THERMAL AND CHEMICAL EFFECTS OF CURRENT

Current produces heating effect. This is obtained from Joule’s Law

Joule’s Law states that, “the rate at which heat is dissipated in a conductor is directly
proportional to the square of the electric current passing through it”.
Let the heating effect (heat energy)=H
Electric current be represented by I ∧t−time
Mathematically,
H 2
∝I
t
H 2
=k I
t
2
H=I Rt … … … … … … … …(1)
From the above equation, the constant of proportionalityk =R=¿ the resistance of the
conductor.
From Ohm’s Law, I =V / R ……..into eqtn(1), we have

V2t
H= … … … … … … … …(2)
R
Also, V =IR ……..into eqtn(2), we have
H=IVt … … … … … … … …(3)
From eqtn(3). Electrical Power, P=IV
⟹ H=Pt … … … … … … … (4)
NB: The heat produced due to Joule’s law is independent of the direction of the current.
Alternating current and direct currents obey Joule’s law
Also, when there is an electric current in a resistor, the thermal energy of the resistor
increases.
Let the potential difference between the terminals of a resistor is V and a current I passes
through it, the work done by the electric field on the free electrons in time t is given by
W =( potential difference)×(charge)
W =V (¿)
∴ W =H =IVt

It follows from equation (1) that

(a) the heat produced in a given resistor in a given time is proportional to the square of the
current in it, i.e.,
H ∝ I2
(b) the heat produced in a given resistor by a given current is proportional to the time for
which the current exists in it, i.e.,
H ∝t
(c) the heat produced in a resistor by a given current in a given time is proportional to its
resistance, i.e.,
H ∝R

Electric Power is the rate of consumption/conversion of electrical energy.

V2 2 H
P=IV = =I R=
R t
(i) Power of electrical appliances connected in series
Let R1 , R 2 , R3 , R 4 be the resistances of appliances connected in series.
Let P1 , P2 , P 3 , P4 be the powers across R1 , R 2 , R3 , R 4 respectively
Then the total power P is given by
P=IV 1+ IV 2+ IV 3 + I V 4 ……………………i
since appliances are∈ series , same current runs through then . only pd varies
From Ohm’s law, V =IR
P=I ( I R1 ) + I ( I R2 ) + I ( I R 3 ) + I ( I R 4 )
P=I 2 R 1+ I 2 R 2+ I 2 R 3+ I 2 R4 ¿
P=I 2 ( R1+ R 2+ R 3+ R 4 ) =I 2 R
P=(P ¿ ¿ 1+ P2+ P 3+ …)¿

Therefore, when appliances are connected in series, the total power dissipated
across the appliances is equal to the sum of individual powers across each
component.

(ii) Power of electrical appliances connected in parallel

Let R1 , R 2 , R3 , R 4 be the resistances of appliances connected in series.
Let P1 , P2 , P 3 , P4 be the powers across R1 , R 2 , R3 , R 4 respectively. Then

VERIFICATION OF JOULE’S LAW

(a) Oil is poured in a well-lagged copper
calorimeter provided with a non-
conducting lid and a stirrer. A resistor
 is dipped in the oil. It is joined to the external circuit through the lead of the
calorimeter. A thermometer is provided to measure the temperature of the oil. The
calorimeter used in this special case is called Joule’s calorimeter.
2
H ∝I
The electrical circuit
The circuit consists of a battery, a rheostat an ammeter and a key in series with the
resistor.
The initial temperature θ1 of the oil is recorded by the thermometer.
The key is closed, current flows through the circuit for some time t. The value of the
current I 1 is measured by the ammeter. The liquid is stirred continuously with the
stirrer and the final temperature θ2 is recorded.
The change in temperature is calculated as
△ θ 1=θ2−θ 1
The liquid is then allowed to cool and the process repeated for a different value of
resistance on the rheostat, the new current is recorded within the same time used in
the first case. The new temperature is recorded as θ2. The change in temperature is
recorded as
△ θ 2=θ2−θ 1
From the experiments, it can be concluded that, the heat produced in the resistor
changed the temperature of the oil.

