Module 1

Electrochemistry and Corrosion Science

(Electrochemical Cell- Electrode potential- Nernst equation for single electrode and cell (Numerical problems)-
Reference electrodes – SHE & Calomel electrode –Construction and Working - Electrochemical series - Applications –
Glass Electrode & pH Measurement-Conductivity- Measurement using Digital conductivity meter. Li-ion battery & H2-
O2 fuel cell (acid electrolyte only) construction and working.

Corrosion –Electrochemical corrosion mechanism (acidic & alkaline medium) - Galvanic series - Corrosion control
methods - Cathodic Protection - Sacrificial anodic protection and impressed current cathodic protection –Electroplating
of copper - Electroless plating of copper.)

Electrochemistry is the study of production of electricity from energy released during

spontaneous chemical reactions and the use of electrical energy to bring about non-spontaneous
chemical transformations. The subject is of importance both for theoretical and practical
considerations. A large number of metals, sodium hydroxide, chlorine, fluorine and many other
chemicals are produced by electrochemical methods. Batteries and fuel cells convert chemical
energy into electrical energy and are used on a large scale in various instruments and devices. The
reactions carried out electrochemically can be energy efficient and less polluting. Therefore, study
of electrochemistry is important for creating new technologies that are eco-friendly.

Electrochemical Cells
These are devices that convert chemical energy of some redox reactions to electrical
energy. They are also called Galvanic cells or Voltaic cells. In this device the Gibbs energy of the
spontaneous redox reaction is converted into electrical work. An example for Galvanic cell is Daniel
cell. It is constructed by dipping a Zn rod in ZnSO4 solution and a Cu rod in CuSO4 solution. The two
solutions are connected externally by a metallic wire through a voltmeter and internally by a salt
bridge.
A salt bridge is a U-tube containing an inert electrolyte like NaNO3 or KNO3 in a jelly like
substance. The functions of a salt bridge are:
1. To complete the electrical circuit
2. To maintain the electrical neutrality in the two half cells.
3. To prevent intermixing of solutions.
4. To eliminate liquid junction potential.
The reaction taking place in a Daniel cell is
Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
This reaction is a combination of two half reactions:
(i) Cu2+ + 2 e- → Cu(s) (reduction half reaction)
(ii) Zn(s) → Zn2+ + 2 e- (oxidation half reaction)
These reactions occur in two different portions of the Daniel cell. The reduction half
reaction occurs on the copper electrode while the oxidation half reaction occurs on the zinc
electrode. These two portions of the cell are also called half-cells or redox couples. The copper
electrode may be called the reduction half-cell and the zinc electrode, the oxidation half-cell. It
has an electrical potential equal to 1.1 V when concentration of Zn2+ and Cu2+ ions is unity (1 mol
dm-3). If an external opposite potential is applied [Fig(a)] and increased slowly, we find that the
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reaction continues to take place till the opposing voltage reaches the value 1.1 V [Fig(b)] when, the
reaction stops altogether and no current flows through the cell. Any further increase in the external
potential again starts the reaction but in the opposite direction [Fig.(c)]. It now functions as an
electrolytic cell, a device for using electrical energy to carry non-spontaneous chemical reactions.

Difference between electrolytic and electrochemical cell

Sl. No Electrochemical Cell Electrolytic Cell
1. It is a device to convert chemical energy It is a device to convert electrical energy
to electrical energy. to chemical energy.
2. The redox reactions occurring at the The redox reactions occurring at the
electrodes are spontaneous. electrodes are non-spontaneous and
these reactions takes place only when
electrical energy is supplied.

3. The electrodes are of dissimilar types. The electrodes may be dissimilar or of

same metal
4. Each electrode is dipped in its own ions Both the electrodes are inserted in the
and both have separate compartments same electrolyte solution

5. The electrolytes are connected by salt No salt bridge is used

bridge

6. Anode is negative and cathode is positive. Anode is positive and cathode is negative.
The reaction at anode is oxidation and The reaction at anode is oxidation and
that at cathode is reduction. that at cathode is reduction.

7. Electrons are supplied by the species The external battery supplies the
getting oxidised. They move from anode electrons. They enter through the
to cathode in the external circuit cathode and come out through the
anode.

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Reversible and Irreversible Cells

When a cell work in a thermodynamically reversible manner it is called reversible cell. A cell
is said to work reversibility when it is sending out infinitesimally small current so that the reaction
of the cell remains virtually in a state of equilibrium. A reversible cell will have to satisfy the
following conditions:
a. If an emf exactly equal to the cell emf is applied from an external source, the cell reaction
will stop and hence no current will be given out.
b. When an opposing emf greater than the cell is applied, the reaction is reversed.
c. If the external emf is less than that of the cell, current will flow through the cell.

