• Recognise the conductivity of electrolytic

solution
• Define the terms resistivity, conductivity
equivalent and molar conductivity
• Factors affecting equivalent conductance
INTRODUCTION
 We have come across many materials in our life, and they can be broadly
classified into conductors, semiconductors and insulators based on their
electrical conductivity.
 You might have noticed that conducting materials such as copper, aluminium
etc., are used to transport electrical energy from one place to another place,
and the insulating materials such as PVC, Bakelite etc., in switches, circuit
boards etc., Do you know how the electrical energy is generated?
 We know from first Law of thermodynamics that energy can neither be created
nor be destroyed, but one form of energy can be converted into another form.
 It is not possible to create electrical energy but we can generate electrical
energy in many ways i.e., by converting solar energy, wind energy, tidal energy
etc.... one such a way is converting chemical energy into electrical energy as in
the case of batteries.
 We cannot imagine a modern technological world without
batteries.
 Hence it is important to know the principles behind this type of
energy conversion.
 The branch of chemistry that deals with the study of electrical
energy transport and the inter conversion of electrical and
chemical energy is called electrochemistry.
 Electrochemical reactions are redox reactions and they involve the
transfer of electron from one substance to another.
 In this unit, we will learn about the electrical conduction,
construction of batteries and the thermodynamic principles involved
in electro chemical reactions.
Conductivity of electrolytic solution:
 We have already learnt that when an electrolyte such as sodium
chloride, potassium chloride etc... is dissolved in a solvent like
water, the electrolyte is completely dissociated to give its
constituent ions (namely cations and anions).
 When an electric field is applied to such an electrolytic solution,
the ions present in the solution carry charge from one electrode to
another electrode and thereby they conduct electricity.
 The conductivity of the electrolytic solution is
measured using a conductivity cell.
 A conductivity cell consists of two electrodes
immersed in an electrolytic solution.
 It obeys Ohm's law like metallic conductor. i.e., at a
constant temperature, the current flowing through
the cell (I) is directly proportional to the voltage
across the cell (V).
Resistivity
 Let us consider a conductivity cell in which the electrolytic solution is confined
between the two electrodes having cross sectional area (A) and are separated
by a distance ‘l ’ .
 Like the metallic conductor, the resistance of such an electrolytic solution is
also directly proportional to the length (l ) and inversely proportional to the cross
sectional area (A).

 Where ρ (rho) is called the specific resistance or resistivity, which depends

on the nature of the electrolyte.
 If l / A = 1 m-1 , then, ρ = R . Hence the resistivity is defind as the
resistance of an electrolyte confined between two electrodes having unit
cross sectional area and are separated by a unit distance.

 The ratio l / A is called the cell constant, Unit of resistivity is ohm metre
(Ωm).
 Conductivity(C)
 It is more convenient to use conductance rather than resistance.
 The reciprocal of the resistance (1/R) gives the conductance of an
electrolytic solution.
 The SI unit of conductance is Siemen (S).

Substitute (R)

 The specific conductance is defined as the conductance of a cube of an

electrolytic solution of unit dimensions. The SI unit of specific conductance is
Sm-1 .
----------------- 1
 Therefore, Volume of the solution containing one mole of solute = 1/M (mol-1 L

--------------- 2

Substitute equation 2 in equation 1

--------------------- 3

• The above relation defines the molar conductance in terms of the

specific conductance and the concentration of the electrolyte
 Equivalent conductance is defined as the conductance of 'V’ m3 of
electrolytic solution containing one gram equivalent of electrolyte
in a conductivity cell in which the electrodes are one metre apart.

 The relation between the equivalent conductance and the

specific conductance is given below.

