Chemical Effects of Current

1. Chemical Effects of Electric current

When we pass current through a solid conductor, it gets heated and also a magnetic field is produced around the
conductor. It shows that there is a heating effect as well as magnetic effect of current, but there is no chemical
effect in a solid conductor .On the other hand if current is passed through a liquid it may or may not allow the
current to pass through it. On the basis of the electric behavior, the liquids can be classified in to three
categories.

(1) Insulators: These are those liquids which do not allow current to pass through them. For example,
vegetable oil, distilled water etc.
(2) Good conductors: These are those liquids which allow current to pass through them but do not dissociate
into ions. For example, mercury, (a liquid metal at ordinary temperature)
(3) Electrolytes: The liquids which allow the current to pass through them and also disassociate into ions on
passing the current through them are called electrolytes. For example, the solution of salts, acids and
bases in water, alcohol etc.

2. Terms used in connection with Electrolysis

Electrolysis: The process of decomposition of electrolyte solution into ions on passing the current through it
is called electrolysis.

Electrolyte: The substance which decomposes into positive and negative ions on passing current through it
is called electrolyte.

For example; acids, bases, salts dissolved in water, alcohol ,etc. are common electrolytes. Pure salt like KCl,
NaCl etc. are electrolyte, in their molten state. AgCl is a solid state electrolyte in which silver ions (Ag+) are
mobile.

Electrodes: These are the two metal plates which are partially dipped in the electrolyte for passing through
the current through the electrolyte.

Anode: The electrode connected to the positive terminal of the battery i.e the electrode at higher potential is
called anode.

Cathode: The electrode connected to nagative terminal of the battery i.e the electrode at lower potential is
called cathode.

The current flows through the electrolyte from anode to cathode.

 Ions : The charged constituents of the electrolyte which are liberated on passing current are called ions.

Anions : The ions which carry negative charge and move towards the anode during electrolysis are called
anions. The ions formed when chemical reaction involves addition of electrons (i.e. reduction) are called
anions.

Cations: The ions which carry positive charge and move towards the cathode during during electrolysis are
called cations. The ions formed when chemical reaction involves removal of electrons (i.e. oxidation) are
called cations.

Voltameter: The vessel in which the electrolysis is carried out is called a voltameter. It is a vessel which
contains two electrodes and a solution electrolyte. It is also known as electrolytic cell.

The above things are shown in Fig.2(d).1.

FIGURE: 2(d) 1

3. Theory of Electrolysis
The process of electrolysis was explained by Arrhenius in 1887 by a very simple theory called Theory of
ionic dissociation. According to this theory the molecule of an electrolyte exists in the form of positive
and negative ions even if the electrolyte is in the solid form. When an electrolyte is dissolved in water i.e. a
solution of an electrolyte is prepared, some of the molecules of the electrolyte break up into two
parts called ions having opposite charges. Their number increases with the increase in dilution of the
solution and no external field is required for this purpose.
For example, a sodium chloride molecule (NaCl) consists of sodium and chlorine ions (Na+ and Cr).
They are held together by electrostatic force of attraction in electrolytic medium which is given by
1 q1q2
F
4 0 K r 2

where K is dielectric constant. For air, K = 1 and for water at room temperature K = 81.
Therefore, when NaC1 is dissolved in water, the force of attraction binding the two ions (Na+ and Cl - )
into the sodium chloride molecule becomes very small which is insufficient to hold them together and
thus the two ions get separated.
When a potential difference is established bet ween t he t wo el ect rodes placed i n the electrolyte, the
positive ions move towards the cathode and the negative ions move towards the anode. These ions on
reaching their respective electrodes give their charge to them and become neutral and then appear as free gas or
get deposited as a thin layer on the electrodes. This is how the electrolysis takes place.
It should be noted that the movement of the positively charged ions towards the cathode and negatively
charged ions towards the anode is equivalent to a current flowing from anode to cathode. This
explains how the electric current is conducted through an electrolytic solution.

