Module 1

Electrochemistry and corrosion

1. Derive an expression connecting electrolyte concentration to
electrode potential (Nernst equation) (KTU MAY 2017)
 Derivation of Nernst’s equation
for single electrode potential
General reversible reaction

Vant Hoff’s reaction G = G0 + RT ln Q

isotherm
Reaction Quotient Q = [Products]/[Reactants] = [M] / [Mn+]

Electrical energy is produced at the expense of decrease in free

energy

Relation between Free energy and -G = n F E

EMF
Under standard conditions -G˚ = n F E˚

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 On substituting the values of K, G and G˚in Vant Hoff’s reaction isotherm

Dividing throughout by -nF, we have,

As [M] = 1,

Therefore, Nernst’s equation

Substituting, R = 8.314 JK-1mol-1, F=96500 C mol-1, T= 298 K (25 ˚C), the above
equation becomes

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2. Write electrode reaction and expression for the
electrode potential of following electrodes: i)
Metal-metal ion electrode ii) Gas electrode iii)
Metal-metal insoluble salt electrode iv) Redox
electrode. (KTU MAY 2016) and (KTU JAN 2017)
Metal-metal ion electrodes
Consists of a pure metal rod dipped in a solution of its own
metal ions.
Eg: 1. Zn electrode in which Zn rod dipped in Zn 2+ (ZnSO4) solution
2. Cu electrode in which Cu rod dipped in Cu 2+ (CuSO4) solution

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Metal-metal insoluble salt electrode
Consists of a metal coated with a paste of its insoluble metal salt and is in
contact with a solution containing a common ion with the insoluble salt
−
Electrode representation: 𝑋𝑎𝑞 /𝑀𝑋(𝑠) /𝑀(𝑠)
Electrode reaction: 𝑀𝑋(𝑠) + 𝑒 − −
M + 𝑋𝑎𝑞
2.303 𝑅𝑇
Electrode potential: 𝐸 = 𝐸𝑜 − 𝑙𝑜𝑔[𝑋 −]
𝑛𝐹

Eg: Calomel electrode (KCl/ Hg2Cl2 (s)/Hg)

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Gas electrode
In this type, the gas is passed through an inert electrode like
platinum which is immersed in a solution containing ions of gas.

Eg: Standard hydrogen electrode (SHE), Chlorine electrode

Electrode reaction: 2H+ + 2e- → H2 (g)

+
Electrode representation: 𝐻(1𝑀) / 𝐻2(1 𝑎𝑡𝑚) / Pt

2.303𝑅𝑇
Electrode potential: 𝐸 = 𝐸 𝑜 + log[𝐻+]2
2𝐹
2.303𝑅𝑇
i.e. 𝐸 = 𝐸 𝑜 + log[𝐻+]
𝐹

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Image courtesy: https://byjus.com/chemistry/standard-hydrogen-electrode/
Redox electrode
Consists of an inert electrode like Pt dipped in a solution
containing ions of same metal in 2 different oxidation states.

Eg: Platinum wire dipped in a solution containing Fe2+ and Fe3+

3+ 2+
Electrode representation: 𝐹𝑒(𝑐1)
, 𝐹𝑒(𝑐2) /Pt
Electrode reaction: Fe3+ + e– ⇌ Fe2+
𝑜 2.303 𝑅𝑇 [𝐹𝑒 3+ ]
Electrode potential: 𝐸 = 𝐸 + 𝑙𝑜𝑔
𝑛𝐹 [𝐹𝑒 2+ ]

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3. Draw a well labeled diagram of calomel electrode.
Write electrode reaction and representation of the
electrode. (KTU JAN 2016)
 CALOMEL ELECTRODE (MERCURY MERCUROUS CHLORIDE ELECTRODE)
Calomel electrode is used as a secondary reference electrode for potential measurements. It contains mercury, solid
mercurous chloride (calomel) and a solution of KCl.
Construction
▪ Calomel electrode consists of a long glass tube with two side
tubes.

▪ One of the side tubes is connected to salt bridge and the other
one is to add the solution of KCl.

▪ Bottom of the glass tube contains mercury in to which a

platinum wire is dipped.

▪ Mercury is covered with a paste of mercurous chloride

(calomel)

▪ The remaining portion is filled with KCl solution through one of

the side tubes.