 Where κ the specific conductance and N is the concentration of

the electrolytic solution expressed in normality
Factors affecting electrolytic conductance
• If the interionic attraction between the oppositely charged ions of
solutes increases, the conductance will decrease.
• Solvent of higher dielectric constant show high conductance in
solution.
• Conductance is inversely proportional to the Viscosity of the
medium. i.e., conductivity increases with the decrease in viscosity.
• If the temperature of the electrolytic solution increases,
conductance also increases. Increase in temperature increases the
kinetic energy of the ions and decreases the attractive force
between the oppositely charged ions and hence conductivity
increases.
• Molar conductance of a solution increases with increase in
dilution. This is because, for a strong electrolyte, interionic forces
of attraction decrease with dilution. For a weak electrolyte, degree
of dissociation increases with dilution.
Example
A conductivity cell has two platinum electrodes separated by a distance 1.5 cm and
the cross sectional area of each electrode is 4.5 sq cm. Using this cell, the resistance
of 0.5 N electrolytic solution was measured as 15 Ω . Find the specific
conductance of the solution.
Example
Calculate the molar conductance of 0.025M aqueous solution of
calcium chloride at 250C. The specific conductance of calcium
chloride is 12.04X10 -2 Sm-1 .
• Measurement of conductivity of
ionic solutions

• Conductivity calculation
Measurement of conductivity of ionic solutions

• We have already learnt to measure thespecific resistance of a

metallic wire usinga metre bridge in your physics
practicalexperiment.

• We know that it works on the principle of wheatstone bridge.

• Similarly, the conductivity of an electrolytic solution is

determined by using a wheatstone bridge arrangement in
which one resistance is replaced by a conductivity cell filled
with the electrolytic solution of unknown conductivity.
• In the measurement of specific resistance of
a metallic wire, a DC power supply is used.
• Here, if we apply DC current through the
conductivity cell, it will lead to the
electrolysis of the solution taken in the cell.
• So, AC current is used for this measurement
to prevent electrolysis.
• A wheat stone bridge is constituted using
known resistances P, Q, a variable resistance
S and conductivity cell (Let the resistance of
the electrolytic solution taken in it be R) as
shown in the figure .
• An AC source (550 Hz to 5 KHz) is
connected between the junctions A and C.
• Connect a suitable detector E (Such as the
telephone ear piece detector) between the
junctions ‘B’ and ‘D’.
• The variable resistance ‘S’ is adjusted until
the bridge is balanced and in this conditions
there is no current flow through the detector.
• The resistance of the electrolytic solution (R) is calculated from
the known resistance values P, Q and the measured ‘S’ value
under balanced condition using the above expression
Conductivity calculation
• Specific conductance (or) conductivity of an electrolyte can be
calculated from the resistance value using the following
expression.

• The value of the cell constant l / A is usually provided by the

cell manufacturer. Alternatively the cell constant may be
determined using KCl solution whose concentration and
specific bconductance are known.
 Variation of molar conductivity with
concentration
Debye - Huckel and Onsager equation
 Kohlraush's law
 Variation of molar conductivity with
concentration
 Friedrich Kohlraush studied the molar conductance of
different electrolytes at different concentrations.
 He observed that, increase of the molar conductance of an
electrolytic solution with the increase in the dilution.
 One such experimental results is given in the following table for
better understanding.
 Based on the above such results, Kohlraush deduced the following
empirical relationship between the molar conductance( Лm) and
the concentration of the electrolyte (C).

Лm – Molar conductance

Л0m – Limiting molar conductance

• For strong electrolytes
such as KCl, NaCl etc.,
the plot, Лm Vs C , gives a
straight line as shown in
the graph.
• It is also observed that
the plot is not a linear one
for weak electrolytes
(CH3COOH).
• For a strong electrolyte, at high concentration, the
number of constituent ions of the electrolyte in a given
volume is high and hence the attractive force between the
oppositely charged ions is also high.
• Moreover the ions also experience a viscous drag due to
greater solvation.
• These factors attribute for the low molar conductivity at
high concentration.
• When the dilution increases, the ions are far apart and
the attractive forces decrease.
• At infinite dilution the ions are so far apart, the
interaction between them becomes insignificant and
hence, the molar conductivity increases and reaches a
maximum value at infinite dilution.
• For a weak electrolyte, at high
concentration, the plot is almost
parallel to concentration axis with
slight increase in conductivity as the
dilution increases.
• When the concentration approaches
zero, there is a sudden increase in the
molar conductance and the curve is
almost parallel to Λm axis.
• This is due to the fact that the dissociation of the weak electrolyte
increases with the increase in dilution (Ostwald dilution law).

