jelled (with agar agar) KCl,or KNO3, or NH4NO3 solution whose ions have the same
migration velocities are filled ia a glass tube bent twice at right angle act as a salt bridge. Its open
ends dip into the electrolyte solutions. Electrolyte concentration is very large in the salt bridge and
hence ions of considerably dilute solutions of the cell make only negligible contribution to the
junction potential.
Since the positive and negative ions of the salt bridge possess equal mobilities, complete
neutralization of charge developed in the two solutions of the cell occurs due to the release of
positive and negative ions of the salt bridge to the two solution at equal rates across the two ends of
the salt bridge. This prevents charge build up in the two solutions across the junction. The
contribution of the liquid junction to the potential can be reduced (to about 1 to 2 mV)
The salt bridge is prepared by dissolving 5g agar in 100 mL aqueous solution of KCl containing 35 g
of KCl and filling in a U-tube. On cooling, the agar forms a jell with KCl solution in it. A salt bridge
has the following functions:
1. It provides electrical contact between the two electrolyte solutions of a cell
2. It minimizes liquid junction potential in galvanic cells containing two electrolyte
solutions in contact. i.e., it reduces the LJP to a minimum by nearly equal diffusion rates
of cations and anions.
3. It maintains electrical neutrality of the two half cells.

1.4 ELECTROMOTIVE FORCE OF THE CELL

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Electric current is generated in agalvanic cell by the difference in electric potential between the two
half-cells of the cell. This potential difference is called the cell potential Ecell of the the galvanic cell
or (e.m.f.) of the cell and is expressed in volts V. The EMF of a cell is given by:

Ecell = Ecathode- Eanode

It is also the equilibrium potential difference between the two half cells of a galvanic cell.
To facilitate comparison of different galvanic cells, their standard emf, denoted by E0 cell is used.
Standard emf of a cell is defined as the voltage of a cell measured under standard conditions which
are : the reactants & products of the cell reaction are at unit concentration or unit activity, at 298 K
and at 1 atmospheric pressure including pure solids and liquids.
The emf of a cell represents the driving force of a cell reaction. As represented by the
thermodynamic relation,
G = -nFE
where G is the free energy change accompanying a cell reaction, n is the number of electron
transfer during the cell reaction, and F is the Faraday constant, F = eN A, the magnitude of the charge
per mole of electrons.
The cell reaction is spontaneous or feasible when G is negative. G can be negative only if emf of
the cell is positive, because, the other two factors, n & F are always positive. The positive emf value
indicates the spontaneity of cell reaction in the given direction.
1.4.1 Measurement of emf of a cell
The emf cannot be measured accurately by connecting directly a voltmeter between the two
electrodes, because during such a measurement, a part of the cell current is drawn to deflect the
needle as part of the emf is used to overcome the internal resistance of the cell. Consequently, such a
measurement would indicate a potential difference less than the actual emf of the cell. For precise
emf measurements potentiometers are used, which require extremely small current at balance point.
The potentiometric measurement of emf of a cell works based on Poggendorffs compensation
method. In this method, emf of a test cell is opposed by the impressed emf from an external source of
emf, and the measurement is made when there is no net flow of current in the circuit. The basic
principle is that the EMF of the cell to be measured is exactly balanced by an equal and opposite
known EMF so that no current flows in the circuit (nul point) A schematic diagram of potentiometer
is shown in Figure1. 5.

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 S Rh
+ - C

D D
A
B
Ex
J
G
Es

Figure 1.5 Schematic diagram of an Poggendorfs method

AB- Potentiometric wire
S- Storage battery
ES- Standard cell
Ex- unknown cell
G- Galvanometer
J- Sliding contact.
Rh adjustable resistance

The two terminals of a storage battery(S) which has a constant and higher emf than the test cell, is
connected to two ends of a long uniform wire AB of high resistance. The positive terminal of the test
cell is connected to the end A, to which the positive terminal of S is connected & the negative
terminal is connected to a sliding contact J through a galvanometer (G). The sliding contact is moved
along the wire AB until the null point is reached, which is indicated by no current flow in the
galvanometer. The position of null point is noted & the distance AD is measured. The EMFof the
unknown cell Ex is proportional to the length AD.
Ex AD

Then the test cell Ex is replaced by a standard cell Es, whose EMF, is known the position of the
sliding contact is readjusted by moving it over AB, as before, till null point D 1 is reached .The
length AD1 is measured. The EMF of the standard cell Es is proportional to the length AD1.
Es AD1
Ex AD
Es AD1
Ex = AD x Es
ADI
Thus the EMF of the test cell is calculated by substituting the emf of the standard cell in the above
equation.