∆θ∝I2
∆ θ1 I 21
⟹ =
∆ θ2 I 22

Or
2
H ∝I
As the key is closed and current runs through the resistor, the temperature is recorded at
regular time intervals. It is found that the temperature rises uniformly as the time
increases.It increases by equal amounts in equal times. This shows that equal amounts of
heat are produced in equal time intervals. Therefore, the heat produced is proportional to
the time.
H ∝t

Two Joule’s calorimeters are taken. Equal amounts of K-oil are taken in the two
calorimeters. Different resistances R1 and R2 are dipped in the oil and the two are joined in
series. The system is connected to a battery, a rheostat and a key. The initial temperatures
of the two calorimeters are noted and a current is passed for some time. The final
temperatures of the two calorimeters are noted at the end.
Let △ θ 1 be the rise in the temperature of the content of the first calorimeter and △ θ 2 be
the rise in the temperature of the second calorimeter.
The heat produced in each resistor is proportional to the rise in temperature in the
corresponding calorimeter.
It is follows from observation that
△θ∝ R
∆ θ1 R1
⟹ =
∆ θ2 R2
⟹H∝ R
NB: The calorimeters are connected in series so that the same current passes through
them.

Seebeck Effect:
If two dissimilar metal wires or strips, say A and B, are connected or joined end to end to
form two junctions, a thermocouple is made.
Refer to the diagram below
If two junctions of a thermocouple are kept at
different temperatures, an electric current is
induced in the
loop due to the
difference in
temperature.
This is the
Seebeck Effect.
The type of emf
generated from
this effect is
termed Seebeck
Emf or thermo emf. The magnitude of the emf produced depends on
the type of metals used and also on the temperature difference
between both hot and cold junctions.
The induced thermo emf is obtained from the equation
 2
βθ
E=αθ+ , where θ is the temperature difference between the hot and cold junctions.
2

Thermoelectric effect is the direct conversion of temperature differences to electric

voltage and vice versa via a thermocouple. Thermoelectric devices create a voltage when
there is a different temperature on each side.
Conversely, when voltage is applied to it, heat is transferred from one side to the other,
creating a temperature difference.
At the atomic scale, an applied temperature gradient causes charge carriers in the material
to diffuse from the hot side to the cold side.
This effect can be used to generate electricity, measure temperature or change the
temperature of objects. Because the direction of heating and cooling is determined by the
polarity of the applied voltage, thermoelectric devices can be used as temperature
controllers.
The term "thermoelectric effect" encompasses three separately identified effects: the
Seebeck effect, Peltier effect, and Thomson effect.
Seebeck Effect In 1821 Thomas Seebeck, a German physicist discovered that when two
dissimilar metal (Seebeck used copper and bismuth) wires are joined at two ends to form a
loop, a voltage is developed in the circuit when the two junctions are kept at different
temperatures. The pair of metals forming the circuit is called a thermocouple. The effect is
due to conversion of thermal energy to electrical energy.
 The Seebeck effect is a phenomenon in which a temperature difference between two
dissimilar electrical conductors or semiconductors produces a voltage difference
between the two substances.

 When heat is applied to one of the two conductors or semiconductors, heated

electrons flow toward the cooler one. If the pair is connected through an electrical
circuit, direct current (DC) flows through the circuit.

 The voltages produced by Seebeck effect are small, usually only a few microvolts
(millionths of a volt) per kelvin of temperature difference at the junction.

 If the temperature difference is large enough, some Seebeck-effect devices can

produce a few millivolts (thousandths of a volt).
Numerous such devices can be connected in series to increase the output voltage.
The numerous devices can also be connected in parallel to increase deliverable
current.
  Large arrays of Seebeck-effect based devices provide useful, small-scale electrical
power if a large temperature difference is maintained across the junctions.

Explanation of Seebeck Effect

 The valence electrons in the warmer part of metal are solely responsible for that
and the reason behind this is thermal energy.

 Also because of the kinetic energy of these electrons, these valence electrons
migrate more rapidly towards the other (colder) end as compare to the colder part
electrons migrate towards warmer part.