4. Copper Voltameter
A copper voltameter consists of a glass vessel containing aqueous solution of CuSO 4 which acts as
electrolyte. There are two copper plates partly immersed in the electrolyte which act as electrodes, Fig. 2(d).2.
The electrodes are connected to battery B in series with ammeter A, rheostat Rh and key K. When a steady
current is passed through the CuSO4 solution, copper is deposited on the cathode C and an equivalent amount
of copper is lost by the anode and is dissolved into solution.

FIGURE 2(d) 2

Explanation. Copper sulphate in water dissociates as follows

CuSO4 Cu+ + + SO4 - -
When current is passed through solution, the copper ions drift towards the cathode and there, they get
neutralized by electrons flowing in from the negative terminal of the battery. Hence
At cathode : Cu + + + 2 e- Cu
The Cu atoms so produced get deposited on the cathode. Similarly, the SO4-- -- ions move towards the anode
and on reaching there they loose their two electrons and become neutral. The electrons so released flow
towards the positive terminal of battery. The neutral sulphate ions react with copper atoms of anode, form
copper sulphate which get dissolved into solution. Hence
 At anode :
Cu + SO4- = (Cu++ SO4- -) + 2e
Thus the copper is lost from the anode. Inside the copper voltameter, the Cu+ + and SO4-- carry

the current from anode to cathode. In the external circuit, the current is due to flow of electrons.
In the above process the copper is deposited on the cathode and an equivalent amount of copper is lost by the
anode, but the concentration of copper sulphate solution remains the same. In this process, two electrons per
reaction are active and valence of copper atom is also two.

5 Water Voltameter
Water voltameter consists of a glass vessel at the base of which two platinum electrodes El and E2 are fitted.
The platinum electrodes are dipped in water in which a small quantity of sulphuric acid is mixed. This makes
the water more conducting because extra ions are made available for conducting electricity. Two
graduated tubes T1 and
T2 filled fully with acidulated water are inverted over the two electrodes Fig. 2(d).3.

FIGURE 2(d) 3

W h e n c u r r e n t i s p a ss e d t h r o u gh t h e acidulated water, the electrolysis of water takes place. The

hydrogen gas is collected in the inverted tube T2 placed over the cathode E2 and oxygen gas is collected in the
inverted tube T1 placed over the anode El. The hydrogen collected is always twice the volume of oxygen.
Explanation : In the electrolysis of water, the following reactions take place.

At the cathode, the electrons flowing in from the negative terminal of the battery reduce the water i.e.
4H2O + 4e- 4O H - + 2 H 2 . ( 1 )

Thus hydrogen gas is evolved at cathode and concentration of OH - ions increases near the cathode.
At the anode, the concentration of OH - ions is low. Due to dissociation of sulphuric acid (in order to make
acidulated water), SO4- - ions are also present at the anode and they are difficult to oxidise. Under these
conditions, the direct oxidation of water takes place i.e.
2H2O 4H+ + O2 + 4e-...................... (2)
The oxygen gas is liberated at the anode. The electrons so released flow towards the positive terminal of
battery and the concentration of H + ions increases near the anode. In the electrolyte. H + and OH - m ove
t owards t he opposi t e electrodes and get neutralised, according to following reaction :
4H+ + 4 OH- 4 H2OAdding (1), (2) and (3), we get
2 H2 O 2 H2 + O2
This shows that the decomposition of every two molecules of water will result in the four electrons
flowing in the circuit and the net effect of the electrolysis is the decomosition of water into hydrogen and
oxygen. At any instant of time, the hydrogen collected at cathode is twice the oxygen collected at anode.
6 Silver Voltameter

A silver voltameter consists of a glass vessel containing aqueous solution of silver nitrate (AgNO3) which
acts as electrolyte. There are two silver plates which are partly immersed in the electrolyte which act as
electrodes. Fig. 2(d).4.

The electrodes are connected to ammeter A, battery B, rheostat Rh and key K.