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1.4.2 Standard Weston cadmium cell Standard
cell requirements:
1. Its emf should remain constant for a longer period of time.
2. It should be capable of providing highly reproducible emf.
3. The temperature coefficient of emf should be negligibility small i.e ( E/ T)= 0
4. The cell reaction should be reversible.
5. It should not be subjected to permanent damage due to passage of current.
A standard cell is one which has a constant and reproducible known emf with a negligible variation
of emf with temperature e.g. Weston standard cell or Weston cadmium cell.

Construction: It consists of an H-shaped glass vessel as shown in figure 1.6 below, with the lower
ends of both arms closed, having platinum wire scaled into the bottom of the each arm. The positive
electrode contains mercury over which a paste of mercurous sulphate (Hg2SO4) and mercury is
placed. The negative electrode consists of an amalgam of Cd and Hg, containing about 12-15% Cd
by weight. Over both electrodes are sprinkled some crystals of solid CdSO4. 8/3 H2O are added to
keep the electrolyte solution saturated at all temperatures. The remaining part of the cell is filled with
a saturated solution of cadmium sulphate that acts as an electrolyte. The upper ends of the tube are
closed with corks and sealing wax.

Figure 1.6 Schematic diagram of a Weston cadmium cell.

Working: When the cell operates, the following reactions occur at the two electrodes.
Anode: Cd (s) Cd2+ (aq) + 2e

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Cathode: Hg2SO4 (s) + 2e 2 Hg (l) + SO42 (aq)
cell reaction : Cd (s) + Hg 2SO4 (S) CdSO4 (s) + 2 Hg (l)
The potential of this cell is 1.018 volts at 298 and it varies slightly (-0.09046 volt per degree
centigrade). The cell works for many years, without any voltage changes and reproducible value of
emf. It is used as a standard cell in accurate emf measurement of other cells.

1.4.3 Energetics of cell reactions:

1.4.3.1 The relation between E and G:
The maximum electrical work as per thermodynamics, chemical reaction can do is given by the value
G for the reaction.
We, max = G (1)
where, We is electrical work
The net electrical energy and the EMF of the cell produced in a cell is the product of the quantity of
electricity that passes through the cell and the EMF of the cell.
We = QE Joules. (2)
Q is the quantity of electrical charge in coulombs produced by the reaction and E is the EMF of the
cell in volts.
Charge on 1 mol (6.02 x 10 23) electrons is F coulombs, where F is Faraday constant. When
electrons take part in the cell reaction, n mols of electrons are involved per mole of reactant of
the reaction. Hence charge on n mol of electrons = nF coulombs.
This is the charge, Q in coulombs produced by the reaction. For 1 mole of electrons transferred
in the cell reactions, the quantity of electricity = 1F
If n moles of electrons are transferred in the cell reactions, the quantity of electricity Q = n F
Therefore We = nFE, (3)
The cell does net work at the expense od decrease in free energy, accompanying the cell reaction.
Electrical energy produced = decrease in free energy for cell reaction i.e. G = nFE
or G = nFE Joules-------(4)
If we know EMF (E) , G can be calculated. The larger the value of cell potential the further the
reaction is from equilibrium. The sign of cell potential tell us the direction in which reaction must
shift to reach equilibrium.
1.4.3.3 Relation between E and H
From GibbsHelmholtz equation: G = H T [(G)/ T]P
G = H + T [(G)/ T]P (5)

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 nEF = H + T [(nEF)/T]p
nFE = H + TnF(E/T)P { as n & F are constants}
H = TnF(E/T)P nFE
Enthalpy Change H = nF[T(E/T)P E] (6)
If we know EMF and temperature coefficient of emf, H can be calculated..