Electrode Potential
When a metal rod is dipped in its own salt solution, there is a tendency of metal ions from
the solution to deposit on the metal electrode. At the same time, metal atoms of the electrode
have a tendency to go into the solution as ions. This tendency of a metal to lose or gain electron
when it is in contact with its own solution is called electrode potential. When the concentrations of
all the species involved in a half-cell is unity then the electrode potential is known as standard
electrode potential.
Mn+ + n e- → M(s) (reduction half reaction)
M(s) → Mn+ + n e- (oxidation half reaction)
According to IUPAC convention, standard reduction potential is taken as the standard
electrode potential.
In a galvanic cell, the half-cell in which oxidation takes place is called anode and it has a negative
potential. The other half-cell in which reduction takes place is called cathode and it has a positive
potential. In a cell, the electrons flow from negative electrode to positive electrode and the current
flows in opposite direction. The potential difference between the two electrodes of a galvanic cell
is called the cell potential and is measured in volts(V). The cell potential is the difference between
the electrode potentials (reduction potentials) of the cathode and anode. The electromotive force
(emf) of the cell is the potential difference between the two electrodes, when no current flows
through the cell.
• By convention, while representing a galvanic cell, the anode is written on the left side and the
cathode on the right side.
• Metal and electrolyte solution are separated by putting a vertical line and a salt bridge is denoted
by putting a double vertical line.
• For Daniel cell, the cell representation is
Zn(s)|Zn2+(aq)||Cu2+(aq)|Cu(s)
• Under this convention the emf of the cell is positive and is given by the potential of the half-cell on
the right-hand side minus the potential of the half-cell on the left-hand side
i.e. Ecell = Eright – Eleft

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Helmholtz Electrical Double Layer

When a metal rod is dipped in its own salt solution, it may
undergo oxidation or reduction. Because of this, negative or positive
charge is developed on the metal, which attracts positively or negatively
charged free ions in the solution. This leads to the formation of a layer
of negative or positive ions around metal electrodes. Thus, a dynamic
equilibrium is established between the +ve/-ve charges at the
electrodes. Therefore, due to the interaction of opposite charges at the
respective electrodes, +ve/-ve ions remain close to the metal surface.
This charged layer around an electrode is called Helmholtz Electrical
Double Layer. Because of its formation, a potential difference exists
between the metal and its ionic solution. This potential difference will
persist as long as the charge is allowed to remain on the metal. This
potential difference becomes constant at equilibrium and is known as Helmholtz Electrical Double
electrode potential of a metal. Layer

Single electrode potential can be defined as the equilibrium potential difference exists at
the interface between the metal electrode(M) and its ionic solution (Mn+), when it is in contact with
a solution of its own ions. It depends on:
a. Nature of the metal, M
b. Concentration of the metal ions, Mn+
c. Temperature
The constant potential difference developed when a metal is in contact with its own salt
solution of concentration 1 M at 250C is called the standard electrode potential of the metal.

Nernst Equation
The relationship between the electrode potential and the concentration of the electrolyte
solution is given by Nernst Equation. We have assumed in the previous section that the
concentration of all the species involved in the electrode reaction is unity. This need not be always
true.
Consider a general reduction reaction,
Mn+(aq) + ne–→ M(s)
The decrease in free energy, ΔG accompanying this process is given by the well-known
thermodynamic equation (Vant Hoff’s Equation).
ΔG = ΔG0 + RT lnQ, (1)
where Q is called the reaction quotient, which is the ratio of activities of products to the reactants
in a non-equilibrium situation. (At equilibrium, ΔG = 0 and Q = K)
In a reversible cell, electrical energy is produced at the expense of decrease in free energy, and free
energy is related to EMF of the cell by the equation,
ΔG = - nFE (2)
Substituting equation (2) in (1)

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-nFE = -nFE0 + RTlnQ

Dividing by -nF,
𝑅𝑇
E = E0 - 𝑛𝐹 lnQ (3)

Substituting the values of constants at the temperature, T = 298K, R =8.314 JK–1mol–1 (Gas Constant)
and F =96500 C mol–1 (Faraday constant), and converting ln to log10
8.314 𝑥 298 𝑥 2.303
E = E0 - logQ
𝑛 𝑥 96500
0.0591
E = E0 - logQ (4)
𝑛

Equations 3 and 4 are the different forms of Nernst Equation.

Nernst Equation for single electrode
For a single electrode reaction,
Mn+(aq) + ne–→ M(s)
[𝑀]
reaction quotient Q can be written as 𝑄 = [𝑀𝑛+ ][𝑒]𝑛

In dilute solution, activities are replaced by molar concentration, also concentration terms [e] is
taken as one and for pure solid [M] is also taken as one. Therefore, Q becomes
1
𝑄=
[𝑀𝑛+ ]
Substituting in equation 4,
0.0591 1
E = E0 - log[𝑀𝑛+] (5)
𝑛

Nernst Equation for complete cell

For a cell reaction, aA + bB → cC + dD, reaction quotient Q can be written as
[𝐶]𝑐 [𝐷]𝑑
𝑄=
[𝐴]𝑎 [𝐵]𝑏
Substituting in equation 4,
0.0591 [𝐶]𝑐 [𝐷]𝑑
E = E0 - log[𝐴]𝑎[𝐵]𝑏 (6)
𝑛

