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MODULE 1 : ELECTRODE SYSTEM

Electrochemistry is a branch of physical chemistry which delas with (a) properties and
behaviors of electrolytes (b) interconversion of electrical and chemical energy. A system
which converts chemical energy into electrical energy is known as electrochemical cell. An
electrochemical cell is an arrangement consisting of two electrodes, and an electrolyte
connected externally by means of electric wire. Eg : Daniel Cell. Here zinc is anode where
oxidation reaction take place and copper is cathode where reduction take place.

At the anode: Zn → Zn2+ + 2e-

At the cathode: Cu2+ + 2e- → Cu

Net reaction: Zn(s)+ Cu2+(aq)→ Zn2+(aq)+ Cu(s)

A potential difference exists between anode and cathode. This is known as EMF of the
cell. It is given by Ecell = Ecathode − Eanode ( Considering reduction potentials)
Single electrode and Single electrode potential
One half of a galvanic cell where either oxidation half- reaction or the reduction-
reaction of the cell occurs is called a single electrode. A single electrode is an arrangement
where a metal electrode is immersed in a solution containing its own ions. A single electrode
develops a definite electric potential due to the spontaneous oxidation or reduction half-
reaction occurring at it. It is called single electrode potential
Potential developed at the interface of an electrode and electrolyte, when metal is
immersed in a solution containing its own ions (ions reversible to itself) is known as single
electrode potential. If measurements are done under standard condition of temperature (298 K)
pressure ( 1atm) and unit concentration of electrolyte is known as standard electrode potential.
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Evaluation if Single electrode potential:

Single electrode potential can be calculated using Nernst equation. Nernst equation is
an expression of a quantitative relationship between electrode potential/cell potential and
concentration of the electrolyte species in an electro-chemical reaction.

Mn+(aq) + ne- M(s)

E = Eo + 2.303RT/nF log [Mn+]

E= Electrode potential

E0= Standard electrode potential

R= Universal gas constant (joules per mol per 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
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 the Nernst equation for electrode potential at 298 K. From
these equations, it is clear that,
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i) If the concentration of the solution (Mn+) is increased, the electrode potential

increases and vice versa.
ii) If the temperature is increased, the electrode potential increases and vice versa.
Measurement of Single electrode potential:
It is not possible to determine experimentally the potential of a single electrode. What
can be measured is EMF of the cell by clubbing the electrode under consideration with an
electrode whose potential is known.
Electrode, whose potential is either arbitrarily fixed as zero, or whose potential is
exactly known is termed as reference electrode.
Reference electrodes
In order to measure the potential of any single electrode it should be combined with another
electrode of known potential to form a galvanic cell. The criteria for an electrode to act as a
reference electrode are;
1. The potential of that electrode should be known, under the condition of utility. It must
be reliable, stable, and reproducible.
2. The potential of the electrode should be of minimum variation with temperature.
Reference electrodes are the electrode with reference to those, the electrode potential of any
electrode can be measured

Types of reference electrodes.

1) Primary reference electrode: Standard hydrogen electrode (SHE) is the only primary
reference electrode. The potential of all other electrodes is measured with respect to the
hydrogen electrode. For all practical purpose, electrode potential of standard hydrogen
electrode is fixed as zero.
2) Secondary reference electrode: Due to the difficulties involved in the use of SHE as a
reference electrode, some other electrodes of constant electrode potential are referred
to as secondary reference electrodes. E.g., calomel electrode.
Calomel electrode :
Calomel electrode is an example for metal-metal insoluble salt electrode. Here mercury
is in contact with its sparingly soluble salt mercurous chloride. It is immersed in a solution
containing chloride ions ( KCl solution). 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.
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Construction and working of calomel electrode

Schematic diagram of calomel electrode.