1.4.3.2 Relation between E and S :

According to Gibbs Helmholtz equation the change in free energy, G, enthalpy H and entropy
S, accompanying a reaction at a constant temperature, T are related as
G = H TS (7)
Substituting the values for G & H
nFE = nF[T(E/T)P E] T S
: S = nF(E/T)P (8), S can be calculated
Note: G = H- TS Do not use in the calculations !
1.4.3.4 Numerical Problems
1. 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
2. The emf of the cell Cd|CdCl2. 2.5 H2O (saturated) || AgCl(s)| Ag is 0.6753V and 0.6915 V at
298 K and 273 K respectively. Calculate G, H and S of the cell reaction at 298 K.
Solution. Here n = 2, E = 0.6753 V at 298 K and 0.6915 at 273 K.
(E/T)p = (0.6753-0.6915) V/ (298-273) K = - 0.00065 V/K

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 Now at 298 K, H = nF [ T (E /T)P E]
= 2 mol x 96,500 C mol-1{ [298 K x (- 0.00065 V/K)] 0.6753 V }
= -167. 7 KJ
G at 298 K ; G = - n FE = -2 x 96,500 x 0.6753 = -130.33 KJ
S = nF(E / T) P
= 2 x 96,500 x (0-00065) = -125.45 J.K-1
1.5 SINGLE ELECTRODE POTENTIAL
One half of a galvanic cell where either oxidation half- reaction or the reduction half-reaction
of the cell occurs is called a single electrode. A single electrode develops a definite electric potential
due to the spontaneous oxidation or reduction half-raection occurring at it. It is called single
electrode potential .Single electrode potential means always reduction potential, according to the
accepted convention
Example: In case of Zn in ZnSO4 solution, both the solution and metal contain Zn2+ ions and they
can be transferred between the two phases across the electrode-electrolyte interface.
Zn2+(s) Zn2+(aq.) : anodic process
Zn2++(aq.) Zn2+(s) : cathodic process

Initially the anodic rate predominates the cathodic rate. This gives rise to development of negative
charge due to the accumulation of electrons on the metal. The negative charge retards the anodic
process and accelerates the cathodic process. Eventually, a steady state is reached by these opposite
processes At equilibrium, the metal has net negative charge and the solution equal positive charge,
leading to the formation of an electric layer of negative charge on the metal and an electric layer of
positive charge in the solution. The electric layer on the metal is a thin single layer. The electric layer in
the solution is thick diffused layer. It contains both positive and negative ions. But it contains excess
positive ions due to which it acquires net positive charge which is equal to the negative charge of the
single layer on the metal. This is shown in figure 1.7 below.

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 Figure 1. 7 Schematic representation of an electrical double layer.
The electric layer on the metal has a definite electric potential, (M). The diffuse electric layer in the
solution also has a definite electric potential, (aq). The difference between the two electric potentials,
is the single electrode potential, E of the zinc electrode.

At the copper half-cell : CuSO4 / Cu of the Daniel cell, The cathodic rate predominates the anodic
rate, before the equilibrium is reached betweenthe opposite processes. Thus electric layer on the metal
has definite positive charge due to net gain of Cu2+ ions from the solution. The electric layer in the
solution has an equal negative charge due to SO42- ions left behind by the Cu2+ ions deposited on the
metal from the solution.

Electric potential difference between the electric double layer existing across the electrode-
electrolyte interface of a single electrode is called single electrode potential.

1.5.1 Measurement of electrode potential

It is impossible to determine the absolute half cell potential .We can only measure the
difference in potential between two electrodes potentiometrically, by combining them to form a
complete cell.
Electrode potential cant be measured with one wire. All voltage measuring devices measure only the
difference in potential. Voltmeter has two knobs to measure the potential of an electrode.
One contact of an voltmeter is connected to the test electrode. The other contact from the voltmeter
must then be brought into electrical contact with the solution in the electrode compartment via
another conductor. So this second contact inevitably involves solid/ solution interphase. This acts as
a second half cell at which chemical change must occur if charge is to flow and potential is to be
measured. So a potential is associated with this second reaction. Absolute half cell potential is not
obtained but difference between the half cell is measured. Therefore, absolute electrode potentials
cannot be measured. We can only determine the relative value of electrode potential, if we can fix
arbitrarily the potential of any one electrode. For this purpose, the potential of a standard hydrogen
electrode (SHE) or normal hydrogen electrode (NHE) (i.e., a platinum electrode in contact with 1 M
H+ ion concentration and hydrogen gas at atmospheric pressure is constantly bubbled through it) has
been arbitrarily fixed as zero and the numerical values of electrode potentials of different
electrodes are relative values w.r.t SHE. Therefore, single electrode potentials of electrodes are
referred to as potentials on the hydrogen scale.