For Daniel Cell,

Zn(s) + Cu2+(aq) → Zn2+(aq) + Cu(s)
[𝑍𝑛2+ ][𝐶𝑢]
𝑄=
[𝑍𝑛][𝐶𝑢2+ ]
Here concentration of pure solids is taken as one, hence
[𝑍𝑛2+ ]
𝑄=
[𝐶𝑢2+ ]

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Substituting in equation 6,
0.0591 [𝑍𝑛2+ ]
Ecell = E0cell - log [𝐶𝑢2+]
𝑛

Variation of EMF with Temperature

Consider the Daniel cell reaction, Zn(s) + Cu2+→ Cu(s) + Zn2+,
Nernst equation is given as,
𝑜 2.303𝑅𝑇 [𝑍𝑛2+ ]
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log[𝐶𝑢2+ ]
𝑛𝐹

Case I: When [Zn2+] = [Cu2+], logarithmic term becomes zero. Then Ecell = Eocell & EMF of the cell is
independent of temperature.
Case II: When [Zn2+] > [Cu2+], logarithmic term becomes negative. Then Ecell < Eocell & EMF of the cell
decreases with rise in temperature.
Case III: When [Zn2+] < [Cu2+], logarithmic term becomes positive. Then Ecell >Eocell & emf of the cell
increases with rise in temperature.
Applications of Nernst Equation:
a. It can be used to study the effect of electrolytic concentration on electrode potential.
b. It can be used for the calculation of the potential of a cell under non-standard conditions.
c. The unknown concentration of one of the ionic species in a cell can be determined with the
help of Nernst equation, provided that E0cell and concentration of other ionic species are
known.
d. The pH of a solution can be calculated.
e. Can be used for finding the valency of an ion or the number of electrons involved in the
electrode reaction.
f. Solubility of sparingly soluble salt at any temperature can be determined.

Standard Hydrogen Electrode (SHE) or Normal Hydrogen Electrode

• It is an example of a gas electrode.
• It consists of a platinum electrode coated with platinum black.
• The electrode is dipped in an acidic solution of one molar concentration and pure hydrogen
gas at 1 bar pressure and 298K is bubbled through it.
• It is represented as Pt(s)|H2(g)|H+(aq)
• By convention, the electrode potential of SHE is taken as
zero.
• It is a reversible electrode; can act as anode and cathode
depending on the potential of the electrode to which it is
coupled.
If the potential of the coupled electrode is -ve (< 0),
reduction reaction takes place in the SHE and it acts as cathode.
Eg. Zn, Mg, Li etc.

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H+(aq) + e– → ½ H2(g)
If the potential of the coupled electrode is +ve (> 0), oxidation reaction takes place in the
SHE and it acts as anode. Eg. Cu, Ag, F2 etc.
½ H2(g) → H+ + e-
Limitations of SHE
a. It is very difficult to set up SHE.
b. Difficult to maintain pressure of hydrogen at 1 atm and concentration of acid at 1M.
c. Cannot be used in solutions containing redox systems.
d. It requires considerable volume of solution.
e. It is readily affected by Hg, As, S etc and oxidising agents like Fe3+, Mn4+, Cr2O72- etc and cannot
be used in solutions containing these ions.

Measurement of Electrode Potential

The potential of individual half-cell cannot be measured. We can measure only the difference
between the two half-cell potentials that gives the emf of the cell. For this purpose, primary
reference electrode, standard hydrogen electrode (SHE) is used.
To determine the electrode potential of an electrode, it is connected in series with the standard
hydrogen electrode and the emf of the resulting cell is determined by the equation,
Ecell = ER – EL
Since the electrode potential of SHE is zero, the value of Ecell is equal to the electrode potential of
the given electrode. If the standard electrode potential of an electrode is greater than zero (i.e.,
+ve), then its reduced form is more stable compared to hydrogen gas. Similarly, if the standard
electrode potential is negative then hydrogen gas is more stable than the reduced form of the
species.
The -ve or +ve values for standard electrode(reduction) potential is obtained depending on
whether the half-cell acts as anode or cathode with respect to SHE. Eg. Zn electrode has -ve value
since the electrode acts as anode with respect to SHE.

Electrochemical series
It is a series in which various electrodes are arranged in the decreasing order of their
reduction potential. In this table, fluorine is at the top indicating that fluorine gas (F 2) has the
maximum tendency to get reduced to fluoride ions (F–). Therefore, fluorine gas is the strongest
oxidising agent and fluoride ion is the weakest reducing agent. Lithium has the lowest electrode
potential indicating that lithium ion is the weakest oxidising agent while lithium metal is the most
powerful reducing agent in an aqueous solution.
Applications:
1. Reactivity of metals: Electrodes having negative values of standard electrode potential with
respect to hydrogen have a tendency to undergo oxidation whereas electrodes having positive
values have a tendency to undergo reduction in aqueous solution.