It consists of a tube, in the bottom of which is a layer of mercury, over which is placed a
paste of mercury and mercury chloride. The remaining portion of container is filled with a
solution of normal or decinormal or saturated solution of 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 represented as Hg (l) /Hg2Cl2 (sat’d) /KCl-(sat’d/ xM)

The calomel electrode can act as anode or cathode depending on the nature of another
electrode with which it is contact with
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)
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The net reversible electrode reaction is,

Hg2Cl2(s) + 2e- 2 Hg (l) + 2 Cl-(aq)
After applying Nernst equation, electrode potential is given by
E = Eo – 2.303 RT log [Cl-]2
2F
= Eo - 0.0591 log [Cl-] at 298 K
Variation of electrode potential of calomel electrode with concentration of KCl

KCl concentration Electrode potential ( Volt)

0.1N 0.3335
1.0 N 0.2810
Saturated 0.2422

Applications:
(i) To determine the electrode potential of the unknown electrode
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)
The EMF of the so formed cell is determined experimentally by potentiometric method.
Then
E cell = E cathode – Eanode = 0.2444 – Ezn
Ezn = 0.2444 – E cell

(ii) To determine the pH of a solution cell:

Pt, H2(1atm) H+ (x) // Hg2Cl2(s) / Hg (l)
E cell = E cathode – E anode
= 0.242 – (− 0.0592 pH)
pH = E cell – 0.242/0.0592

Advantageous of calomel electrode:

(i) Simple in construction, easy to handle
(ii) Electrode potential remains constant over a period of time
(iii) Electrode potential is reproducible
(iv) Electrode potential does not vary with temperature
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Limitations of calomel electrode

(i) Mercury compounds are poisonous in nature
(ii) It can not be operated at higher temperature as the decomposition of Hg2Cl2 take
place
(iii)
Concentration Cell:

The galvanic cell in which t h e electrode and electrolytes present in both half cells
are the same but only the concentration of the electrolyte is different iscalled the electrolyte
concentration cell.

The above concentration cell can be represented as:

Zn| ZnSO4 (C1) || ZnSO4 (C2)| Zn

The electrode reactions are

At Anode: 𝑍𝑛 → 𝑍𝑛2+ (𝐶1 ) + 2𝑒

At Cathode:𝑍𝑛2+ (𝐶2 ) + 2𝑒 − → 𝑍𝑛

Overall reaction: 𝑍𝑛2+ (𝐶2 ) → 𝑍𝑛2+ (𝐶1 )

Where C1 and C2 are concentrations of ZnSO4 solution at anode and cathode

respectively & C2> C1
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑅 − 𝐸𝐿

0.0591 0.0591
= [𝐸 0 + 𝑙𝑜𝑔(𝐶2 )] − [𝐸 0 + 𝑙𝑜𝑔(𝐶1 )]
𝑛 𝑛
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Where E0 is the standard electrode potential of the species in the concentration cell.

0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔 ( )
𝑛 𝐶1

Note: Concentration cell will have positive EMF, only when C2 > C1

Cell will stop functioning when C2 = C1

Numerical problems

1. A concentration cell was constructed by immersing two silver electrodes in 0.02M and
2M AgNO3 solutions. Write the cell representation, cell reactions, and calculate the emf
of the cell at 250C.

(i)Cell representation:

Ag|AgNO3 (0.02 M) || AgNO3 (2M)|Ag

(ii) Electrode reactions:

At anode: Ag Ag+ (0.02M) + e¯

At cathode: Ag+ (2M) + e¯ Ag

NCR: Ag+ (2M) Ag+ (0.02M)

(iii)The emf of the concentration cell:

0.0591 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛 𝐶1

0.0591 2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
1 0.02

𝐸𝑐𝑒𝑙𝑙 = 0.0591 𝑙𝑜𝑔100

𝐸𝑐𝑒𝑙𝑙 = 0.0591 × 2

𝐸𝑐𝑒𝑙𝑙 = 0.1182𝑉

2. Represent the cell formed by the coupling of two Cu electrodes immersed in CuSO4
solutions. The concentration of cupric ions in one electrode system is 100 times more
concentrated than other. Write the cell reaction and calculate the potential at 300K.

(i)Cell representation:
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Cu|CuSO4 (1M )|| CuSO4 (100M)|Cu

(ii) Electrode reactions:

At anode: Cu Cu2+ (1M) + 2e¯

At cathode: Cu2+ (100M) + e¯ Cu

NCR: Cu2+ (100M) Cu2+ (1M)

(iii)The emf of the concentration cell:

2.303𝑅𝑇 𝐶2
𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
𝑛𝐹 𝐶1

2.303 × 8.314 × 300 100

𝐸𝑐𝑒𝑙𝑙 = 𝑙𝑜𝑔
2 × 96500 1

𝐸𝑐𝑒𝑙𝑙 = 0.0297 𝑙𝑜𝑔100

𝐸𝑐𝑒𝑙𝑙 = 0.0297 × 2

𝐸𝑐𝑒𝑙𝑙 = 0.0595𝑉

Ion Selective Electrode:

The electrode which is sensitive to a specific ion present in an electrolyte whose

potential depends upon the activity of a specific ion in the electrolyte is called an ion selective
electrode. The magnitude of the 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.