Sign of electrode potential: When an electrode is coupled with a SHE, if reduction occurs then EP is
given a +ve sign e.g Copper electrode + SHE
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Cu2+ +2e- Cu(s) reduction at copper electrode (cathode)
H2(g) 2H+ +2e- oxidation at hydrogen elecrode (anode) E0 = 0.34 volt
A +ve sign on the EP value indicates that the half cell acts as cathode and acepts electrons from the
hydrogen electrode.
Similarlly, when an electrode is coupled with a SHE, if oxidation occurs then EP is given a -ve sign
e.g . Zinc electrode + SHE
Zinc elecrode : Zn (s) Zn2+(aq) +2e- (oxidation)
Hydrogen elecrode: 2H+ (aq) + 2e - H 2 (g) (reduction) E0 = - 0.76 volt
A ve sign on the electrode potential value indicates that the half cell acts as anode by releaseing
electrons to the hydrogen electrode
.
1.5.2 Standard electrode potential
Standard electrode potential is the electrode potential when the electrode is in contact with a
solution of unit concentration at 298 K involving pure solids and liquids. If the electrode involves a
gas, then the gas is at 1 atmospheric pressure. It is denoted by Eo. When elements are arranged in
increasing order (downwards) of their standard electrode potential, a series called electrochemical
series is obtained. In a cell, the electrode with lower electrode potential has less tendency to undergo
oxidation and it acts as anode similarly electrode with higher electrode potential has higher tendency
to undergo reduction and acts as cathode.

Reducing agents Stable ions Electrode half reaction E0

volts
Lithium Li+ -3.03
Potassium K+ -2.92
Aluminium Al3+ -1.66
Zinc Zn2+ -0.76
Iron Fe3+ -0.44
Lead Pb2+ -0.13
H2 2H+ 0
Copper Cu2+ 0.34
Silver Ag+ 0.80
Gold Au3+ 1.52

Selected standard electrode potentials

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1.5.3 Nernst equation
Nernst equation is an expression that relates the potential of an electrode to the concentrations of
those species in solution that are responsible for the potential. Consider the following redox
reaction: Mn+(aq) + ne M(s)
We know that G = nFE
Under standard conditions Go = -nFEo
The free energy change for a spontaneous reaction is related to the equilibrium constant Kc
G = Go + RT ln Kc
Putting G = nFE
nFE = nFEo + RT ln [M] / [Mn+ ]
Dividing by nF, we get
E = Eo RT/nF ln 1/ [Mn+] ; since [M] = 1
E = Eo + 2.303RT/nF log [Mn+]
E= Electrode potential
E0= Standard electrode potential
R= Universal gas constant ( joules per mol K)
T = Temperature in Kelvin scale F= Faraday constant (96,500 Coulumbs)
n = Number of electrons transferred in the half reaction/ cell reactions
[Mn+] = Concentration of metal ion at that moment in time (moles per litre).
At 298 K, when the values of R.T and F are substituted, the equation reduces to,

E = Eo + (0.0592/n) log [Mn+]

This expression is known as Nernst equation for electrode potential at 298 K.

The Nernst equation can also be applied for the calculation of emf of a cell.
Consider the cell reaction aA+ bB cC +dD
The Nernst equation for the emf of the cell is
Ecell = Eocell 2.303RT/nF log [C]c [D]d /[A]a [B]b
At 298 K,
Ecell = Eocell (0.0591/n) log [C]c [D]d /[A]a [B]b
Where n is the number of electrons transferred during the cell reaction and Eocell is the standard emf
of the cell.

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1.5.3.1 Significance of the Nernst equation
It can be used to calculate the potential of a cell that operates under non-standard
conditions.
It can be used to measure the equilibrium constant for a reaction. At equilibrium the
overall cell potential for the reaction is zero. i.e. E=0

1.6. Calomel electrode

The calomel electrode), a mercury mercurous chloride electrode develops + 0.242 V at 289 K when
the KCl solution is saturated. It has been found that the potential of the calomel electrode, on the
hydrogen scale varies with the concentration of the potassium chloride solution used. The
concentration of KCl solution used is either decinormal, normal or saturated. Correspondingly, the
electrode is known as decinormal, normal or saturated calomel electrode respectively.
Figure1.8 shows the schematic diagram of a calomel electrode

