EIZREEN BINTI EIZUDDIN (D20182085830)

ASSIGNMENT SKF3023-PHYSICAL CHEMISTRY II

1. Differentiate between Galvanic cell and electrolytic cell.

GALVANIC CELL ELECTROLYTIC CELL

Spontaneous redox reactions convert the Non-spontaneous redox reactions convert

chemical energy to an electric energy the electric energy to a chemical energy

Electric energy is generated by redox Electric energy brings about the chemical
reactions reaction with the help of an external
source

The cathode is the positive electrode(+) The anode is the positive electrode(+) and
and anode is the negative electrode(-) cathode is the negative electrode(-)

The process of oxidation takes place at The oxidation process occurs at the
the anode and the reduction process cathode while the reduction process takes
occurs at the cathode place at the anode

Half cells are set up in different containers Electrodes are kept in the same container
and are connected through salt bridges in a molten or solution electrolyte

Application lies in batteries Application lies in purifying copper and

electroplating

2. How would you determine the standard electrode potential of the system Mg2+|Mg
By using the standard hydrogen electrode as anode and Mg2+|Mg as the cathode.
Standard hydrogen electrode, represented by Pt(s), H2(g) (1atm)|H+(aq) and dip the
electrode of magnesium wire in a 1M of MgSO4 solution. The standard hydrogen
electrode is always zero. The formula is
E°cell = E°right - E°left
The standard hydrogen electrode is always zero. Hence, the value of E°left = 0.
Thus,
E°cell = E°Mg|Mg2+
3. How is electrode potential different from cell potential
Electrode potential is the tendency of an electrode in an electrochemical cell to get
reduced or oxidized. It is the electromotive force of a cell. Whereas for cell potential, it
is the difference between the electrode potentials of the electrodes present in an
electrochemical cell.

4. Describe the construction and working of standard hydrogen electrode.

Standard hydrogen Electrode are reference electrodes whose potential marks the zero
level for all redox half reactions. It is used as a reference electrode when calculating the
standard electrode potential of a half cell. Normal hydrogen electrode set up consists of
platinum wire or sheet coated with platinum salt to form a layer of metallic platinum
and immerse in the solution of 1M HCl and hydrogen gas is bubbled at 1atm pressure
through the solution. The gas molecules are absorbed to the platinum layer forming a
hydrogen electrode and increase the space for chemical reaction. The platinum surface
appears dark due to absorption of light. The hydrogen electrode is the only metallic
electrode which does not consists of solid metal in equilibrium. The parts that make up
a Standard Hydrogen Electrode are listed below.
 A platinum electrode which is covered in finely powdered platinum black
(platinized platinum electrode).
 A hydrogen Blow.
 A solution of acid having a H+ molarity of 1 mole per cubic decimeter.
 The SHE also contains a hydroseal which is used to prevent the interference of
oxygen.
 The other half-cell of the entire Galvanic cell must be attached to the Standard
Hydrogen Electrode through a reservoir in order to create an ionically conductive
path. This can be done through a direct connection, through a narrow tube, or
even through the use of a salt bridge.
5. What is the purpose of salt bridge placed between two half cells of a galvanic cell?
The purpose of a salt bridge is not to move electrons from the electrolyte, rather to
maintain charge balance because the electrons are moving from one half cell to the
other. Without the salt bridge, the solution in the anode compartment would become
positively charged and the solution in the cathode compartment would become
negatively charged, because of the charge imbalance, the electrode reaction would
quickly come to a halt, therefore It helps to maintain the flow of electrons from the
oxidation half cell to a reduction half cell.

6. Give the representation of the Daniel cell.

Representation of Daniell cell in Zn and Cu electrodes :
Zn(s) | Zn2+(aq) || Cu2+(aq) | Cu(s)

7. Define resistivity and conductivity.

Resistivity measures the obstruction to the flow of current. The resistance of any
conductor is directly proportional to the length (l) and inversely proportional to the area
of cross section (a).
Conductivity measures of the ease with which current flows through a conductor. It is
inversed of the resistance.

8. What is cell constant? How is it determined?

Cell constant is the ratio of distance between conductance-titration electrodes to the
area of the electrodes, measured from the determined resistance of a solution of known
specific conductance. Cell constant is of particular cell is determined as the ratio of the
distance between the electrodes of the cell to the area of the electrodes. The formula of
cell constant : cell constant K = l/A = cm
The cell constant is usually determined by measuring the resistance of the cell
containing a solution whose conductivity is already known.
9. What are the problems faced in measuring R of ionic solutions and how are they
overcome?
In measuring the resistance of ionic solutions, there will be two difficulties faced:
 For electrolytic solution, direct current cannot be used because it can cause
electrolysis of the solution.
How to solve the problem: Alternating current in the audio frequency ranging
from 550 to 5000 cycles per second is provided by using a more suitable
electronic circuit commercially available. Since the alternating current is within
the range of human ear, the galvanometer can be replaced by a set of
headphones.