• Λ0m values for strong electrolytes can be obtained by

extrapolating the straight line, as shown in figure .

• But the same procedure is not applicable for weak electrolytes, as

the plot is not a linear one, Λ0m values of the weak electrolytes can
be determined using Kohlraush's law.
 Debye - Huckel and Onsager
equation
 The influence of ion-ion interactions on the conductivity of strong
electrolytes was studied by Debye and Huckel.
 They considered that each ion is surrounded by an ionic
atmosphere of opposite sign, and derived an expression relating
the molar conductance of strong electrolytes with the
concentration by assuming complete dissociation.
 Later, the equation was further developed by Onsager.
 For a uni – univalent electrolyte the Debye Huckel and Onsager
equation is given below.

• Where A and B are the constants which depend only on the nature of the
solvent and temperature. The expression for A and B are

• Here, D is the dielectric constant of the medium, η the viscosity of the

medium and T the temperature in Kelvin.
 Kohlraush's
• law
The limiting molar conductance Л0m is the basis for kohlraush
law.

 “At infinite dilution, the limiting molar conductivity

of an electrolyte is equal to the sum of the limiting
molar conductivities of its constituent ions. i.e., the
molar conductivity is due to the independent
migration of cations in one direction and anions in
the opposite direction”.
• For a uni – univalent electrolyte such as NaCl, the Kohlraush's
law is expressed as
 In general, according to Kohlraush's law, the molar conductivity
at infinite dilution for a electrolyte represented by the formula Ax
By , is given below.

• Kohlraush arrived the above mentioned relationship based on the

experimental observations such as the one as shown in the table.
 These result show that at infinite dilution each constituent ion of
the electrolyte makes a definite contribution towards the molar
conductance of the electrolyte irrespective of nature of other ion
with which it is associated
 SESSION - 4
Applications of Kohlrausch's Law
1. Calculation of molar conductance at infinite dilution of a
weak electrolyte.

2. Calculation of degree of dissociation of weak electrolytes.

3. Calculation of solubility of sparingly soluble salts

1. Calculation of molar conductance at infinite dilution of a
weak electrolyte.
 It is impossible to determine the molar conductance at infinite
dilution for weak electrolytes experimentally. However, the same
can be calculated using Kohlraush’s Law.
 For example, the molar conductance of CH3COOH, can be
calculated using the experimentally determined molar
conductivities of strong electrolytes HCl, NaCl and
CH3COONa .
2. Calculation of degree of dissociation of weak electrolytes
 The degree of dissociation of weak electrolyte can be calculated
from the molar conductivity at a given concentration and the
molar conductivity at infinite dilution using the following
expression

 Calculation of dissociation constant using Лm values.

 According to Ostwald dilution Law,
3. Calculation of solubility of sparingly soluble salts
 Substances like AgCl, PbSO4 etc., are sparingly soluble in water.
 The solubility product of such substances can be determined
using conductivity measurements.
 Let us consider AgCl as an example

 Let the concentration of [Ag ]+ be ‘C’ mol L-1.

 then [Cl-] also equal to ‘C’ mol L -1 .
 We know that the concentration (in mol dm-3) is related to the
molar and specific conductance by the following expressions.

 Substitute the concentration value in the relation KSP = C2

 SESSION - 5
Electrochemical Cell
• Galvanic cell
• Oxidation half cell
• Reduction half cell
• Joining the half cells
• Anodic oxidation
• Cathodic reduction
• Salt bridge
• Completion of circuit
• Consumption of Electrodes
• Galvanic cell notation
• emf of a Cell
 Electrochemical Cell
 Electrochemical cell is a device which converts chemical energy
into electrical energy and vice versa.
 It consists of two separate electrodes which are in contact with
an electrolyte solution.
 Electrochemical cells are mainly classified into the following two
types.