.
Figure1.8 Schematic diagram of a calomel electrode

1.6.1.1 Construction & Working:

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 It consists of a tube, in the bottom of which is mercury is placed , over which is a paste of
mercury and mercury chloride. The remaining part of the tube is filled with a solution of either
normal or decinormal or saturated KCl. A platinum wire sealed at its end fixed into the main tube
dipping into the mercury layer is used for making electrical contact. The electrode can be
schematically represented as Hg (l) /Hg2Cl2 (satd) /KCl-(satd/ xM) .
The calomel electrode can act as anode or cathode depending on the nature of other electrode of
the cell. When it acts anode, the electrode reaction is

2Hg (l) Hg22+ (aq) + 2e- Hg22+(aq)

+ 2Cl- (aq) Hg2Cl2

2Hg(l) + 2Cl- (aq) Hg2Cl2 (s)+ 2e-

---------------------------------------------

When it acts as cathode, the electrode reaction is,

Hg22+(aq) + 2e- 2Hg(l)
Hg2Cl2 (s) Hg22+ (aq) + 2Cl-
_____________________________
Hg2Cl2(s) + 2e- 2Hg (l) + 2 Cl-(aq)

The net reversible electrode reaction is,

Hg2Cl2(s) + 2e- 2 Hg (l) + 2 Cl-(aq)
Electrode potential is given by
E = Eo 2.303 RT log [Cl-]2
2F

= Eo - 0.0591 log [Cl-] at 298 K

1.6.1.2 Uses:
Since the electrode potential is a constant it can be used as a secondary reference electrode to replace
the inconvenient SHE for potential measurements. It can also be used to determine pH of any given
solution.
For example: The test electrode, Zn(s) /Zn2+(aq) is coupled with a saturated calomel electrode.
Zn(s) / Zn2+ (aq) Cl- (saturated soln) /Hg2Cl2(s) / Hg (l)

17
The emf of this cell is determined experimentally by potentiometric method.
Then E cell = E cathode E anode
= 0.2444 Ezn
Ezn = 0.2444 E cell
ii) To determine the pH of a solution cell:
Hg(l) / Hg2Cl2 (s) // H+ /pt,H2 (g)
E cell = E cathode E anode
= - 0.0592 pH - 0.242
pH= 0.2422 - E cell /0.0592
1.6.1.3 Advantages
It is very simple to construct.
It can be used for a long time without much attention.
Electrode potential is stable over a long period ( reproducibly).
It hash low temperature coefficient of emf.
As the mercury/ mercurous chloride interface is protected inside a tube It is less prone to
contamination.
1.6.1.4 Disadvantages
Calomel electrodes are not be used above 50oC as the mercurous chloride breaks down,
yielding unstable readings.
Calomel electrode should be used with proper precaution as mercury compounds are toxic.
1.7 Ion Selective Electrode.
The electrode which is sensitive to a specific ion present in an electrolyte whose potential depends
upon the activity of specific ion in the electrolyte is called ion selective electrode. The magnitude
of potential of this electrode is an indicator of the activity of the specific ion in the electrolyte.
Example for this type of electrode is glass electrode.

1.7.1 Glass electrode:

Construction

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 Figure 1. 9 Schematic diagram of aglass electrode.

The electrode consists of a thin glass membrane, typically about 0.03 to 0.1 mm thick, sealed onto
one end of a heavywalled glass tube. A special variety of glass (corning 0l5 glass with
approximate composition 20 % Na2O, 6 % CaO & 72 % SiO2) is used which has low melting point
and high electrical resistance. The glass bulb is filled with a solution of constant pH (0.1 M HCl).
Ag/ AgCl reference electrode . The internal reference electrode is a part of the glass electrode and it
is not the pH sensing element. Only the potential that occurs between the outer surface of the glass
bulb and the test solution responds to pH changes. The above figure 1. 9 is a schematic diagram of a
glass electrode.