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2. Displacement reactions: To predict whether a given metal will displace another from its salt
solution. A metal with lower E0 will displace metal with higher E0 from its salt solution. Eg. Zn
will replace Cu from CuSO4 solution.
a. Metals with negative reduction potential can displace hydrogen from acids. Eg. Fe, Zn, Al etc.
can liberate H2 gas from acids.
b. Non-metal having higher reduction potential can displace a non-metal having lower reduction
potential.
2NaCl + F2 → NaF +Cl2
F2 + 2e- → 2F-; E0 = +2.87V
Cl2 + 2e- → 2Cl-; E0 = +1.36V
3. Determines the standard emf of a cell: Standard emf of cells can be calculated from the
standard electrode potentials.
4. Spontaneity of redox reactions: The spontaneity of a chemical reaction can be judged based
on the standard reduction potential. Eg. If we add potassium dichromate to acidified mixture
of ferric chloride and potassium iodide, the oxidation of I- to I2 takes place first than oxidation
of Fe2+ to Fe3+. The reaction having more cell emf is more spontaneous
Cr2O72- + 14H+ + 6 e- → 2 Cr3+ + 7 H2O; E0 = +1.33V
Fe3+ + e- → Fe2+; E0 = +0.77V
I2 + 2e- → 2I-; E0= +0.54V
5. Analysis of products of electrolysis: It can be analysed by taking the cell emf which has less -
ve value. Eg. If we electrolyse a mixture aqueous solution of KCl and KI using Pt electrodes, H2
is liberated at cathode (-ve) and I2 is liberated at anode(+ve).
6. Decomposition potential: Decomposition potential of water can be calculated from the
electrochemical series. Water can be split into hydrogen and oxygen just by applying 1.23V.
O2 + 4H+ + 4e- → 2H2O (1M acid medium); E0 = +1.23V
2H+ + 2e- → H2 (1M acid medium); E0 = 0

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Electrochemical Series

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Secondary Reference Electrodes

1.Calomal Electrode
Calomel electrode is an example of metal – metal insoluble metal salt electrode and a
solution of its common ion (mercury-mercurous chloride electrode, KCl.)
Construction
It consists of a glass tube at the bottom of which, a small amount of Hg is placed. This is
covered with a paste of solid mercurous chloride (HgCl2 or calomel) which is further in contact with
a solution of KCl.
A Pt wire dipped into the Hg layer is used for making electrical contact. The side tube is used for
making electrical contact with a salt bridge. The electrode may be represented as Hg/Hg2Cl2(s)/KCl.
The electrode reaction is given by:
Hg2Cl2 + 2e- → 2Hg(l) + 2Cl-; E0 = 0.2810 V
The calomel electrode can act as anode or cathode depending on
the electrode potential of the coupled electrode. If the electrode
potential of the coupled electrode is lower than the calomel
electrode, then calomel electrode undergoes reduction and act
as cathode.
If the electrode potential of the coupled electrode is greater than
the calomel electrode, then calomel electrode undergoes oxidation and act as anode and the
reverse of the above reaction takes place.
The anode and cathode reactions are as follows
Anode: 2Hg → 2Hg+ + 2e- Cathode: Hg2Cl2 → 2Hg+ + 2Cl-
2Hg+ + 2Cl- → Hg2Cl2 2Hg+ + 2e- → 2Hg
Net Reaction
2Hg + 2Cl- → Hg2Cl2 + 2e- Hg2Cl2 + 2e- → 2Hg + 2Cl-
The Nernst equation of this electrode at 250C is given by
0.0591
Ecal = E0cal - log [Cl-]2
2

= E0cal – 0.0591 log [Cl-]

Thus, the potential of the calomel electrode varies with the concentration of the concentration of
KCl solution as shown in the Table below. Normally a saturated KCl solution is used since the emf
will not vary with chemical reaction and it is also easy to set up.

0.1 N 1N Saturated
KCl concentration
(DNCE) (NCE) (SCE)

Electrode potential (Volts) 0.3335 0.2810 0.2422

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Determination of electrode potential using calomel electrode

In order to measure the electrode potential of an electrode, (Zn
electrode) it is coupled with SCE using a digital volt meter.
The volt meter reading will give the cell emf.
The reduction potential of SCE is 0.2422V is higher than the
reduction potential of Zn2+/Zn (-0.76V). Therefore, reduction
reaction takes place at SCE.
Hg2Cl2 + 2e- →2Hg + 2Cl-
Zn → Zn2+ + 2e-
The resultant cell can be represented as
Zn/Zn2+||KCl(sat)/Hg2Cl2(s)/Hg(l)/Pt
Ecell = ER – EL
= Ecal – EZn/Zn2+
= 0.2422 - EZn/Zn2+
EZn/Zn2+ = 0.2422 - Ecell
Ecell can be read directly from volt meter.
Advantages of Calomel electrode
• It is very easy to set up.
• Cell potential measurements are reproducible and stable over a large period and doesn’t vary
with T.
• It is having least potential gradient with T
Disadvantages of calomel electrode
• It should not be used above 50oC because Hg2Cl2 breaks down, yielding an unstable reading.
• Toxicity of mercury
2. Glass electrode
Glass electrode is a secondary reference electrode. Corning 015 glass has been used for
making glass electrode. It is a special type of glass with low melting point and high electrical
conductivity. It consists of 72% SiO2, 6% CaO & 22% Na2O.
Construction
• It consists of a thin glass bulb in which Ag wire coated AgCl is used as an internal reference
electrode. It is then filled with 0.1N HCl solution. Ag|AgCl(S)|0.1N HCl|Glass
• Glass electrode works on the principle that potential difference between the surface of the glass
membrane and a solution is a linear function of PH.
• Here the glass membrane acts as an ion selective membrane sensitive to [H+].