 At hot side Fermi distribution is soft i.e. the higher concentration of electrons above
the Fermi energy but on cold side the Fermi distribution is sharp i.e. we have fewer
electrons above Fermi energy.

 Electrons go where the energy is lower so therefore it will move from warmer end
to the colder end which leads to the transporting energy and thus equilibrating
temperature eventually
Applications of Seebeck effect
There are many applications of the Seebeck effect. In addition to its use in thermocouples
to measure temperature differences, the phenomenon is also used in the following ways:
i. in thermopiles (that is, in a setting where a number of thermocouples are connected
in series)
ii. in thermoelectric generators that function as heat engines
iii. in power plants to convert waste heat into (extra) power
iv. in automobiles as automotive thermoelectric generators, to increase fuel efficiency
v. in high-frequency electrical power sensors
vi. to verify material degradation and radiation level, and to perform strength testing of
radioactive materials (which vary with temperature over a given time period)
vii. to actuate security alarms or switches.

Thompson’s effect
Peltier effect
Thermoelectric generator
Sample questions
CHEMICAL EFFECTS
ELECTROLYSIS
Electrolytes are liquids which conduct electricity. This is due to the presence of ions in
them. Aqueous solutions of inorganic salts, acids and bases (alkaline) are good electrolytes.
Examples of these solutions are dil NaOH, dil HCl, aqueous NH 4Cl, dil H2SO4, etc.
In electrolysis, a vessel with the electrolyte in it is called electrolytic cell. Consider a
solution of silver nitrate in an electrolytic cell. Let us immerse two silver rods labeled rod-A
and rod-C as shown in the figure below.
Electric current is passed through the solution
by connecting the rods to an external
source(battery).
The electric current enters the solution
through the rod-A, in this case called the
anode and it leaves the solution through the
rod-C, called the cathode. These rods are
collectively called electrodes.
It can be observed that as time passes, silver
gets deposited on the cathode C and an equal
amount of silver is removed from the anode A.
+¿¿ −¿¿
The silver nitrate molecule breaks down in solution producing Ag and NO 3 each of
which carries electric charge. These are called ions. An ion with positive charge is called
+¿¿ −¿¿
cation and an ion with negative charge is called anion. The Ag is the cation and NO 3 is
the anion.
These ions move freely in the solution. When the electrodes are connected to an external
circuit and the circuit turned on, an electric field is set in the solution from the anode
towards the cathode. Therefore, cations move towards the cathode and the anions toward
the anode. The ions give up their charges at the electrodes and the substance making up the
ions is liberated. The liberated substance may get deposited on the electrodes or may take
part in some secondary chemical reaction. In the case of AgNO3, the Ag+¿¿ ions (cation)
move to the cathode, the charge is given up there and the silver atoms are deposited on the
cathode. In fact, an Ag+¿¿ ion receives an electron from the cathode to become neutral Ag
atom
+¿+e= Ag ¿
Ag
−¿¿ −¿¿
The NO 3 ion moves to the anode and gives an extra electron to it. The NO 3 is then
converted to NO 3.
−¿=NO +e ¿
N O3 3

The NO 3formed reacts with a silver atom from the anode to form AgNO3 which gets into
solution. This process continues, silver is continuously removed from the anode and
deposited on the cathode with the concentration of electrolyte remaining unchanged.
The movement of cations (positive charge) towards the cathode and anions (negative
charge) towards the anode make the current in the electrolyte. The electron liberated by
the anion is passed through the battery back to the cathode which has given off one
electron to the cation. This action helps maintain the potential difference.
Note here that the number of electrons passed through the battery is equal to the number
of electrons absorbed or released at each electrode.
When current passes through an electrolyte, chemical changes occur in the electrolyte and
substances are liberated at the electrodes. This process is ELECTROLYSIS.

Faraday’s laws of electrolysis

Faraday discovered two laws of electrolysis:
1. The mass of a substance liberated at an electrode is proportional to the charge
passing through the electrolyte.

2. The mass of a substance liberated at an electrode by a given amount of charge is

proportional to the chemical equivalent of the substance.