When a steady current is passed through AgN 03 solution, silver is deposited on the cathode
C and an equivalent amount of silver is dissolved from the anode A1.
Explanation. Silver nitrate in water dissociates as follows
AgNO3 Ag+ + NO3 -

When current is passed through AgNO3 solution, the Ag+ ions drift towards the cathode and there, they get
neutralized by electrons flowing in from the negative terminal of the battery. Hence
 At cathode. Ag+ + e- Ag
The Ag atoms so produced get deposited on the cathode. Similarly the NO3- ions move towards
the anode and on reaching there, they loose their electrons become neutral. The electrons so released flow
towards the positive terminal of the battery. The neutral nitrate ions react with silver atoms forming silver nitrate.
These silver nitrate molecules get dissolved into the solution, due to which the concentration of solution remains
unchanged. Hence
At anode :
Ag + NO3 - (Ag+ NO3 -) +e-
Thus in the above process, the silver dissolves from the anode and gets deposited on the cathode. During this process,
the concentration of the electrolyte remains unchanged. In this process one electron per reaction is active and
valence of Ag atom is also one.
7. Faraday's Laws of Electrolysis
Faraday, from his experimental study, arrived at the two laws of electrolysis which are given below:
First law. The mass of the substance liberated or deposited at an electrode during electrolysis is directly
proportional to the quantity of charge passed through the electrolyte.
If m is the mass of a substance deposited or liberated at an electrode during electrolysis when a charge q passes
through electrolyte, then according to Faraday's first law of electrolysis,
mq
or m = zq .(4)
where z is a constant of proportionality and is called electrochemical equivalent (E.C.E.) of the substance.
If an electric current I flows for a time I to pass the charge q through the electrolyte, then q = lt
From (4), m = zlt When q = 1, from (4), m = z x 1 = z
Hence electrochemical equivalent (E.C.E.) of a substance is defined as the mass of the substance liberated or
deposited on an electrode during electrolysis, when one coulomb of charge (or1 ampere current for 1
second) is passed through the electrolyte.
Generally, the E.C.E. of a substance is expressed in gram/coulomb (gC-1). The value of E.G.E. of copper and
hydrogen are 0.0003294 gC-1 and 0.0000105 gC-1 respectively.

One ampere current flows for one minute through a silver voltameter.If 0.067 gm of silver is deposited
on the cathode, find the electrochemical equivalent of silver.

0.067
Sol. z = 1 = 1 60

= 1.117 x 10-3 g/C.

 Second law: When the same amount of charge is made to pass through any number of electrolytes, the
masses of the substances liberated or deposited at electrodes are proportional to their chemical equivalents.

If m1 and m2 = masses of the substance liberated or deposited on various electrodes when same current is
passed for the same time through their electrolytes.

E1, E2 = chemical equivalents* = of the substances liberated or deposited.

Then according to Faradays second Law of electrolysis

m1 E1

m2 E2

When copper and silver voltameters are connected in series and electric current is passed through them,
1.6 gm of copper is deposited .Find the mass of silver deposited. Given chemical equivalent of copper and
silver are 32 and 108 respectively.

m1 E1 E
Sol: or m2 = m1 1
m2 E2 E2

1.6108
= = 5.4 gm
32
Another form of Faradays Second Law of electrolysis
Consider during electrolysis one mole of a substance of atomic mass M is liberated on an electrode. If N is the
Avagardos number, then the number of atoms liberated at an electrode = N. If p is the valence of atom involved
and e is the charf\ge of an electron, then,
Charge flowing for decomposition of one atom = pe.
Total charge flowing for decomposition of N atoms = Npe
Now, for one mole of substance,
M =m and q = Npe
From Faradays first law of electrolysis
M = zq
We get, M = zNpe
1
Or z = ..( 7)

Or z ( N and e are constant)

Or z E
The quantity M/p = E, chemical equivalent of the substance and the fundamental constant Ne is called Faraday
constant(F).
The Faradays second law of electrolysis is also states that the electrochemical equivalent of a substance is
directly proportional to its chemical equivalent.
If E1, E2 = chemical equivalent of two substances.
z1, z2 = E.C.E of those substances.
Then from Faradays second law of electrolysis
z1 E1
(9)
z 2 E2

8. Faraday Constant
From Faradays second law of electrolysis

z E or E z or E =Fz

E
or z =F=a constant, called Faradays constant.