▪ The platinum wire which is dipped in mercury is used for

Image courtesy: https://www.embibe.com/ask/question/the-standard-reduction-potential-of-a-calomel-half-cell-
external connection
 Working of Calomel electrode

As anode:

2 Hg + 2 Cl- → Hg2Cl2 + 2 e-

Electrode representation: Hg / Hg2Cl2 / KCl

As Cathode:

Hg2Cl2 + 2 e- → 2 Hg + 2 Cl-

Electrode representation: KCl / Hg2Cl2 / Hg 12

4. How will you employ the calomel electrode for the determination of
electrode potential of copper and zinc? (KTU DEC 2017)

Or the same question can be asked as

How the electrode potential of an electrode can be determined using calomel
electrode

The calomel electrode can act as cathode or anode , depending up on

the nature of other electrode with which it is coupled. Thus , it is a
reversible electrode.
 From the digital voltmeter, Ecell will be obtained

Ecell

If the unknown electrode is Cu, then SCE will be the anode and Cu electrode will be the cathode
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5. Describe the principle and working of glass
electrode. Give the standard representation. (KTU
APR 2018)
or

How is glass electrode constructed? What is its

use? (KTU MAY 2016)
Ion-selective electrode- glass electrode
Consists of a glass bulb of low melting point and high
conductivity. The composition of Na2 O in this glass
membrane is slightly more than ordinary glass. Inside this
glass bulb 0.1N HCl will be taken and a platinum wire or
an AgCl coated Ag wire will be immersed in it.
Glass membrane is selective to H+ ions in the solution.
There is also specialized ion sensitive glass electrodes
used for determination of lithium, sodium, and
ammonium ions.
Electrode representation of Glass electrode

Ag/AgCl/H+(0.1M) /glass

This electrode is dipped in a solution of

unknown pH to find the pH of the solution.
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Glass electrode
When 2 solutions of different pH are separated by a thin glass membrane,
an electric potential is developed on the surface of glass electrode.
H+ + Na+(glass) → Na+ + H+(glass)

The electrode potential of glass electrode varies with H+ according to the

equation,

EG =E˚G + 0.0591 log[H+] at 25˚C

EG =E˚G - 0.0591 pH
where E˚G is a constant which depends on the nature of the glass

H+ ion conc: (0.1N) inside the glass electrode is a constant. So when the
glass electrode is dipped in a solution of unknown pH the electrode
becomes sensitive only to the outside H+ ion conc: and produces a
corresponding potential.
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6. Explain the construction and working of Li ion
cell. (KTU JAN 2017)
Lithium-ion battery (Rechargeable secondary cell)

Anode- Layered graphite

intercalated with lithium atoms

Cathode- is a mixed metal oxide

such as LiCoO2, LiMnO2 , LiFePO4

Electrolyte- Lithium salt (such as

LiPF6, LiBF4 or LiClO4) in an organic
solvent such as ether.

A separator separates the anodic

and cathodic compartments.

Discharging
Anode
Lix C6→ 6C + xLi+ +xe-
Cathode
Li1-xCoO2 + xLi+ + xe- → LiCoO2
Li ions move from the anode to
cathode through the electrolyte
while the electrons flow through
the external circuit from anode to
cathode to produce power
Charging
Anode
LiCoO2 →Li1-xCoO2 + xLi+ + xe-
Cathode
6C + xLi+ +xe- → LiC6
An external voltage source pulls the
electrons from cathode through
external circuit to the anode and
cause Li+ ions to move from
cathode to anode by transport
through a liquid electrolyte
 Advantages Limitations
➢Lighter than other
rechargeable battery ➢Extremely sensitive to
➢Have no memory effect high temperature
➢Can handle hundreds of ➢Heat causes lithium-ion
charge/discharge cycles battery pack to degrade
➢Can form wide variety of much faster than they
shapes and sizes so as normally would
to efficiently fill the
available space in the ➢Expensive to
device they power manufacture
➢Contains no toxic metals
➢Low maintenance
battery

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Application
Ideal for portable devices such as notebook
computers
Small portable electronic devices such as watches,
camcorders, digital cameras, thermometers,
calculators etc

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7.Explain the mechanism of electrochemical
corrosion of iron in oxygen rich and oxygen
deficient acidic and basic environments.
Evolution of hydrogen
a. In acid medium:
When metals like Fe or Al are in contact with acidic solution in the absence of
sufficient oxygen, metal ions are produced due to oxidation at anodic area and
hydrogen is released at cathodic area.

At anode: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − ; 𝐸 0 = −0.44𝑉
At cathode: 2𝐻+ + 2𝑒 − → 𝐻2 ↑ ; 𝐸0 = 0𝑉
Net reaction: : 𝐹𝑒 + 2𝐻+ → 𝐹𝑒 2+ + 𝐻2 ↑
0
𝐸𝑐𝑒𝑙𝑙 = 0-(-0.44V) = +0.44V

In this type of corrosion, displacement of hydrogen from acidic solution by the metal takes place. So.
metals with negative reduction potential than hydrogen will be anodic and suffer corrosion.
Evolution of hydrogen

b. In alkaline medium:

The reaction occurring at cathodic area for the evolution of hydrogen in alkaline media is given below

BUT for Fe, this reaction will not take place

Absorption of oxygen
a. In acid medium:
This occurs when metals are in contact with water having
dissolved oxygen in acidic environment or even neutral
environment

At anode: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − ; 𝐸 0 = −0.44𝑉
At cathode: 1Τ2 𝑂2 + 2𝐻 + + 2𝑒 − → 𝐻2 𝑂 ; 𝐸 0 = 1.23𝑉
or, 𝑂2 + 4𝐻 + + 4𝑒 − → 2𝐻2 𝑂

Fe2+ produced will be further oxidized to Fe3+ in acidic or neutral environment in presence of
oxygen and water to form insoluble precipitate of Fe(OH)3 called yellow rust. If the amount of
moisture is less, the corrosion product is anhydrous magnetite, Fe3O4 and is known as black rust.