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• So, an ion exchange reaction occurs between singly charged cations of glass (Na +) & H+ ions of
solution.
• Finally, an equilibrium is established between (Na+) ions of glass
& H+ ions of solution.
H+(solution) + Na+Gl- → Na+(solution) + H+Gl-
EG = E0G + 0.0591 log [H+] = E0G - 0.0591 PH
• The potential of glass electrode varies with concentration of H+ ions.
E0G is constant and it depends on the nature of the glass and also
the PH of the solution taken inside the glass bulb.
E0G= 0.6990 V
• The concentration of H+ ion inside the glass is constant, i.e. PH is
constant. But when it is dipped into a solution of unknown PH,
concentration of H+ ion inside the glass bulb changes. As a result, PH changes. This results in the
development of a potential difference.
Determination of PH using glass electrode
• Glass electrode is used as an internal reference electrode. In order to determine the unknown
PH of a solution, glass electrode is coupled with SCE and the resultant cell can be represented
like this,
Ag|AgCl(S)|0.1N HCl|Glass|Solution of Unknown PH||KCl (sat)|Hg2Cl2(s)|Hg(l)|Pt
• Ecell = ER - EL = ESCE - EG
= 0.2422 – (E0G - 0.0591 PH)
= 0.2422 – E0G + 0.0591 PH
• E0G of glass electrode can be determined by using
a solution of known PH.
• 0.0591 PH = Ecell + E0G – 0.2422
𝐸𝑐𝑒𝑙𝑙 +𝐸𝐺0 −0.2422
PH = 0.0591

Advantages of glass electrode

• It is very simple to operate.
• It can be used to find the PH of oxidizing, reducing and even colored solutions.
• Glass electrode works effectively in the PH range of 1-9 and is unaffected by oxidizing,
reducing and poisoning agents.
• Electrodes made of special glasses can be used up to a PH of 12.
Drawbacks of glass electrode
• It cannot be used as a reference electrode for solutions having PH greater than 12.

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• Glass membrane has very high resistance. So ordinary potentiometers cannot be used for
determining potential of electrode instead special electronic potentiometers has to be
used.

Fundamentals for the measurement of conductivity

• Ohm’s law:
It states that current passing through the conductor is directly proportional to the potential
difference.
IαV
V = IR
• Resistance:
It is the measure of obstruction to the flow of current. Its unit is Ω
R α l and R α 1/A
𝑙
R=ρx𝐴

• Conductance:
It is the reciprocal of resistance.
C= 1/R
• Specific Resistance (Resistivity):
It is the resistance of a conductor of unit length and unit area of cross section. Or it is the
resistance of unit volume of a conductor. Its unit is Ωcm
𝐴
ρ=Rx 𝑙

• Specific Conductance (Conductivity):

It is the reciprocal of resistivity. It is also defined as the conductance of unit length and unit
area of cross section of a conductor. Its unit is Scm-1
1 𝑙
𝜿=ρ=Cx𝐴

• Molar conductance:
Molar conductance is the conductance of a solution containing 1mol of an electrolyte which
is placed between two electrodes which are separated by unit distance. It is denoted by the
letter λm. Its unit is Scm-1mol-1.
1000𝜿
λm = 𝐶

Cell constant
• It is defined ratio of the distance between two electrodes (l) to area (A) of the electrodes. Unit
of cell constant is cm-1 or m-1.

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• Cell constant is determined experimentally by measuring the conductance of a 0.1 M solution

of KCl of known conductivity (specific conductance) .
• The conductivity of 0.1 M KCl solution is 0.01288 S cm-1
• Conductivity of a solution is measured using conductivity cell.
• Conductivity cell consists of two electrode plates coated with
finely divided platinum black, which are welded with the ends of
platinum wire that are sealed strongly, through two glass tubes.
• The tubes are strongly fixed such that distance between
electrodes remain unaltered
Measurement of Conductivity of a solution:
• Modified Wheatstone bridge is used for determining conductance and hence the conductivity
of solution.
• In this method, a conductivity cell containing the solution is made one arm of the wheat stone
bridge apparatus.
• The electrodes of the cell are made up of platinum
coated with platinum black.
• Then the conductivity cell is placed in a thermostat to
keep the temperature constant.
• In order to prevent electrolysis, an Alternating Current
is used.
• When current passes through the circuit, the resistors R2, R3 and R4 are so adjusted that a null
point is obtained in the detector.
• At null point,