If an electric current I is passed through an electrolyte for a time t, the amount of charge
passed is Q = it. According to the first law, the amount of the substance liberated at an
electrode is
m∝ Q … … … … … … … … … … … . … ..(i)
But Q=¿ ⟹ m∝¿
m=ZIt
where Z is a constant for the substance being liberated. This constant is called the
Electrochemical equivalent. Its SI unit is kilogram per coulomb (kg C -1)
its relative atomic mass
this constant Z=
its valency
1
Relative atomic mass of a substance is the ratio of the mass of its atom to the of the mass
12
of a C atom. For instance, the atomic mass of silver is 108 and its valency is 1. Therefore,
12

the chemical equivalent of silver is 108. In same way, the atomic mass of copper is 63.5 and
its valency is 2. The chemical equivalent is 31.75. oxygen has 8.

If we denote the chemical equivalent of a substance being liberated at an electrode with E.

from the second law of electrolysis
m∝ E
Combining the two laws we have
m∝ EQ … … … … … … … …(ii)
1
m= EQ … … … … … … ..(iii)
K
where K is a universal constant with value 9.6485 ×107 C kg−1

Example:
Calculate the electric current required to deposit 0.972 g of chromium in three hours. ECE
of chromium is
0.00018 g C−1.
Solution:
m 0.972
m=ZIt . I= = =0.50 A
Zt 0.00018 ×3600

Verification of Faraday’s Laws

1st law
An electrolytic cell is connected to a battery, a rheostat, a key and an ammeter in series as
in figure below
The cathode is cleaned, dried, weighed and then inserted in
the electrolytic cell. A constant current I 1 is passed for a
measured time t.

The current is measured by the ammeter. The current is

maintained.
The cathode is taken out, washed, without rubbing, in gently-
flowing water and dried. It is weighed again and the mass m1
of the deposit is obtained.

The cathode is reinserted in the cell and the rheostat position changed. This will allow a
different current I 2 when the circuit is closed. This current is passed for the same time t
and the mass m2 of the deposit is obtained.

It is found that
m1 I 1
=
m2 I 2
∴ m∝ I … … …( a)
In Similar manner, two experiments are done with the same current but for different times
t1 and t2. If the masses of the deposits are m '1 and m'2 respectively, it is found that:
'
m1 t 1
=
m2 t 2
'

∴ m∝t … . … … …(b)
Combining (a) and (b), we have
m∝¿ m ∝Q

2nd law
To verify the second law, one can take two electrolytic cells containing different
electrolytes. For example, one may contain CuSO 4 solution with copper electrodes and the
other AgNO3 solution with silver electrodes. The electrodes are connected in series with an
external circuit as shown in figure below. This arrangement ensures that the currents in
the two cells are the same.
 The cathodes are cleaned, dried,
weighed and then inserted in the
respective cells. The current is passed
for some time and then the cathodes
are taken out.

They are washed without rubbing in

gently-flowing water, dried and
weighed. Thus, the masses of the deposits are obtained. If m1 and m2 are the masses of
copper and silver deposited, it is found that
m 1 E1
=
m 2 E2
where E1 and E2 are the chemical equivalents of copper and silver respectively. So, the
second law is verified.

Faraday’s Laws and Ionic Theory

Faraday’s laws of electrolysis can be easily understood in terms of the ionic character for
the conduction in an electrolyte. Suppose a substance of valency v is liberated at an
electrode. Its ion will carry a positive or a negative charge of magnitude ve. To neutralise
this ion, the battery has to supply or take up a charge ve. If the total charge passing through
the battery is Q, the number of ions neutralised N , is
Q
N=
ve

1
Let the relative atomic mass of the substance be A. Then of the mass of a12C atom is one
12
−27
atomic mass unit (amu) and has a value of 1.6605 ×10−27 kg . Let mu=1.6605 ×10 kg . Then,
the mass of an atom of the substance is given by
m a= A . m u