1. Galvanic Cell ( Voltaic

cell)

2. Electrolytic cell
1. Galvanic Cell ( Voltaic cell) :
• It is a device in which a spontaneous chemical reaction generates
an electric current i.e., it converts chemical energy into electrical
energy. It is commonly known as a battery.
2. Electrolytic cell :
• It is a device in which an electric current from an external source
drives a nonspontaneous reaction i.e., it converts electrical energy
into chemical energy.
• We have already learnt in XI standard that when a zinc metal strip
is placed in a copper sulphate solution, the blue colour of the
solution fades and the copper is deposited on the zinc strip as red –
brown crust due to the following spontaneous chemical reaction.

• The energy produced in the above reaction is lost to the

surroundings as heat.
• In the above redox reaction, Zinc is oxidised to Zn2+ ions and the
Cu2+ ions are reduced to metallic copper. The half reactions are
represented as below.
• If we perform the above two half reactions separately in an apparatus as
shown in below, some of the energy produced in the reaction will be converted
into electrical energy.
• Let us understand the function of a galvanic cell by considering Daniel cell as
an example. It uses the above reaction for generation of electrical energy.
• The separation of half reaction is the basis for the construction of Daniel cell. It
consists of two half cells.
Oxidation half cell:
• A metallic zinc strip that dips into an aqueous solution of zinc sulphate taken in a

beaker

Reduction half cell:

•Joining
A copper stripcells:
the half that dips into an aqueous solution of copper
• sulphate
The zinc taken in a beaker.
and copper strips are externally connected using a wire
through a switch (k) and a load (example: volt meter).
• The electrolytic solution present in the cathodic and anodic
compartment are connected using an inverted U tube containing a
agar-agar gel mixed with an inert electrolytes such as KCl,
Na2SO4 etc.,
• The ions of inert electrolyte do not react with other ions present in
the half cells and they are not either oxidised (or) reduced at the
lectrodes.
• The solution in the salt bridge cannot get poured out, but through
which the ions can move into (or) out of the half cells.
• When the switch (k) closes the circuit, the electrons flows from
zinc strip to copper strip.
• This is due to the following redox reactions which are taking place
at the respective electrodes.
Galvanic cell
notation
 emf of a Cell
 We have learnt that when two half cells of a Daniel cell are connected, a
spontaneous redox reaction will take place which results in the flow of electrons
from anode to cathode.
 “The force that pushes the electrons away from the anode and pulls
them towards cathode is called the electromotive force (emf) (or) the
cell potential.”
 The SI unit of cell potential is the volt (v).
 When there is one volt difference in electrical potential between the anode and
cathode, one joule of energy is released for each columb of charge that moves
between them. Ie, 1J = 1C X 1V
 SESSION - 6
Measurement of electrode
potential
Thermodynamics of cell reactions
• Nernst equation
Measurement of electrode potential
• The overall redox reaction can be considered as the sum of two
half reactions i.e., oxidation and reduction.
• Similarly, the emf of a cell can be considered as the sum of the
electrode potentials at the cathode and anode,

• Here, (EOX)anode represents the oxidation potential at anode

and(EOX)cathode represents the reduction potential at cathode.
• It is impossible to measure the emf of a single electrode, but we
can measure the potential difference between the two electrodes
(Ecell) using a voltmeter.
• If we know the emf of any one of the electrodes which constitute
the cell, we can calculate the emf of the other electrode from the
measured emf of the cell using the above expression
• Hence, we need a reference electrode whose emf is known
STANDARD HYDROGEN ELECTRODE (SHE)
• For that purpose, Standard Hydrogen
Electrode (SHE) is used as the
reference electrode.
• It has been assigned an arbitrary emf
of exactly zero volt.
• It consists of a platinum electrode in
contact with 1M HCl solution and 1
atm hydrogen gas.
• The hydrogen gas is bubbled through
the solution at 25C as shown in the
figure .
• SHE can act as a cathode as well as
an anode.
• The Half cell reactions are given
below.
 Thermodynamics of cell
 We have reactions
just learnt that in a galvanic cell, the chemical energy is
converted into electrical energy.
 The electrical energy produced by the cell is equal to the product
of the total charge of electrons and the emf of the cell which
drives these electrons between the electrodes.
 If ‘n’ is the number of moles of electrons exchanged between the
oxidising and reducing agent in the overall cell reaction, then the
electrical energy produced by the cell is given as below.
 Electrical energy = Charge of ’n’ mole of electrons Ecell
Charge of 1 mole of electrons = one Faraday (1F)
Charge of ’n’ mole of electrons = nF
Electrical energy = nFEcell
RELATIONSHIP BETWEEN emf AND FREE ENERGY
Nernst equation
 SESSION - 7
Electrolytic cell and electrolysis