• The reciprocal of this resistance will give the conductance of the solution.
• From the conductance we get the specific conductance of the solution. Since conductivity of the
𝑙
solution = C x 𝐴, where ‛l’ is the distance between the electrodes and ‛A’ is the area of cross
section of electrodes.
𝑙
• For a particular conductivity cell, 𝐴 is constant and is called cell constant

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Determination of conductance using digital conductivity meter

Contacting meters have conducting electrodes made of metal that are in direct contact with the
solution. The meter applies an alternating voltage to the electrodes, and the electric field created
in the solution causes the ions to move back and forth.
This creates a current between the two conductivity meter electrodes.
Another conductivity meter principle that must be taken into account
when using a conductivity meter is the temperature of the solution.
Conductivity is highly dependent on the temperature; therefore, you
must choose a temperature-compensated device. you
should calibrate the device to be the same temperature as the solution
under testing.

Secondary cell (Accumulators) (Storage cells)

Cells which can be recharged again and again by passing direct current through them. They can be
reused. So, they are called repeated action cells. They can store electrical energy in the form of
chemical energy. Hence, they are called storage cells (accumulators).
Lithium-ion cell
Lithium-ion cell is a secondary cell in which lithium ions
moves between cathode and anode during charging and
recharging.
In this cell, cathode is LiCoO2, anode is lithiated graphite &
electrolyte is an aprotic organic solution or a polymer that
can transport Li ions.
Anodic reaction: LiMO2 ⇌ Li(1-x)MO2 + xLi+ + xe-
Cathodic reaction: CG + xLi+ + xe- ⇌ LixCG
Overall reaction: LiMO2 + CG ⇌ Li(1-x)MO2 + LixCG
(Forward reaction is ‘charging’ and backward reaction is ‘discharging’)
Thus, there is the movement of lithium ions between the cathode and anode during charging and
recharging. The main electrochemical reaction in lithium-ion cell is the uptake of lithium ion at the
cathode and their release during discharging.
Cell representation is LixCG|LiX in PC-EC|Li(1-x)MO2, where LiX is lithium salt such as LiClO4, PC-EC is
a mixed poly propylene carbonate and ethylene carbonate solvent & M is a transition metal such
as Co, Mn or Ni.
Uses:
• It is used in lap tops.
• It is used in mobile phones.

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• It is used in iPods.
• It is used in MP3 players.

Hydrogen-Oxygen (H2-O2) Fuel Cell

A hydrogen-oxygen (H2-O2) fuel cell with an acid electrolyte is a type of proton exchange membrane
fuel cell (PEMFC).
Construction:
1. Anode: Hydrogen gas is supplied to the anode.
2. Cathode: Oxygen from the air is fed to the cathode.
3. Electrolyte: An acid electrolyte such as phosphoric acid or sulfuric acid serves as the proton
conductor.
4. Catalyst layers: The anode and cathode have catalyst layers that facilitate the electrochemical
reactions.
Principle:
The H2-O2 fuel cell operates based on the electrochemical reaction between hydrogen and oxygen
in the presence of an acidic electrolyte. At the anode, hydrogen molecules are split into protons
(H+) and electrons (e-). The protons pass through the electrolyte to reach the cathode while
electrons travel through an external circuit, generating electrical energy.
At the anode:
2H2(g) → 4H+(aq) + 4e-
This reaction involves the oxidation of
hydrogen gas to form protons and electrons.
At the cathode:
O2(g) + 4H+(aq) + 4e- → 2H2O(l)
This reaction involves the reduction of oxygen
gas using protons and electrons to form water.
Overall cell reaction:
2H2(g) + O2(g) → 2H2O(l)
The net result is that hydrogen gas and oxygen gas are reacted in a controlled manner to produce
water, while generating electricity through the movement of electrons from the anode to the
cathode.
Working:

• Hydrogen gas is supplied to the anode where it dissociates into protons and electrons.

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• Protons travel through the acid electrolyte to reach a cathodic compartment while electrons
flow externally producing electricity
• At the cathodic compartment, oxygen from air reacts with protons and electrons to form
water as a byproduct.
Applications:
- Portable electronic devices
- Backup power systems
- Automotive vehicles
Advantages:
- High efficiency
- Low emissions
- Quiet operation
- Suitable for various applications
Disadvantages:
- Costly catalysts such as platinum are required at electrodes
- Sensitivity to impurities in hydrogen fuel supply
This type of fuel cell offers promising potential in various fields due to its efficiency and clean energy
generation capabilities but requires further advancements particularly related to cost reduction
before widespread adoption can occur.

