IMPORTANT QUESTIONS

APPLIED CHEMISTRY (SEM I)

MODULE IV

ELECTROCHEMISTRY-PART II

(ELECTROCHEMICAL CELLS, CORROSION)

Q.1.What is Galvanic Cell (Electrochemical cell)?

A galvanic cell is a device in which electricity is generated due to a spontaneous redox (oxidation-
reduction) reaction. In this cell, chemical energy is converted into electrical energy.Galvanic cell is also
known as voltaic cell or electrochemical cell.

A galvanic cell has an anodic part and a cathodic part. They are also called anode half cell and the
cathode half cell. The two half cells usually consists of dissimilar metal rods dipped in their salt solutions.
The metal rods are called electrodes. So the metal electrodes are in contact with their ions in their salt
solution. The salt solution containing the metal ions is called the electrolytes. The two half cells are
connected internally through a salt bridge and externally through a metal wire. The metal electrode which
has more tendencies for oxidation acts as the anode and the other act as the cathode. Therefore the anode
metal loses electrons as a result of oxidation and goes to the solution as positive ions. The electrons lost from
the anode metal, move towards the cathode through the metal wire. At the cathode, the metal ions in the
cathode half cell combine with the electrons and get discharged (reduction). The flow of electrons from
anode towards the cathode is called the electric current. The electric current is produced due to the difference
in electrode potential. It is called the cell emf or cell potential.

Q.2.Explain the working of Daniel cell.

Daniel cell consists of an anode half cell, a cathode half cell and a salt bridge. The anode is a zinc rod
dipped in a ZnSO4 solution and the cathode is a copper rod dipped in a CuSO4 solution.

The two half cells are connected externally through a metallic wire and internally through a salt bridge.

The salt bridge is an inverted U-shaped glass tube containing an aqueous solution of an inert electrolyte
like KCl or KNO3 in a gel form using a substance called agar-agar. The ends of the U-tube are closed with
glass wool.
 Zn loses electrons as a result of oxidation and goes to the solution as Zn 2+ ions. These electrons move
to the cathode through the metal wire. At the cathode, Cu2+ ions in the cathode half cell combine with the
electrons and get reduced. It is the movement of electrons from zinc to copper which produces a current in the
external circuit.

The electrode reactions can be represented as:

Anode reaction (oxidation) Cathode reaction(reduction)

Zn  Zn 2+ + 2e- Cu2+ + 2e-  Cu

The overall cell reaction can be written as:

The emf of Daniel cell is 1.1 volt. It is the difference between the electrode potentials.

3. What is salt bridge? What are its functions?

The salt bridge is an inverted U- tube containing an aqueous solution of an inert electrolyte like KCl or
KNO3 in a gel form by the addition of agar-agar . Inert means chemically inactive. Such electrolytes have
almost equal speed for their cations and anions. The ends of the U-tube are closed with glass wool.

The functions of salt bridge are;

i) it helps to complete the circuit.

ii) it helps to maintain the electrical neutrality of the solution by preventing the accumulation of charges
in the anode or cathode half cells.

iii) it prevents the intermixing of the solution.

4. Give the symbolic representation of Daniel Cell.

In the symbolic representation of the cell, the anode is shown on the left side and cathode on the right
side. Two close vertical lines are used to represent the salt bridge. C1 and C2 are the concentrations (molarity)
of the salt solutions (electrolytes). Zn2+ is the metal ion in ZnSO4 solution. Cu2+ is the metal ion in CuSO4
solution.

5. Distinguish between Electrolytic Cell and Galvanic Cells

Galvanic Cell Electrolytic Cell

1. Chemical energy is converted into electrical 1. Electrical energy is converted into chemical
energy energy
2. Electrical energy is generated by a redox 2. Electrical energy is required for the redox
reaction reaction
3. Anode is negative while cathode is positive. 3. Anode is positive while cathode is negative.
4. Oxidation and reduction reactions are carried 4. Oxidation and reduction reactions are carried
out separately. out in the same container (vessel).

5. Salt bridge is generally used. 5. Salt bridge is not used.

6.The cell reaction is spontaneous. 6. The cell reaction is non spontaneous.

6. What are the Types of Galvanic Cells? Give two examples for each

There are two types of galvanic cells.

(i) primary cells (ii) secondary cells.

i)Primary cells

Primary cells are non rechargeable galvanic cells. The cell reaction is not reversible in primary cells.
The redox reaction occurs only once, and then the cell becomes inactive.