Electrolysis of molten NaCl

Faraday’s Law – first and second law

Electrolytic cell and electrolysis

 Electrolysis is a process in which the electrical energy is used to

cause a non-spontaneous chemical reaction to occur; the energy is
often used to decompose a compound into its elements.
 The device which is used to carry out the electrolysis is called the
electrolytic cell.
 The electrochemical process occurring in the electrolytic cell and
galvanic cell are the reverse of each other.
 Let us understand the function of a electrolytic cell by considering
the electrolysis of molten sodium chloride.
 Electrolysis of molten sodium chloride
 The electrolytic cell consists of two iron electrodes dipped in
molten sodium chloride and they are connected to an external
DC power supply via a key as shown in the figure.
 The electrode which is attached to the negative end of the power
supply is called the cathode, and the one which attached to the
positive end is called the anode.
 Once the key is closed, the external DC power supply drives the
electrons to the cathode and at the same time pull the electrons
from the anode.
Faraday’s Laws of electrolysis
First Law
 The mass of the substance (m) liberated at an electrode during
electrolysis is directly proportional to the quantity of charge
(Q) passed through the cell.

 We know that the charge is related to the current by the equation

(or)

 Where is Z is known as the electro chemical equivalent of the

substance produced of the electrode.
 When, I = 1A and t = 1sec, Q = 1C , in such case,

 Thus, the electrochemical equivalent is defined as the amount of

substance deposited or liberated at the electrode by a charge of 1
coulomb.

(Or)
Second Law
 When the same quantity of charge is passed through the solutions
of different electrolytes, the amount of substances liberated at the
respective electrodes are directly proportional to their
electrochemical equivalents.
 Let us consider three electrolytic cells connected in series to the
same DC electrical source as shown in the figure . Each cell is
filled with a different electrolytes namely NiSO4, CuSO4 and
CoSO4, respectively.
 SESSION - 8
 Batteries

 Leclanche cell

 Mercury button cell

Batteries
 Batteries are indispensable in the modern electronic world.
 For example, Li – ion batteries are used in cell phones, dry cell in
flashlight etc…. These batteries are used as a source of direct
current at a constant voltage.
We can classify them into
• Primary batteries (non – rechargeable)
• Secondary batteries (rechargeable).
• In this section, we will briefly discuss the electrochemistry of
some batteries.
Leclanche cell
Mercury button cell
 SESSION - 9
Secondary batteries
 Lead storage battery
 The lithium – ion Battery
 Fuel cell
Secondary batteries
 We have already learnt that the electrochemical reactions which take place in a
galvanic cell may be reversed by applying a potential slightly greater than the
emf generated by the cell.

 This principle is used in secondary batteries to regenerate the original

reactants.

 Let us understand the function of secondary cell by considering the lead storage
battery as an example
Lead storage
battery
 The emf of a single cell is about 2V .
 Usually six such cells are combined in series to produce 12volt .
 The emf of the cell depends on the concentration of H2SO4.
 As the cell reaction uses SO42- ions, the concentration
H2SO4decreases.
 When the cell potential falls to about 1.8V, the cell has to be
recharged.

Recharge of the cell:

 As said earlier, a potential greater than 2V is applied across the

electrodes, the cell reactions that take place during the discharge
process are reversed.