This can also be taken as the mass of an ion because the difference in ionic mass and atomic
mass is negligible. The mass of the N ions neutralised at the electrode is
m=NA m u
Q A mu
¿
ne
A
The quantity =the chemical equivalent , E . So
v
EQ
m=
e /mu
e
=K
mu
EQ
⟹ m=
K
 −19
e 1.6022 ×10 C 7 −1
=mu = −27
=9.6485 ×10 C kg
mu 1.6605 ×10 kg

The Unit “faraday” and Faraday Constant

The charge of 1 mole of electrons is called 1 faraday. So, faraday is a unit of charge and its
relation with coulomb is;
1 faraday=( 1.6022 ×10 C ) × ( 6.022× 10 ) =96485 C ≅ 96500C
−19 23

The Faraday, F, is the quantity of charge per mole of electrons.

F=96485 C mol−1 ≅ 96500 C mol−1=1 faraday mol−1

Let 1 faraday of charge be passed through an electrolyte. The number of electrons taken up
or supplied at an electrode is 1 mole. Since each ion takes up or gives up v electrons, the
1
number of ions liberated is moles . The mass of 1 mole of the substance is A grams
v
A
(A=relative atomic mass), so that the mass of these ions is gram=E gram.
v

The amount E gram of a substance is called 1 gram-equivalent of this substance.

So, 1 faraday of charge liberates one gram-equivalent of any substance in electrolysis.

VOLTAMETER OR COULOMBMETER
An electrolytic cell can be used to measure electric current or amounts of charge. The
current, I, to be measured is passed through the electrolytic cell for a known time t. If the
mass deposited in time t is m and the electrochemical equivalent of the material is Z,
m
m=ZIt ,then I =
Zt

m
The charge passed is ¿= .
Z

When an electrolytic cell is used to measure electric current, it is called a voltameter or a

coulombmeter. Quite often, the word voltameter is used to mean just the electrolytic cell
whatever be its use.

A copper voltameter may be used for routine laboratory measurements. The electrolyte is
CuSO 4 solution in water in the ratio of about 1 :4 by weight.

A copper plate placed in the middle serves as the

cathode and two connected copper plates on the two
sides of the cathode are used as the anode. In this
arrangement, both sides of the cathode plate receive the
deposit.
A silver voltameter is used when high accuracy is needed. The electrolyte is silver nitrate
solution in water in the ratio of 1 :5¿ 1 :6. The solution is taken in a platinum cup.
The cup itself acts as the cathode.
The anode is made of a silver
rod placed in the middle.

A porcelain cup which is porous

to the electrolyte surrounds the
anode. This prevents the
impurities in the anode to reach
the cathode.

Because of the high accuracy

attainable, silver voltameters are used in laboratories for standardization purposes.

ELECTROCHEMICAL/ELECTRIC CELLS
When a metal electrode is dipped in an electrolyte, negative or positive ions tend to go
from the electrolyte to the electrode. Thus, an emf is produced between the electrolyte and
the electrode. If two electrodes of different metals are dipped in an electrolyte, the emf’s
produced at the two electrodes are different and there is a net emf between the electrodes.
This forms a voltaic cell, also called simply a cell. The electrode at higher potential is called
the positive electrode and that at lower potential is called the negative electrode. Terminals
connected to these electrodes are called positive and negative terminals respectively.
This is the basic theory of a voltaic cell in which electrolysis is used to produce an emf
between two terminals.

An electrochemical cell is a device that can generate electrical energy from the chemical
reactions occurring in it. This device is capable of converting chemical energy into electrical
energy. Their reactions are spontaneous. An example of electrochemical cell is a standard
1.5 V cell. This is commonly used in many devices such as TV remotes, flashlights and
clocks. Such cells are called Galvanic cells or Voltaic cells. Electrochemical cells can also use
the electrical energy supplied to it to facilitate chemical reactions in it.
NB: For our studies in this book, we will limit the term
(a) “Electrochemical cells” to those which convert chemical energy from
chemical (reduction/oxidation) reactions to electrical energy.
(b) “Electrolytic cells” to cells which convert electrical energy to non-
spontaneous chemical reactions.
An electrolytic cell is an electrochemical device that uses electrical energy
to facilitate a non-spontaneous redox reaction. They convert electrical energy
to chemical energy
A cell is called primary if it is used only for discharge. It cannot be recharged. The chemical
reaction producing the electrical energy is irreversible.