Corrosion Science
Corrosion is the slow process of deterioration or destruction of the metal through the
chemical or electrochemical changes taking place at its surface. Corrosion reactions are of two
types. On the basis of this, theories of corrosion are of two types.
I. Dry corrosion (Chemical corrosion)
Corrosion of this type gases occurs by the direct chemical attack of atmospheric gases on the metal
in the absence of moisture. They are of three types.
1. Oxidation corrosion
2. Corrosion by other gases
3. Liquid metal corrosion
II. Electrochemical corrosion or wet corrosion:
Takes place under moist conditions through the formation of Galvanic cells. This type of corrosion
involves
1. Anodic oxidation

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2. Cathodic reduction
3. Diffusion of metallic and nonmetallic ions towards each other
4. Formation of separate anodic and cathodic areas due to the deposition of products between
which current flows through the conducting medium.
This mechanism can be outlined in the following four aspects.
1. Hydrogen evolution corrosion in acid medium
This occurs when metals are in contact with acid solution in absence of sufficient oxygen. Eg: Fe or
Al in contact with HCl.
This is because hydrogen electrode potential in acid medium (E0H+/H2) = 0, is higher than electrode
potential in acid medium(E0Fe2+/Fe) = -0.44 V).
Here electrode with higher E0 value will be reduced and act as cathode.
The reactions involved in this type of corrosion are as follows
Anode: Fe → Fe2+ + 2e- E0 =-0.44V (1)
Cathode: 2H+ + 2e- → H2 E0H+/H2 = 0 (2)
Net Reaction: Fe + 2H+ →Fe2+ + H2 ; E0cell = 0—(-0.44) = 0.44V
Since corrosion cell potential is positive, this corrosion reaction is feasible.
2. Hydrogen evolution corrosion in alkaline medium
Corrosion of Fe will not take place when Fe is immersed in an alkaline medium because hydrogen
electrode potential in alkaline medium (E0H2/OH) = -0.82V), is lower than electrode potential of Fe
(E0 = -0.44 V, while metals like Al can give hydrogen evolution corrosion in alkaline medium also
because of the reason that electrode potential of hydrogen in alkaline medium (E0H2/OH = -0.82V) is
higher than Al (E0 =-1.66 V)
Anode: Al → Al3+ + 3e- E0Al3+/Al = -1.66 V (1)
Cathode: 2H2O +2e- → H2 + 2OH- ; E0H+/H2 =-0.828 (2)
0
E cell = -0.828 – (-1.66) = 0.832 V.
Since corrosion cell potential is positive, this corrosion reaction is feasible.
3. Oxygen absorption corrosion in acid medium

This occurs when metals are in contact with water having high dissolved oxygen in acidic or neutral
medium.
Anode: Fe → Fe2+ + 2e- E0 = -0.44 V
+ -
Cathode: O2 + 4H + 2e → 2 H2O E0 = 1.23 V

E0 for net cell reaction in acid medium is E0cell = Ecathode – EAnode = 1.23 – (-0.44) = 1.67 V
Fe2+ produced here is further oxidised to Fe3+ in acidic or neutral environment since oxygen
electrode potential is greater than E0Fe3+/Fe2+ = +0.77V.
Fe2+ → Fe3+ + 2e- E0 =+ 0.77 V

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Fe3+ formed here forms an insoluble precipitate of Fe(OH)3 called yellow rust. If the amount of
moisture is less, black rust, FeO.Fe2O3 (magnetite) is formed. This rust formation leads to intense
localised corrosion called pitting corrosion.

4. Oxygen absorption corrosion in alkaline medium

This type of corrosion occurs when metals are in contact with water having high dissolved oxygen
in alkaline medium
Anode: Fe → Fe2+ + 2e- E0 = -0.44 V
Cathode: O2 + 2H2O +4e- → 4OH- E0 = 0.40 V

E0 for Net cell reaction in acid medium is E0cell = Ecathode – EAnode = 0.40 – (0.44) = 0.84 V
Here Fe2+ thus produced cannot be further oxidized to Fe3+.
Because oxygen electrode potential in alkaline medium (E0(O2/OH) = 0.40 V) which is less than
E0(Fe3+/Fe2+) = 0.77 V .
Hence no insoluble precipitate of Fe(OH)3 is formed, and hence no localized corrosion.

Galvanic series
Galvanic series is a series in which the metals and alloys are arranged in the order of their corrosion
tendencies.
Comparison between Electrochemical series and Galvanic Series

Sl.No Electro chemical Series Galvanic series

Series in which various electrodes are Series in which the metals and alloys
1. arranged in the decreasing order of their are arranged in the order of their
reduction potential. corrosion tendencies.

E0 is measured for metals and non- E0 is measured for metals and alloys
2.
metals
E0 is measured by dipping pure metals in E0 is measured by dipping pure metals
3. and alloys in unpolluted seawater
their salt solutions of 1M concentration
E0 is measured by using standard E0 is measured by using calomel
4. hydrogen electrode as reference electrode as reference electrode
electrode
Position of the metal and alloy may
5. Position of the metal is fixed change

Predicts relative displacement Predicts relative corrosion tendencies

6.
tendencies
7. Alloys are not included Alloys are included

Cathodic Protection
In this method, the metal to be protected is made as cathode so that corrosion will not
occur. The following methods are employed for cathodic protection.