Example: Daniel cell, Dry cell, Mercury cell, etc.

ii) Secondary cells

 Rechargeable galvanic cells are called secondary cells. In a secondary cell, the cell reaction is reversible.
These cells can be used again and again by recharging. It means that the used up electrode materials can be
regenerated by recharging (passing current from an external source in the opposite direction.)

Examples: Lead storage battery (Automobile battery), Nickel - Cadmium cell (NiCad cell)

7. What are fuel cells? What are its advantages?

Fuel cells are electrochemical cells in which chemical energy of fuels is directly converted into
electrical energy. The fuels such as H2, CO, CH4 (gases) and alcohols (liquids) can be used to produce
electricity. Here electricity is produced using electrochemical process without physically burning it.

In fuel cells, the fuel and oxygen gas is made into contact with an electrolyte through porous
anode and cathode respectively. Consequently a redox reaction occurs and electrons flow from anode to
cathode through an external metal wire .

Fuel cells can convert about 75 % of the available chemical energy into electrical energy.

Advantages:

1. Efficiency is very high (about 75%). Energy loss to the surroundings is very low.

2. It is a pollution free and environmental friendly device.

3. This cell works continuously as long as the reactants are supplied

8. Explain the working of H2-O2 fuel cell.

Hydrogen - Oxygen fuel cell is based on the oxidation of hydrogen to form water.

2H2(g)+O2(g)  2H2O

The cell consists of three compartments separated from one another by two porous graphite
electrodes impregnated with platinum catalyst (Pt) . The hydrogen gas is fed into the anodic compartment
and oxygen gas is fed into the cathodic compartment at 50 atm pressure. In the middle compartment
(electrolyte compartment) an aqueous solution of NaOH or KOH is taken as the electrolyte. Hydrogen gas
and oxygen gas are continuously diffuse through the electrodes and undergoes a redox reaction in the
presence of the electrolyte.

The electrode reactions can be represented as:

Anode reaction (oxidation) Cathode reaction(reduction)

2H2 + 4OH–  4H2O + 4e- O2 + 2H2O + 4e-  4OH–
 over all reaction : 2H2 + O2  2H2O + energy

9. Define electrode potential.

Electrode potential is the tendency of an electrode to get oxidized or reduced when it is in contact with its
own ions in solution. The tendency of the electrode to lose electrons or to occur oxidation is called oxidation
potential and the tendency of the electrode to occur reduction (gain electrons) is called reduction potential.
The unit of electrode potential is volt.

[Oxidation potential and reduction potential of an electrode have the same magnitude but have opposite
signs. For example; oxidation potential of Zn/Zn2+ electrode is +0.79V. Its reduction potential is -0.76V. ]

10.Define Standard Electrode Potential (𝑬𝒐𝒆𝒍 )

The electrode potential of an electrode measured at 25°C (298 K) when the concentration of its ion is
unity (1 molar) is called standard electrode potential (𝑬𝒐𝒆𝒍 ).

[According to the IUPAC convention, the reduction potential alone be called as the electrode potential
(𝑬𝒐𝒆𝒍 ). For example: the standard electrode potential of zinc electrode (Zn/Zn2+) is -0.76 V and that of Copper
electrode(Cu/Cu2+) is + 0.34V. It means that copper has more tendency for reduction than the zinc electrode.
Standard reduction potential of hydrogen electrode is arbitrarily fixed as zero.]

11.Define Emf of a cell (cell potential).Give its relation with electrode potential.

Electromotive force ( emf ) is the driving force which enables the flow of electric current through a
circuit. It is equal to the difference in potential between the cathode and anode.

Emf of a cell = Reduction potential of cathode – Reduction potential of anode.

𝑬𝒄𝒆𝒍𝒍 = 𝑬𝒄𝒂𝒕𝒉𝒐𝒅𝒆 – 𝑬𝒂𝒏𝒐𝒅𝒆 and 𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 – 𝑬𝒐𝒂𝒏𝒐𝒅𝒆

The standard emf of a cell is denoted by 𝑬𝒐𝒄𝒆𝒍𝒍 .

12. Calculate the standard emf of Daniel cell. The standard electrode potentials of zinc and copper electrodes are -
0.76 and +0.34 respectively.