1.7.2 Working: A silicate glass used for membranes consists of an infinite 3D- network of SiO44-
groups in which each silicon is bonded to four oxygen and each oxygen is shared by two silicons.
The negative charge of the silicate groups are balanced by sufficient cations. Within the membrane
singly charged cations such as sodium and lithium are mobile in the lattice and are responsible for
electrical conduction. The glass is a partially hydrated aluminosilicate containing sodium or calcium
ions. As the divalent cations are too strongly held within the silicate structure they cannot exchange
with ions in the solution. Hence 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. . The ion-exchange reaction can be written as

H+ + Na+ Na+ + H+
Solution glass solution glass

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The Na+ ions on the glass membrane are exchanged for H+ ions in the solution. The potential of the
electrode is controlled by the difference between the hydrogen ion concentration inside and outside
the thin glass membrane. Since the H+ ion concentration inside the electrode is constant, the
electrodes potential varies only with the concentration of H+ in the solution outside. Thus the
potential arises from the difference in positions of ion-exchange equilibrium on each of the two
surfaces. This charge difference or potential serves as the analytical parameter when the pH of the
solution on one side of the membrane is held constant. Evidently the selectivity of glass electrodes is
related both to the ability of the various monovalent cations to penetrate into the glass membrane and
to the degree of attraction of the cations to the negative sites within the glass.

1.7.3 Electrode Potential of GE

The overall potential of the glass electrode has three components; 1) The boundary potential Eb,
which varies with the pH of the analyte solution.
Eb = E1-E2 (1)
Where Eb is the boundary potential
E1 = potential developed at the interface between the exterior of the glass and the
analyte solution
E2 = Potential developed at the interface between the internal solution and the interior
of the glass. The boundary potential is related to the concentration of hydrogen
ion in each of the solution by the Nernst-like equation.
Eb = E1 E2 = RT/nF(lnC2- lnC1) (2)
Where C1 = concentration of the analyte solution
C2 = concentration of the internal solution
In a glass electrode the hydrogen ion concentration of the internal solution is held constant.
So eqn. (2) becomes
Eb = K + 0.0592 log C1 (3) (Recall pH= -log [H+]
Eb = K - 0.0592 log pH where K= -.0592 log C2
The boundary potential is then a measure of the hydrogen ion concentration of the external solution.

2) The potential of the internal Ag/AgCl reference electrode. E Ag/AgCl.

3) Eb is not equal to zero even if E1 = E2. This is a small unpredictable contribution called the
asymmetry potential, E asym. The sources of the asymmetry potential include the following.

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 a. Differing conditions of strain in the two glass surface during
manufacture

b. Mechanical abrasion on the on the outer surface during use

c. Chemical etching of the outer surface during use.
The asymmetry potential changes slowly with time. The glass electrode potential can be written in
the equation form as
EG = Eb + EAg/ AgCl + E asym (4)

Substitution of eqn (3) for Eb, gives

EG = K + 0.0592 log C1 + EAg/AgCl + E asym

= K 0.0592 log pH + E Ag/AgCl + E asym (5)

EG = EoG 0.0592 pH (6)
where EoG = K + EAg/AgCl + E asym. a combination of three constant terms = constant .To measure
the hydrogen ion concentration of the test solution, the glass electrode (indicator electrode) must
be combined with an external reference electrode, which is required for all kinds of ion-selective
electrode determinations.

1.7.4 Applications: Determination of pH:

The glass electrode has an emf that changes with hydrogen ion concentration, i.e the glass electrode
is the most important indicator electrode for hydrogen ion. It is used for the measurement of pH
under many conditions and normally calomel electrode is used as reference electrode to complete the
cell . Figure1.10 represents the Cell: SCE / Test solution / GE

Figure 1.10 Set up of indicator electrode and reference electrode for the measurement of pH.

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E cell = E glass E calomel where E glass = the electrode potential of glass electrode.
E calomel = the E.P. of the SCE
E cell = EoG 0.0592 pH 0.2422
The EoG value of a glass electrode can be determined by dipping the glass electrode in a solution of
known pH.
Some Applications: Ion selective electrodes are used in determining
i) The concentrations of a number of cations such as H+, Li+, Ca2+, Ag+ etc and also
concentrations of anions such as F-, S2-, CN- and halide ions
ii) The pH of a solution using glass electrode
iii) The concentration of a gas using gas sensing electrodes

1.7.5 Advantages:
It can be used without interference in solutions containing strong oxidants, strong reductants,
proteins, viscous fluids and gases as the glass is chemically robust.
The glass electrode gives accurate results in the pH range 2 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, robust and easy to operate.
The equilibrium is reached quickly & the response is rapid.
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)
The glass electrode is easier to handle than the inconvenient hydrogen gas electrode.
Glass electrodes which are selective for Li+, Na+, Cs+, Ag+ and NH4+ ions are commercially
available and these special electrodes are useful for measuring the above ions.