Glass electrode: Construction

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Schematic diagram of the Glass Line sketch of a glass membrane

electrode showing outer analyte solution
and internal reference solution.

Glass electrode consists of a thin glass membrane, typically about 0.03 to 0.1 mm thick,
sealed onto one end of a heavy–walled glass tube. A special variety of glass (corning 0l5 glass
with approximate composition 20 % Na2O, 6 % CaO & 72 % SiO2) is used which has a low
melting point and high electrical conductance.
The glass bulb is filled with a solution of constant pH (0.1 M HCl). A small volume of
saturated silver chloride is contained in the tube. A silver wire in this solution forms a
silver/silver chloride reference electrode which is connected to one of the terminals of a
potential measuring device. 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.
Glass electrode can be represented as follows:
Ag/AgCl, HCl ( 0.1M) // Glass (x=?)

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.
There are sufficient cations to balance the negative charge of the silicate groups within the
interstices of this structure. Singly charged cations such as sodium and lithium are mobile in
the lattice and are responsible for electrical conduction within the membrane. The glass is a
partially hydrated aluminosilicate containing sodium or calcium ions.
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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 process involves univalent cations exclusively because divalent cations are too
strongly held within the silicate structure to exchange with ions in the solution and hence
immobile. The ion-exchange reaction can be written as
H+ + Na+ Na+ + H+
Solution glass solution glass
The Na+ ions on the glass membrane are exchanged for H+ ions in the solution at the
hydrated layer. 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 electrode’s 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.
The surface exposed to the solution having the higher H+ concentration becomes
positive with respect to the other surface. 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.

Electrode potential of glass electrode

The overall potential of the glass electrode depends upon three parameters
The boundary potential Eb
The potential of the internal Ag/AgCl reference electrode. E Ag/AgCl.
A small unpredictable contribution called the asymmetry potential, E asym.

(1) The boundary potential Eb, : It varies with the pH of the analyte solution. It is made up
of two potentials, E1 & E2 which develop at the two surface of the glass membrane i.e. the
potential developed at the inner glass surface and the potential developed at the outer glass
surface.
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
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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 solutions by the Nernst-like equation.
Eb = E1 – E2 = 0.0592 log Cl / C2 (2)
Where C1 = concentration of the unknown solution
C2 = concentration of the internal / known solution
For a glass pH electrode the hydrogen ion concentration of the internal solution is held
constant.

Eb = K + 0.0592 log C1 (3) (Recall pH= -log [H+]

Eb = K − 0.0592 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) A small unpredictable contribution called the asymmetry potential, E asym.
The sources of the asymmetry potential include the following.
i) Differing conditions of strain in the two glass surfaces during
manufacture
ii) Mechanical abrasion on the on the outer surface during use
iii) 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 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.
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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
Cell: SCE / Test solution / GE

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

E cell = E glass – E calomel where

E glass = Electrode potential of the glass electrode.

E calomel = Electrode potential of the Saturated calomel electrode

E cell = EoG – 0.0592 pH – 0.2444

EoG – 0.2444 – Ecell

0.0592 pH =
0.0592
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The standard glass electrode (EoG) potential can be determined by dipping the glass
electrode in a solution of known pH.

Determination of pH is mainly required in clinical & food analysis, environmental

monitoring (industrial waste acidity of rain) and process control (fermentation, boiler
water, galvanization & precipitation)

Advantageous of glass electrode

(i) Simple and can be easily be used

(ii) Equilibrium is rapidly achieved
(iii) Results obtained are highly accurate
(iv) It is not easily poisoned

Limitations of glass electrode:

(i) Glass electrode must be immersed in distilled water, when it is not used
(ii) Standard glass electrode potential need to be determined frequently
(iii) Can not used in highly acidic and alkaline solution
(iv) Commercial versions are moderately expensive