Ans: 𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 – 𝑬𝒐𝒂𝒏𝒐𝒅𝒆

The cathode is Copper electrode. 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 = 0.34

Anode is zinc electrode. 𝑬𝒐𝒂𝒏𝒐𝒅𝒆 = - 0.76 V

𝑬𝒐𝒄𝒆𝒍𝒍 = 𝑬𝒐𝒄𝒂𝒕𝒉𝒐𝒅𝒆 – 𝑬𝒐𝒂𝒏𝒐𝒅𝒆 = 0.34 - (-0.76) = 1.1 V

13Define Electrochemical series .

The arrangement of various electrodes in the increasing order of standard reduction potentials
from top to bottom is called electrochemical series.

[Different metal electrodes have different values of electrode potentials. It is a list or data of reduction
potentials of various electrodes in its increasing order. Electrode with lower reduction potential is placed
at the top. Electrode with higher reduction potential is placed at the bottom].

14. What does the positive and negative values of reduction potentials indicate?

Negative values of some reduction potentials indicate that such electrodes have less tendency for reduction
compared to standard hydrogen electrode(zero value). Positive values of some reduction potentials indicate that
such electrodes have more tendency for reduction compared to standard hydrogen electrode.

15. What are the applications of electrochemical series?

i) It helps to compare the reduction potential values of various electrodes. It helps to predict which
electrode would act as anode and which electrode would act as cathode. The electrode on the top in the
electrochemical series act as anode.

ii) It helps to compare the reducing and oxidizing powers of various elements used as the electrodes.

iii)It helps to calculate the standard emf of a galvanic cell from the electrode potential values.

iv) It helps to predict whether a metal has the ability to evolve H2 gas from dilute acid .

v) It helps to predict whether a metal has the ability to displace another metal from its salt solution.

[ A metal at the upper position will displace the metal lower in the series from its solution . For example,
copper sulphate solution cannot be kept in iron vessels or aluminium vessels. Because iron will displace
copper from its solution. As a result, the iron vessel gets destroyed. Same is the case of aluminium.]
 vi) The metals which are higher position in this series easily lose electrons (oxidation) and said to be more
active. So the electrochemical series help to compare the activity of various metals or elements.

16. Define corrosion.

Corrosion may be defined as the process of slow conversion of a metal into its undesirable
compounds (usually oxides) by their chemical interaction with its surrounding environment
(moisture and air).

17.What is rusting? Give the chemical form of rust.

The corrosion of a iron into rust is called rusting.

Rust is hydrated ferric oxide. Its formula is Fe2O3. xH2O. Where x ≥3

18 Corrosion of iron is fast, but corrosion of metals such as aluminium, zinc and copper is very slow
.Why?

The rates of corrosion of metals such as aluminium, zinc, copper etc are very slow. Because they
get a coating of a thin oxide film on their surface due to their interaction with atmospheric oxygen
which protect them from further corrosion. In their case, the corrosion product (oxides) is non porous
and act as protective layer which prevent further interaction with surrounding moist air. However in
the case of iron, the rust is brittle and porous. So it allows further interaction with surrounding moisture
and air.

19.What are the types of corrosions?

Two types of corrosion are observed

i) Dry or chemical corrosion: Chemical corrosion occurs due to the direct chemical attack of chemicals
or atmospheric gases such as O2, H2S, SO2, halogens etc. on the metal surfaces. Moisture is not required for this
type of corrosion. It is a fast process.
ii) Wet or Electrochemical corrosion : It is also known as galvanic corrosion. Moisture is required for
this type of corrosion. It is a slow process. Example: rusting.
The metal surface undergoes corrosion when it is in contact with water or moisture. The metal surface
behaves like many galvanic cells having separate “anodic” and “cathodic” areas on the surface. The metal atom
loses electrons from the anodic areas in presence of moisture which act as the electrolyte. The metal ions get
detached from the metal and form the corrosion product.
20 What are the Conditions favouring rusting or factors affecting rate of corrosion.?

i) Impurities in iron. Impurity increases rate of corrosion

 ii) Presence of oxygen and acidic gases such as CO2 or SO2 in its surroundings.

iii) Presence of moisture or wet air. Humidity increase rate of corrosion.

iv) Presence of electrolytes such as sodium chloride. (Rusting is higher in coastal area)

v) Presence of acidic environment. pH below 7 increases rate of corrosion.

vi) Temperature: Corrosion generally increases with rise in temperature of the environment.

vii) Influence of pH : In acid medium (PH < 7) corrosion is faster. In alkaline medium (pH > 7) corrosion is
less. So when pH decreases, the corrosion increases.

21. Explain Electrochemical theory of Corrosion (Mechanism of rusting.)

According to electrochemical theory, Corrosion is considered as an electrochemical process.