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1. Sacrificial anodic protection

• In this method, the metal to be protected is connected by
a wire to a more anodic or active metal. Then the more
active metal will undergo corrosion and the cathode
remains protected.
• Here the more active anodic metal sacrifices for the
protection of cathodic metal and is called sacrificial anode.
• Metals commonly used for this purpose are Mg, Zn, Al and
their alloys.

2. Impressed current cathode protection

• In this method an impressed current is applied in
opposite direction to nullify the corrosion current.
• As a result, corroding metal is converted from
anode to cathode.
• The impressed current required can be obtained
from a battery with an insoluble anode made of
graphite or high silica iron. This method is used for the protection of open water box coolers,
water tanks etc.
Comparison of sacrificial anode protection and impressed current cathodic protection

Sacrificial anode protection Impressed current cathodic protection

1. No external power supply is required. 1. External power supply is required.

2. Economical for short term protection. 2. More suitable for long term protection.
3. Investment is less. 3. High investment is required.
4. Requires periodical replacement of 4. Anodes are relatively stable and do not
anodic material. corrode.
5. Suitable when current requirements and 5. Suitable when current requirements
resistivity of the electrolyte are and resistivity of the electrolyte are
relatively low. relatively high.

Electroless plating (Autocatalytic plating)

• It is the method of depositing a metal from its salt solution on the catalytically active surface of
the metal to be plated using a suitable reducing agent without using electrical energy.
• In this process, metal piece to be plated is immersed in a mixture of reducing agent and a
complex compound.
• The reducing agent reduces metal ion into metal which gets plated over the catalytically active
surface of the metal to produce a thin uniform coating.
• This process is a controlled chemical reduction and is catalyzed by the metal or alloy being
deposited.

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• This method allows the easy preparation of films of low thickness using simple equipment.

Electroless Copper plating

In this method, article to be plated is immersed in a plating bath containing CuSO 4 (As a source of
Cu), formaldehyde (Reducing Agent), buffer solution of NaOH and Rochelle salt and a complexing
reagent like EDTA.
Air is bubbled slowly through the medium to control the formation of cuprous oxide. Electroless
plating of Cu takes place as follows.
Oxidation: 2HCHO + 4OH- → H2 (Gas) + 2HCOO- + 2H2O +2e-
Reduction: Cu2+ + 2e- → Cu
Net reaction: 2HCHO + 4OH- + Cu2+ → H2 (Gas) + 2HCOO- + 2H2O + Cu
Applications of electroless Cu plating
• Widely used for metalizing printed circuit boards.
• Used for plating on non-conductors.
• It is also used for making decorative plating on plastics.

Advantages
• This method produces even coatings.
• It does not use electrical power.
• This coating is having improved hardness, strength, ductility and resistance to corrosion.

Disadvantages
• The reducing agent, formaldehyde is a human health hazard.
• The instability of the electroless copper bath creates difficulties in process control.

Electroplating of Copper
Copper electroplating is the process of electroplating a layer of copper onto the surface of
a metal object. Copper is used both as a standalone coating and as an undercoat onto which other
metals are subsequently plated. The copper layer can be decorative, provide corrosion resistance,
increase electrical and thermal conductivity, or improve the adhesion of additional deposits to the
substrate.
Copper electroplating takes place in an electrolytic cell using electrolysis. Various steps in
the process are:

1. Preparation: The object to be plated must be thoroughly cleaned to remove any dirt, grease, or
oxides that could hinder adhesion.

2. Electrolyte solution: A copper sulphate solution serves as the electrolyte in the plating bath. It
also contains additives to improve the quality and appearance of the plated copper.

3. Anode and cathode: The object being plated acts as the cathode, while a pure copper anode is
used to provide a source of copper ions for plating.

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4. Electrical current: When an electrical current is applied between the anode and cathode, copper
atoms are dissolved at the anode (positive electrode) and deposited onto the cathode (negative
electrode), resulting in a thin layer of metallic copper on its surface. During copper electroplating,
the following reactions occur:

At the anode (copper metal):

Cu(s) → Cu2+(aq) + 2e-

This reaction involves the dissolution of solid copper metal into copper ions in the electrolyte
solution.

At the cathode (object being plated):

Cu2+(aq) + 2e- → Cu(s)

This reaction involves the reduction of copper ions from

the electrolyte onto the surface of the object being
plated, resulting in a thin layer of metallic copper.

Overall cell reaction:

Cu(s) → Cu2+(aq) + 2e- (anode)
2+ -
Cu (aq) + 2e → Cu(s) (cathode)
-------------------------------
Cu(s) → Cu(s)

The net result is that solid copper from the anode is dissolved and then redeposited on the cathode,
forming a thin layer of plated copper.

6. Post-treatment: After plating, rinsing and drying may be necessary for proper finishing.

Applications:

- Printed circuit boards

- Decorative items
- Automotive parts
- Metal finishing

Advantages:

- Enhanced electrical conductivity

- Corrosion resistance
- Improved aesthetics

Disadvantages:

- Environmental concerns related to disposal of waste solutions containing heavy metals such as
copper.

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