4Fe(𝑂𝐻)2 + 𝑂2 + 2𝐻2 O 4Fe(𝑂𝐻)3 or 𝐹𝑒2𝑂3 . 3 𝐻2 O (Rust)

This is because ,
𝐹𝑒 3+ + 𝑒 − → 𝐹𝑒 2+ ; 𝐸 0 = 0.77V which is less than the potential of the reaction occurring at
cathodic area.
Absorption of oxygen

b. In alkaline medium:
This occurs when metals are in contact with water having dissolved oxygen in
alkaline environment.

At anode: 𝐹𝑒 → 𝐹𝑒 2+ + 2𝑒 − ; 𝐸 0 = −0.44𝑉
At cathode: 1Τ2 𝑂2 + 𝐻2 𝑂 + 2𝑒 − → 2𝑂𝐻− ; 𝐸0 = 0.40𝑉

Fe2+ produced here cannot be further oxidised to Fe 3+ in alkaline

environments. This is because comparing the reactions

𝐹𝑒 3+ + 𝑒 − → 𝐹𝑒 2+ ; 𝐸0 = 0.77V and
1ൗ 𝑂 + 𝐻 𝑂 + 2𝑒 − → 2𝑂𝐻− ; 𝐸0 = 0.40𝑉
2 2 2
the electrode potential for the reduction reaction occurring at cathodic area is
0
less than that of 𝐸𝐹𝑒 3+ /𝐹𝑒 2+
8. Describe the methods of Cathodic protection.
(KTU JAN 2021)
• The process of preventing metallic structures from corrosion by forcing
them to behave as a cathode is known as Cathodic protection.There are
two methods:
1. Sacrificial anodic protection
• Metallic structure (Underground pipelines, cables, ship hulls etc)
to be protected is connected by a wire to a more anodic metal. The
structure is forced to become cathode and the more anodic metal
undergoes corrosion, which acts as the sacrificial anode. It is periodically
replaced.

• Metals like Mg, Zn and Al and their alloys are used as sacrificial anodes.
 2. Impressed current cathodic protection
In electrochemcical corrosion, current flows from anodic region to
Cathodic region constitute corrosion current. An impressed current is
applied in opposite direction to neutralize corrosion current. This
converts the corroding metal from anode to cathode. Impressed current
is derived from a direct source. e.g Battery.
A direct current from a DC source is applied to an anode (inert material
like graphite) which is buried inside the soil and to the corroding metal
structure to be protected.
A DC voltage is applied such that corrosion current become zero or
negative.
Ships docked in harbour are protected by this method.
9. Explain how electroless plating of copper and
nickel are carried out.

Electroless plating is defined as the deposition of a metal from its salt

solution on a catalytically active substrate using a suitable reducing
agent without the use of electrical energy.
Electroless plating is defined as the deposition of a metal from its salt
solution on a catalytically active substrate using a suitable reducing
agent without the use of electrical energy.

Electroless Nickel plating

• Metals like Al, Fe, Cu and alloys like brass are plated with nickel.
• Non-metallic metals like glass, plastic and quartz are pre treated with
SnCl2 in acid medium followed by treatment with PdCl2 solution.
• This pre-treated object is immersed in plating bath containing nickel
salt (NiCl2) and reducing agent like sodium hypophosphite for a
certain time and maintain a particular temperature so that following
reactions will occur and nickel gets coated over the object.
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Reactions
At Anode:

At Cathode:

Over all reaction

As H+ ions are released in the reaction, pH decreases. To maintain constant pH,

Buffer solutions (Sodium acetate) is used.

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Electroless copper plating
• It is used to deposit a layer of copper on a substrate without use of
electricity. Commonly used in printed circuit boards.
• The object is degreased by organic solvents followed by acid
treatment.
• This object is then immersed in plating bath containing cupric salt
(copper sulphate), reducing agents (HCHO), buffer (Rochelle salt
+NaOH) and complexing agent (EDTA)

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Reactions:

At Anode:

At Cathode:
Over all reactions (1)+(2)

Reducing agent used is Formaldehyde

pH maintained is above 12 using NaOH of concentration above 0.1 N 35