The metal surface behaves like many galvanic cells having separate “anodic” and “cathodic” areas on
the surface. The metal atom loses electrons from the anodic areas in presence of moisture which act as the
electrolyte. The metal ions thus formed get detached from the metal body and forms the corrosion
product.
22. Explain Electrochemical theory of Rusting.(Not required)
The metal surface undergoes corrosion when it is in contact with water or misture. The metal
surface behaves like many galvanic cells having separate “anodic” and “cathodic” areas on the surface.
The metal atom loses electrons from the anodic areas in presence of moisture which act as the
electrolyte. The metal ions thus produced get detached from the metal and forms the corrosion product.

The electrode reactions can be represented as:

Anode reaction (oxidation) Cathode reaction(reduction)

Fe  Fe2+ + 2e- 𝟏
O2 + 2H+ + 2e-  H2O
𝟐

The net reaction of the corrosion cell can be put as

𝟏
Fe + 𝟐
O2 + 2H+  Fe2+ + H2O E°cell = 1.67 V

The ferrous ions so formed undergoes further oxidation to form ferric oxide by atmospheric
oxygen and combine with water to form the rust ( hydrated iron(III) oxide.)
23 What are the important methods used to prevent corrosion ?

The important methods used to prevent corrosion are

(a) Barrier protection (b) Sacrificial protection (Galvanization) (c) Electrical protection(cathodic
protection) and (d)Anti rust solution

24. Explain Barrier protection .

In this method, the direct contact of the metal surface with the surrounding medium is prevented
by placing a suitable barrier film on the metal (iron) surface. The coating may be metallic or non
metallic.

Examples:-

(i) Painting, plastic coating or rubber coating on the metal surface.

(ii) Coating the metal surface with a thin film of oil or grease. -

(iii) Electroplating iron with some non-corrosive metal such as nickel, chromium, tin etc.

25. Explain sacrificial protection.

In this method, surface of iron is covered with a layer of more active metal like zinc. Here the
more active metal corrode first, then only iron start corrosion. This type of protection is called sacrificial
protection. It is called sacrificial because iron doesn’t corrode as long as the active metal is present on its
surface.

Example: Galvanization

Galvanization is the process of coating iron surface with zinc.

26. Explain electrical protection (Cathodic protection).

 In this method, the iron is protected by connecting it to some more active metal such as
magnesium through a metal wire. The iron article acts as cathode and get protected while the active
metal(Mg) acts as anode and suffers damage by losing electrons. This method is also known as cathodic
protection.

27. Explain Anti rust solution method.

The alkaline solutions of certain phosphate(sodium phosphate) and chromate salts act as anti rust
solutions. To protect from corrosion, the iron articles have to be dipped in to the boiling anti rust solutions. Then
a protective coating of iron phosphate is formed on the surface.

28.Which coating is more useful to prevent rusting-Zinc coating or Tin coating. Explain

Ans: Zinc coating is better than tin coating. Zn is more active than iron. Tin (Sn) is less active than iron.

Zn protects iron by sacrificial protection method, where as Sn protects iron by Barrier protection method.
In the event of a scratch and the iron surface is exposed to the moist air, then region of Zn act as anode,
but Sn act as cathode. So in the case of scratch, tin coated iron corrode fast while Zn coated iron
corrode slowly.

29. Explain the metal –anodic and metal-cathodic coating to prevent corrosion.

Metallic coating is a method of Barrier protection. : Metallic coating can be done by electroplating,
dipping or spraying.

Metal -cathodic protection:

If the metal coating is done using a metal having higher reduction potential, it is called metal- cathodic
coating. These metals are less active than iron and have more chemical resistance to corrosion. Example: Tin,
nickel or chromium coating on iron (steel).

The coated metal have more resistance to corrosion. As long as there is no scratch or crack on the
coating, it is effective. If scratches or cracks appear on the protective layer, then surface of iron may get exposed
and rusting starts. This rusting extends beneath the protective layer and eventually peels off the protective layer.
Metal -anodic protection

If the metal coating is done using a metal having lower reduction potential, it is called metal- anodic
coating. Example: Zinc, magnesium or aluminium coating on iron (steel).

Coating of zinc on iron is called galvanization. Galvanized iron resists corrosion. In this case zinc acts a
sacrificial anode and protects iron, in case of any crack or exposure to moisture. The exposed iron does not
corrode because it act as the cathodic region.

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