MODULE 3: CONCEPT OF ELECTROCHEMISTRY

Q.1) What is elctrochemistry?

The branch of chemistry that deals with the chemical changes produced by electricity and the
production of electricity by chemical changes is called Electrochemistry.

Q.2) Define Anode and Cathode.

Anode: It is defined as an electrode at which oxidation occurs as electrons are lost by some species.
Cathode: it is defined as an electrode at which reduction occurs as electrons are gained by some
species.

Q.3) Explain electrochemical cell.

1) In electrochemical cell, electrochemical reactions are studied. In this cell, two electronic
conductors dip into an electrolyte. The electronic conductor is metal or carbon rod. The electrolyte
is in the form of pure liquid or aqueous solution.
2) The electrochemical reactions are redox reactions and involve electron transfer from one
species to other. At one electrode, oxidation occurs and at other electrode, reduction occurs. The
sum of these oxidation and reduction half reactions is the net cell reaction.

Q.4) What are different types of cells?

There are two types of cells which are as follows:
1) Electrolytic cells:
An electrochemical cell in which a non-spontaneous redox reaction is forced to occur by passing
a direct current from an external source into the solution is called an electrolytic cell. These cells
involve conversion of electrical energy into chemical energy. They are used for decomposition of
water into hydrogen and oxygen,metal plating, purification of metals.
2) Voltaic or Galvanic cells:
An electrochemical cell in which a spontaneous chemical reaction produces electricity is called
voltaic cell or Galvanic cell. These cells involve conversion of chemical energy into electrical
energy. Ex: Dry cell, Fuel cell,etc.

a) Concentration cell:
A concentration cell is an electrochemical device that generates electrical energy when two same
metal is in contact with solution of ions at different concentration. b) Fuel cell:
A fuel cell is an electrochemical cell which converts chemical energy of a conventional fuel and
oxygen into electrical energy.

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Q.5) Define Electrolysis
It is defined as the process in which an electric current is used to bring about a chemical reaction
or a process in which electrical energy is converted into chemical energy.

Q. 6) Describe the electrolysis of molten sodium chloride using inert electrodes or Explain
the construction and working of electrolytic cell.

Principle:- In this process, there is conversion of electrical energy into chemical energy.
Construction:-
1.Fused NaCl is placed in a container.
2. Two graphite electrodes are dip in Fused NaCl and other end is connected to the battery.
3. Cathode is connected to the negative terminal of battery. Anode is connected to the positive
terminal of battery.
Diagram:-

Working:-
1. When the current is flowing, battery takes electron from anode and transfer them to the cathode.
2. Fused NaCl contains Na+ and Cl- ions. When current is flowing is flowing Cathode attracts Na+
ions and anode attracts Cl- ions.
3. As these particles are charged, their motion constitutes an electric current.
Reaction at cathodes
Na+(l) + e- Na(s)
Reaction at Anode
2Cl- (l) Cl2(g) + 2e-

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Net cell reactions
2Na+(l) ++ 2Cl- (l) 2Na(s) + Cl2(g)
Result Of electrolysis
1. A pale green Cl2 gas is released at Anode.
2. A molten Silvery-white Na forms at Cathode.

Q.7 Explain the construction and working of Galvanic Cell or (Daniel cell).
Principle
Daniel cell is primary galvanic cell, which is used to convert chemical energy into electrical energy.
Construction
1. It consist of two separate half cells.
2. One half cell is a beaker containing a strip of metallic zinc immersed in aqueous solution of zinc
sulphate (ZnSO4). Second half cell is a beaker containing a strip of metallic copper immersed
in aqueous solution of Copper sulphate (CuSO4).
3. Two electrode are connected externally by metallic wire.

Diagram

Working:-
1. Reaction at anode
Oxidation of Zn to Zn+2 occurs at anode. Electrons on Zn strip are transferred from Zn to Cu
electrode whereas Zn+2 ions go into solution.
Zn(s) Zn+2 + 2e-

2. Reaction at Cathode
The electrons from Anode reduces Cu+2 ions Cu metal which deposits on cathode.

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Cu+2 + 2e- Cu (s)
Net Cell Reaction
Zn(s) + Cu+2 Zn+2 + Cu (s)

Result
The potential of the cell is 1.1 V

Q.8 Explain the construction and working of Concentration cell.

Principle: A concentration cell is an electrochemical device that generates electrical energy when
two same metal is in contact with solution of ions at different concentration.
Construction:
1. It consist of two separate half cells.
2. One half cell is a beaker containing a strip of metallic copper immersed in aqueous solution of
copper sulphate (concentration 0.01M). Second half cell is a beaker containing a strip of metallic
copper immersed in aqueous solution of Copper sulphate (concentration 1M).
3. Two electrode are connected externally by metallic wire.

Diagram

Working
1. As a result of difference in the concentration of solution, metal which is exposed to less
concentrated solution act as anode and other metal part act as cathode
1. Reaction at anode
Oxidation of Cu to Cu+2 occurs at anode. Electrons on Cu strip are transferred Other electrode
whereas Cu+2 ions go into solution.
Cu(s) Cu+2 + 2e-

2. Reaction at Cathode

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The electrons from Anode reduces Cu+2 ions Cu metal which deposits on cathode.
Cu+2 + 2e- Cu (s)

Net Cell Reaction

Cu(s) + Cu+2 Cu+2 + Cu (s)
Q.9 Explain the construction and working of fuel cell.