 During recharge process, the role of anode and cathode is

reversed and H2SO4 is regenerated
 Thus, the overall cell reaction is exactly the reverse of the redox
reaction which takes place while discharging .
Uses:
Used in automobiles, trains, inverters etc…
The lithium – ion Battery
Anode : Porus graphite
Cathode : Transition metal oxide such as CoO2
Electrolyte : Lithium salt in an organic solvent
• Both electrodes allow Li+ ions to
move in and out of their
structures.
• During discharge, the Li+ ions
produced at the anode move
towards cathode through the non
– aqueous electrolyte.
• When a potential greater than
the emf produced by the cell is
applied across the electrode, the
cell reaction is reversed and now
the Li+ ions move from cathode to
anode where they become
embedded on the porous
graphite electrode.
• This is known as intercalation.
Uses :
Used in cellular phones, laptops, computers, digital cameras, etc…
 Fuel
• cell
The galvanic cell in which the energy of combustion of fuels is
directly converted into electrical energy is called the fuel cell.
• It requires a continuous supply of reactant to keep functioning.
• The general representation of a fuel cell is follows
Fuel | Electrode | Electrolyte | Electrode | Oxidant
• Let us understand the function of fuel cell by considering
hydrogen – oxygen fuel cell.
• In this case, hydrogen act as a fuel and oxygen as an oxidant and
the electrolyte is aqueous KOH maintained at 200oC and
20 – 40 atm.
• Porous graphite electrode containing Ni and NiO serves as the
inert electrodes.
• Hydrogen and oxygen gases are bubbled through the anode and
cathode, respectively.
• The above reaction is the same as the hydrogen combustion
reaction, however, they do not react directly ie., the
oxidation and reduction reactions take place separately at
the anode and cathode respectively like H2 – O2 fuel cell .
Other fuel cells like propane –O2 and methane O2 have also
been developed.
 SESSION - 10
Corrosion
Electrochemical mechanism of
corrosion
Electrochemical series
Corrosio
n
Corrosion
• We are familiar with the rusting of iron. Have you ever noticed a
green film formed on copper and brass vessels?.
• In both, the metal is oxidised by oxygen in presence of moisture.
• This redox process which causes the deterioration of metal is
called corrosion.
• As the corrosion of iron causes damages to our buildings, bridges
etc....it is important to know the chemistry of rusting and how to
prevent it.
• Rusting of iron is an electrochemical process.
Electrochemical mechanism of corrosion
• The formation of rust requires both oxygen and water.
• Since it is an electrochemical redox process, it requires an anode
and cathode in different places on the surface of iron.
• The iron surface and a droplet of water on the surface as shown in
figure , form a tiny galvanic cell.
• The region enclosed by water is exposed to low amount of oxygen
and it acts as the anode.
• The remaining area has high amount of oxygen and it acts as
cathode. So based on the oxygen content, an electro chemical cell
is formed. corrosion occurs at the anode i,e,. in the region enclosed
by the water as discussed below.
Protection of metals form corrosion
This can be achieved by the following methods.

i. Coating metal surface by paint.

ii. Galvanizing - by coating with another metal such as zinc. zinc is

stronger reducing agent than iron and hence it can be more easily
corroded than iron. i.e., instead of iron, the zinc is oxidised.

iii. Cathodic protection - In this technique, unlike galvanising the

entire surface of the metal to be protected need not be covered with
a protecting metal. Instead, metals such as Mg or zinc which is
corroded more easily than iron can be used as a sacrificial anode
and the iron material acts as a cathode. So iron is protected, but
Mg or Zn is corroded.
Passivation - The metal is treated with strong oxidising agents such
as concentrated HNO3. As a result, a protective oxide layer is
formed on the surface of metal.

Alloy formation - The oxidising tendency of iron can be reduced by

forming its alloy with other more anodic metals.
Example, stainless steel - an alloy of Fe and Cr .
Electrochemical series
We have already learnt that the standard single
electrode potentials are measured using standard
hydrogen electrode.
 The standard electrode potential at 298K for various
metal - metal ion electrodes are arranged in the
decreasing order of their standard reduction potential
values as shown in the figure.
This series is called electrochemical series.
The standard reduction potential (E0 ) is a measure of
the oxidizing tendency of the species. The greater the E0
value, greater is the tendency shown by the species to
accept electrons and undergo reduction.
So higher the (E0) Value, lesser is the tendency to
undergo corrosion
UTHRAKUMAR B
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