The current leaves the cell at the positive terminal, goes through the external circuit and
enters the cell at the negative terminal. A secondary cell on the other hand can be
discharged as well as charged; the current can go both ways in the cell.

PRIMARY CELLS
Daniell Cell
In the simplest form, a Daniell cell consists of a zinc electrode in
a dilute H2SO4 solution and a copper electrode in CuSO4
solution. The two solutions are separated by a porous cup
which allows any gas to pass through, but generally prevents
the liquids to mix. The zinc surface is amalgamated to avoid the
local effects of impurities.

The H 2 SO 4 solution consists of H +¿¿ ions and SO 4 ions. The

2−¿ ¿

2−¿ ¿
SO 4 ions move to the zinc electrode to form ZnSO 4. Negative charge is given up to the
+¿¿ +¿¿
zinc electrode in the process. The H ions move out through the porous cup. These H
2−¿ ¿
ions combine with the SO 4 ions in the CuSO 4 solution to form H 2 SO 4 . The Cu 2+¿ ¿ ions in
the outer vessel move towards the copper electrode.

Copper is deposited on the copper electrode and positive charge is given up to this
electrode in the process. This arrangement prevents hydrogen from collecting near the
anode.

Any hydrogen collected near the anode may stop the function of the cell. This problem is
called polarization. The bubbles insulate the anode increasing the internal resistance of the
cell. This prevents electrons from leaving the cell through the electrode.

Because of the chemical actions described, the positive charge is accumulated on the
copper electrode and negative charge on the zinc electrode. Therefore, an emf is produced.
The zinc electrode works as the negative electrode and the copper electrode works as the
positive electrode.

Daniel cell is used when a continuous current is needed. The emf of a Daniell cell is around
1.09 V and its internal resistance is around 1 Ω.

Leclanché Cell (Wet and Dry)

A Leclanche cell has a carbon and a zinc electrode in a solution of NH4Cl. The carbon
electrode is packed in a porous pot containing a mixture of
MnO2 and graphite. The zinc electrode forms the negative terminal and the carbon forms
the positive terminal.
These two are placed in a glass vessel containing dil NH4Cl
−¿¿ +¿¿
When a current passes through the cell, the Cl ions combine with zinc and the NH 4 ions
+¿¿
move towards the carbon electrode. The NH 4 separates into ammonia ( NH 3) and
hydrogen (H+). The H+ ion enters the porous cup. The positive charge is given to the carbon
electrode. The hydrogen reacts with MnO2 present there to form Mn2O3 and water. Thus,
MnO2 prevents hydrogen from collecting on the anode which could otherwise stop the cell’s
function.

The depolarizing action (absorbing hydrogen in some chemical reaction) is quite slow in
Leclanché cell.
Thus, if the cell is used continuously, hydrogen starts collecting at the carbon electrode and
the cell is not able to supply enough current. Its emf is about 1.5 V.

Dry Leclanche Cell

This is a special kind of Leclanche cell in which both NH4Cl and MnO2 are prepared in the
form of a paste. The paste is contained in a zinc container which by itself works as the
negative electrode. The whole system is sealed so that the paste does not dry up. The
internal resistance of a dry cell is very small, of the order of 0.1 Ω

SECONDARY CELL:
This is cell or battery which can be charged, discharged through a load, and
recharged many times. They are also known as storage batteries.
LEAD ACCUMULATOR
In a secondary cell, one can pass current in both directions. When current leaves the cell at
the positive terminal and enters the cell at the negative terminal, the cell is discharged. This
is the normal working of the cell. Chemical energy is converted into electrical energy in this
case. If the cell is connected to some other source of larger emf, current may enter the cell
at the positive terminal and leave it at the negative terminal. The electric energy is then
converted into chemical energy and the cell gets charged. The most commonly used
secondary cell is a lead accumulator.