1.7.6. Disadvantages:
The bulb of this electrode is very fragile and has to be used with great care. The sensitive tip
is easily scratched and ruined.
The measured pH values are low and thus the glass electrode gives erroneous results in
highly alkaline solutions. This alkaline error arises when solutions (having pH values in the
10-12 range or greater) are measured using glass electrode. In the presence of alkali ions, the
glass surface becomes responsive to both hydrogen and alkali ions.

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 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. It is better to determine EoG for a glass electrode before use.
The commercial version is moderately expensive.
Note that EoG depends on a particular glass electrode used & it is not a universal constant.

1.8 CONCENTRATION CELLS
If same electrodes are in contact with same electrolytic solutions of different concentrations,
they differ in their electrode potentials. The coupling of two such electrodes also constitutes a
cell and gives rise to an emf as the electrodes differ in their electrode potentials. Such cells
which consist of two electrode of the same substance in contact with solutions of different
concentrations and the emf arises due to the difference in concentrations are known as
concentration cells. It is represented in figure 1.11 given below. However, the magnitude of emf is
smaller (0.09 V) in concentration cells than in chemical cells (1-2 V).
M / Mn+ [C1] Mn+ [C2] / M
dilute concentrated
As a genereal rule, the negative half cell has the lower concentration of ion and the +ve half cell has
the higher concentration of ions.
e.g. pt / H2(g), H+ (C1) H+ (C2), H2 (g) / pt
Cu (s) / Cu2+ (M1) Cu2+ (M2) / Cu (s) Zn
(s) / Zn2+ (0.1M) Zn2+ (1.0 M) / Zn (s)
Construction:

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 Figure 1. 11 Schematic diagram of a concentration cell

In this concentration cell, two nickel electrodes are immersed in nickel sulfate solutions of
concentrations C1 and C2. The cell is represented as:
Ni2+[0.001 M] Ni/Ni 2+[1.0 M] / Ni
Working:
Anode: Ni (s) Ni2+[C1] + 2e
(Lower concentration reaction)

Cathode: Ni2+[C2] + 2e Ni (s)

(Higher concentration reaction)

Net reaction: Ni2+[C2] Ni2+[C1]

There is a change in concentration due to current flow. The higher concentration is reduced and the
lower concentration is increased. The equilibrium is attained when the two concentration are equal.
Emf of the concentration cell :

Ecell = Ecathode-Eanode
= {E0 + (2.303RT)logC2 }- {E0+(2.303RT)logC1}
nF nF
2.303RT C2
Ecell = log
nF C1
At 298 K,
Ecell = 0.0592/ n log [C2/C1]
The following conclusion can be drawn:
1. When the two solution are at the same concentrations log [C2/C1] = 0, No electricity flows
2. When [C2/C1] > 1, log [C2/C1] is positive and E is positive. Electrode in contact with lower
electrolyte concentration acts as anode and electrode in contact with higher electrolyte
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 concentration acts as cathode. When the cell is in operation, the concentration of ions at the
anode increases and that at cathode decreases.
3. The magnitude of cell potential depends on the ratio of the electrolytic concentration. Higher
the ratio higher is the emf. If [C2/C1] increases from 0.001 to 0.01 voltage doubles.
Numerical problems:
1. Zn/ZnSO4(0.001)||ZnSO4(x M)/Zn is 0.09V at 25C. Find the concentration of the
unknown solution.
Solution: Ecell = 0.0591/n log C2/C1
0.09 =(0.0591/2) 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 Solution: 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+
1.9. Summary: The nature of electrochemical process is introduced in this chapter from the most
basic concepts. It is very important to know the types of electrochemical cells, their representation
and working as electrochemistry has a vital role in electro refining, battery technology, corrosion
control and metal finishing. A brief description about the origin of single electrode potential, its
measurements and sign convention also discussed. We can measure the difference in potentials
which is a key concept in electrochemistry. The Nernst equation is derived for the electrode as well
as to the cell systems and its significance highlighted. Construction and working of calomel and glass
electrodes described to know the basic differences between reference and indicator electrodes. At the
end of the chapter the basic concepts of concentration cell, its construction and working are
described.

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