 A solution of unknown resistance cannot be connected to the bridge like a

metallic wire or other solid conductor.
How to solve the problem: Using a specially designed vessel called conductivity
cell for taking the ionic solution.

10. Differentiate between metallic and electrolytic conduction.

METALLIC CONDUCTION ELECTROLYTIC CONDUCTION

Flow of electricity takes place without the Flow of electricity takes place with the
decomposition of the substance decomposition of the substance

Conduction is due to the flow of electrons Conduction is due to the flow of ions

Conductivity ↓, temperature ↑ Conductivity ↑, temperature ↑

[dissociation due to the increase of

temperature decreases the interionic
attractions]

Resistance offered by the conductor is due Resistance offered by the conducing

to vibrating kernels. electrolyte is due to inter-ionic
attractions, solvent viscosity, etc

Only physical changes take place Physical and chemical changes

No movement of matter Movement of matter takes place

E.g. Metals, graphite E.g. Solutions of acids, bases and salts in

water, fused or molten salts
11. Define the terms conductivity and molar conductivity for solution of an electrolyte.
Discuss their variation with concentration.
 Conductivity - Conductivity of a solution is defined as the conductance of a
solution of 1 cm in length and area of cross-section 1 sq. cm. The inverse of
resistivity is called conductivity or specific conductance.

k=1/p

Conductivity always decreases with a decrease in concentration, both for weak

and strong electrolytes. This is because the number of ions per unit volume that
carry the current in a solution decreases with a decrease in concentration.

 Molar conductivity - Molar conductivity of a solution at a given concentration is

the conductance of volume V of a solution containing 1 mole of the electrolyte
kept between two electrodes with the area of cross-section A and distance of
unit length.

l = 1 and A = V (volume containing 1 mole of the electrolyte)

Am = kV

Molar conductivity increases with a decrease in concentration. This is because

the total volume V of the solution containing one mole of the electrolyte
increases on dilution.

12. What is the unit of molar conductivity?

S cm2 mol-1

13. What is limiting molar conductivity?

Limiting Molar conductivity is the conductivity of the solution at infinite dilution, i.e. all
the ions have dissociated or the ions are farther apart. Conductivity of electrolyte
decreases with decrease in concentration as number of ions per unit cm of surface area
decreases upon dilution.
14. Describe the characteristics of variation of molar conductivity with dilution for a)
strong electrolyte b) weak electrolyte. (or) With the help of a graph explain why it is
not possible to determine the limiting molar conductivity for a weak electrolyte by
extrapolating the concentration-molar conductance curve as for strong electrolytes.
(or) Express the relationship between degree of dissociation of an electrolyte and its
molar conductivities.
(a) Molar conductivity with dilution for strong electrolyte:
In strong electrolytes, the molar conductivity increases slowly with dilution and
there is a tendency for molar conductivity to approach a certain limiting value when
the concentration approaches zero. The molar conductivity when the concentration
approaches zero is called molar conductivity at infinite dilution.
The variation of molar conductivity, Ʌm with square root of concentration, C1/2 is
small so that the plots can be extrapolated to zero concentration. The intercept
gives the limiting value of molar conductivity when the concentration approaches
zero, called molar conductivity at infinite dilution, Ʌm.

(b) Molar conductivity with dilution for weak electrolyte:

The weak electrolyte dissociate to a much lesser extent as compared to strong
electrolytes. Therefore, the molar conductivity is low as compared to strong
electrolytes. However, the variation of molar conductivity Ʌm with C1/2 is ver large
and so much so that we cannot obtain molar conductance at infinite dilution (Ʌm°)
by extrapolation of Ʌm versus C1/2 plots.
15. How is molar conductivity of a weak electrolyte at infinite dilution determined? (or)
State Kohlrausch’s Law. Write two applications.
Kohlrausch’s law states that at infinite dilution when the dissociation is complete, each
ion makes a definite contribution towards molar conductivity of the electrolyte
irrespective of the nature of the other ion in which it is dissociated. The applications of
Kohlrausch’s law:
 Calculation of molar conductance at infinite dilution for weak electrolytes
 Calculation of degree of dissociation of weak electrolytes

16. What is the difference between primary cell and secondary cell?

PRIMARY CELL SECONDARY CELL

Have high energy density and slow in Have smaller energy density
discharge and easy to use

There are no fluids in the cells hence it is There are made up of wet cells (flooded
also called as dry cells and liquid cells) and molten salt (liquid
cells with different composition)

Has high internal resistance Has low internal resistance

Has an irreversible chemical reaction Has a reversible chemical reaction

Smaller and lighter More complex and heavier

Its initial cost is cheap Its initial cost is high