Fuel cells
• A fuel cell is an electrochemical cell which converts chemical energy of a conventional
fuel and oxygen into electrical energy.
• The essentials process in fuel cell is;
Fuel + oxygen → electricity + oxidation products.

Hydrogen-oxygen fuel cell:

i. It contains an electrolytic solution such as 25% KOH. ii. It also has two inert porous electrode;
anode and cathode both made up of material like graphite filled with Pt/Pd/Ag etc.
iii. Through the anode H2 gas is bubbled. Through the cathode oxygen gas is bubbled. The reaction
taking place are, At anode: 2H2 → 4H+ + 4 e-
At cathode: O2 + 4H+ + 4 e- → 2H2O

Net reaction: 2H2 + O2 → 2H2O

The only product discharged by the cell is water. iv.

The standard e.m.f of the cell is 1.23V
v. But in actual practice, e.m.f of the cell is 0.8 to 1.0V
vi. Generally number of such fuel cells are packed together in series to make a battery cell called
fuel cell battery.
Application:
i) They are used as an auxiliary energy source in space vehicles, submarines, and other
military vehicles.
ii) In space craft they are preferred due to their light weight, and by-product water which
is a valuable source of fresh water for astronauts.

Advantage over the conventional power plants:

I) Easy to maintain.
II) They do not cause pollution.
III) As the fuel is completely consumed, it is fuel efficient.
IV) They have high efficiency as it converts energy isothermally. V) Product
obtained water is valuable and is of potable quality.

Limitation:
I) Life time of fuel cell is not accurately known.

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 II) Initial cost is high.
III) Pure hydrogen is costly.
IV) There is lack of infrastructure for the distribution of hydrogen.

Diagram:

Q.10) Distinguish between Electrolytic cell and Voltaic Cell.

Sr no Electrolytic cell Voltaic Cell

1 It is used for the conversion of electrical It is used for the conversion of chemical
energy into chemical energy. energy into electrical energy
2 Electrolysis takes place. Electricity is generated.
3 Anode requires positive charge. Anode requires negative charge.
4 Oxidation occurs at positive electrode Oxidation occurs at negative electrode while
while reduction occurs at negative reduction occurs at positive electrode
electrode
5 Both the electrodes are placed in the Two half cells are setup in different
solution or molten electrolyte in the same containers and are connected through salt
container. bridge or porous partition.
6 Example: Voltameter, Electroplating, etc. Example: Dry cell, Daniel cell, etc.

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Q. 11) Explain the concept of electrode potential:

1) A Galvanic cell is made up of two electrodes. One is anode(-) and other is Cathode(+). In
each
2) half cell,a metal electrode dips into a solution. A potential difference between metal and
solution is present at the surface of separation of metal and solution. This potential
difference is called electrode potential.
2) Electrode potential is thus defined as the difference of electrical potential between metal
electrodes and the solution around it under equilibrium condition.

Q. 12) Explain the origin of electrode potential.

1)When a metal plate is dipped into salt solution, the metal atoms have a tendency for oxidation or
delectronation. They have a tendency to lose electrons and go into the solution. During process
,they leave electrons on the metal plate and try to make the metal plate negatively charged. 2)
Also,the metal ions in the solution have a tendency of reduction or electronation. They have a
tendency to gain electrons and deposit on the metal plate. This process makes the metal plate
positively charged.
3) When equilibrium is reached, the metal plate may acquire positive charge if
reduction(electronation) is faster. However the metal plate may acquire negative charge if
oxidation(delectronation) is faster. Thus the charge acquired by the metal plate depends upon the
rate of oxidation or reduction.
4) Charge separation results in formation of an electrical double layer at the interface between
metal and solution. The charge on the solution is opposite to that of metal plate. The potential
difference between metal and solution at equilibrium is known as electrode potential.

Q. 13) Mention the factors affecting electrode potential.

1) Nature of the element

2) Temperature
3)Concentration or activity of ions in solution.
4)Pressure in case of gas electrode.

Q. 14) Define the terms:

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I) Oxidation potential:- The potential associated with an oxidation reaction at an electrode is
called oxidation potential.

M(s) ↔ Mn+ (aq) + ne-

II) Reduction Potential:- The potential associated with reduction reaction at an electrode is
called reduction potential.

Mn+ (aq) + ne- ↔ M(s)

III) Cell potential or EMF (Electromotive Force ):- It is defined as the difference of potential
between the electrodes corresponding to an external flow of electrons from Anode to Cathode

Ecell = Eoxi (Anode) + Ered (Cathode)

IV) Standard electrode potential

Concept of standard electrode potential with example:

Definition: The potential of an electrode at 25°C (298K) containing all reactants and products at
unit activity (conc. 1M and press. 1atm). It is denoted as E°.
The standard electrode potential for all metals can be obtained by preparing the cells in which one
electrode is standard hydrogen electrode while the other metal is metal immersed in the solution
of its ions. The standard electrode potentials are also known as standard oxidation potentials. It can
be calculated using Nernst equation,
Consider a general redox reaction,

Mn+ + ne- → M
Then,
E = E° + 0.0592 log10[Mn+]
n [M]

Electrode potential indicates tendency of a metal to behave as cathode or anode.

Nernst Equation:
1. Consider a reaction, Mn+ + ne- →nM

2. The equilibrium constant is given by,

K= [𝑃𝑟𝑜𝑑𝑢𝑐𝑡] = [𝑀n+] --------(1)
[𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡] [M ]

3. At equilibrium, Maximum work done

Wmax = nFE

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Where, n – number of electrons, F – Faraday(96500C), E – Cell potential

4. For a spontaneous reaction, change in free energy

∆G = - Wmax = - nFE----------(2)

5. Under Standard Conditions,

∆G° = - nFE ° ----------(3)

6. According to Vant Hoff, the decrease in the above mentioned reaction can be given as
∆G = ∆G° + 2.303RTlog10 K

Substituting equations 1, 2,3

-nFE = - nFE ° + 2.303RTlog10 [𝑀n+]

[M ]
Dividing by –nF,
E = E ° - 2.303 RT
log10 [𝑀n+]
𝑛𝐹 [M ]
OR
Ecell = E °cell - 2.303 RT
log10 [𝑀n+]
𝑛𝐹 [M ]

or Ecell = E °cell - 2.303 RT

log10 1n+
𝑛𝐹 [M ]

Or Ecell = E °cell + 2.303 RT

log10 [Mn+]
𝑛𝐹

Or Ecell = E °cell + 0.0592 log10 [Mn+]

𝑛
0.0592
Or Ecell = E °cell - log10
[𝑀n+]

𝑛 [M ]

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Electrochemical series:
In this the elements are arranged in the increasing order of their standard reduction potential.

element Std. electrode potential at

25°C
Li -3.052
K -2.93
Ca -2.90
Na -2.71
Mg -2.37
anodic
Al -1.66
Zn -0.76
Cr -0.74
Fe -0.44
Ni -0.23
Sn -0.14
H 0.00 Reference electrode
Cu 0.34
Hg 0.79
cathodic
Ag 0.80
Pt 0.86
Au 1.69

Features of Electrochemical series:

Elements at higher position Elements at lower position

Electropositive Electronegative
Tendency to lose electrons (act as anode) Tendency to gain electrons (act as cathode)
Easily oxidized Easily reduced
Corrodes easily Does not corrode easily

Limitations:

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 • Iron corrodes faster than aluminium even though iron is placed below aluminium in
electrochemical series because aluminium forms a nonporous, very thin, tightly adhering
protective oxide film (Al2O3) on its surface and this film does not permit corrosion to occur.
Such cases are not explained by electrochemical series.
• The standard electrode potentials are measured using SHE as the reference electrode whose
electrode potential is taken as zero. But practically the electrode potential of SHE cannot
be zero as it is impossible to get pure H2 gas, 1M conc. Of HCl and 1atm pressure of H 2
gas.
• Also the standard electrode potentials are measured at 25°C, at 1atm pressure and at 1M
conc.
of metal ions which may not be the practical conditions for corrosion of certain metal to occur.

Galvanic Series

• In galvanic series the metals are arranged in the decreasing order of their activity.
• For practical purpose, the electric potentials of many materials are obtained in a
single environment mostly sea water using standard calomel electrode as reference.
Such data in a tabular is called a ‘galvanic series’
• Galvanic series in Sea water of metals & alloys.

Anodic end (corroded)

Magnesium Copper
Zinc Bronze (Cu – Sn)
Aluminium Copper – Nickel alloys
Cadmium Monel Metal
Aluminium alloys Nickel
Mild steel Iconel
Alloy steel Silver
Cast iron Titanium
Stainless Steel Graphite
Muntz Metal Gold, Platinum
Brasses (Cu – Zn) Cathodic (protected) end

• In the galvanic series chemically more active metals are given higher position. These
metals easily react with oxygen, sulphur etc. hence corrode readily.
• The noble metals at the lower end do not easily react.
• Greater the difference in their position in galvanic series the faster will be the corrosion.
• Metals close to each other in the galvanic series show fewer tendencies to corrode when in
contact with each other.

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Distinguish between Electrochemical series and galvanic series.

Electrochemical series Galvanic series.

1. It is developed by arranging the electrode 1. It is developed by studying corrosion of

potentials of metals, which are measured by metals and alloys in unpolluted sea water using
dipping pure metals in their salt solution of 1M standard calomel electrode.
concentration at 25°C & at 1 atm pressure.
2. Position of a given metal is fixed on the basis 2. The position of a given metal may shift in
of its electrode potential. galvanic series.
3. It does not give any information regarding 3. It gives information regarding position of
position of alloys. alloys.
4. This series comprises of both metals and 4. This series comprises of both metals and
nonmetals, but not alloys. alloys, but not non-metals.
5. It is unable to predict correct corrosion 5. It predicts corrosion behavior more correctly.
behavior of metals.

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