Thus Faraday constant,

E E qE
F= z = m / q = m ( m=zq)

If m = E, then F=q

Hence, Faraday constant is equal to the amount of charge required to liberate the mass of a substance at an
electrode during electrolysis, equal to its chemical equivalent.(in gram).

For example E.C.E. of copper = 0.0003294gC-1

Chemical equivalent of copper = 31.75g

31.75
One Faraday = 0.0003294

= 96500C/gram equivalent

It means 96500C of charge is required to liberate one gram equivalent of a substance at an electrode during
electrolysis.
Note, Faraday constant F= Ne.
=6.023x 10 23 x 1.602 x 10-19
= 96500 C/gram equivalent.
9. Experimental Verification of Faradays Laws
( a) First law. Take a copper voltameter. Connect it to a battery B, ammeter A, rheostat Rh and key
K in series as shown in Fig. 2(d).5. Take out the copper plate from copper voltameter to be used as cathode.
Clean, wash, dry and weigh it. Now insert this plate into copper voltameter at its initial location.

FIGURE 2.d. 5

Close key K. Adjust rheostat for suitable current in the circuit so that electrolysis may take place in
copper voltameter. Pass the current I for a suitable known time t. Again note the weight of copper plate used
as cathode and find the mass of copper deposited, say m.

Repeat the experiment by passing the current 2I for the same time t. We shall note that the mass of the
copper deposited on cathode becomes 2rn. This shows that
mI
Repeat the experiment again by passing the current 21 for time 2t. We shall note that the mass of the
copper deposited on cathode becomes 4m. This shows that
mt
m lt or m q [where It = q]
This proves the first law of electrolysis.
Second law. Take a silver voltameter, copper voltameter and water voltameter. Connect them in series
with a battery B, ammeter A, key K and rheostat Rh, as shown in Fig. 2(d).6.

Close key K. Adjust rheostat Rh for a suitable current in the circuit so that electrolysis may take place in all
the three voltameters. Pass the current for a suitable time. Note the masses of Ag and Cu deposited by
weighing the cathode plates of the two voltameters before and after the experiment. Note the volume of the
hydrogen collected at cathode in water voltameter. Reduce it to volume at N.T.P. and multiply it with the density
of hydrogen at N.T.P. We shall get the mass of hydrogen liberated at cathode in water voltameter. Find the
ratio of masses of Ag, Cu and H2 deposited or liberated at various
cathodes in different voltameters, which is found to be 108 :
31 75 : 1. This is the ratio of the chemical equivalents of the respective substances. This proves the second
law of electrolysis.

FIGURE 2.d. 6

Summery :

1. Chemical equivalent E = atomic weight (A) / Valency (p)=A/p.

2. Chemical equivalent expressed in grams is called gram equivalent and chemical equivalent expressed in kilo
grams is called kilogram equivalent.

3. To liberate one atom at an electrode during electrolysis, the charge to be passed through electrolyte is valence
of atom times the charge of an electron.

4. The ratio of equivalent (E) and electro chemical equivalent (z) is same for all elements and is called
Faradays constant F i.e. E/z=F=faradays constant.

5. The charge required to liberated one gram equivalent of one substance by electrolysis is called one faraday
which is equal to 96,500 coulomb/gram equivalent.

6. Charge required to liberate 1 kilo-gram equivalent of any substance by electrolysis is 9.65 x 107 coulomb / kg
equivalent.

7. Faraday constant F=Ne , where N is the Avogardos number and e is the electronic charge.

10 Practical Applications of Electrolysis

Some of the applications of electrolysis are as follows:

(i) Electroplating: It is a process of depositing a thin layer of one metal over another metal by the
method of electrolysis. The articles of cheap metals are coated with precious metals like silver and
gold to make their look more attractive. The article to be electroplated is made the cathode and the
 metal to be deposited is made the anode. A soluble salt of the precious metal is taken as the
electrolyte. When current is passed, a thin layer of the metal (made anode ) is deposited on the
article(made cathode).
(ii) Extraction of metals from the ores: Certain metals like Na, Al, Mg, ca, Zn, Cu etc are extracted
from their ores by electrolysis.
(iii) Purification of metals: Metals can be purified by electrolysis. The impure metal sheet is made the
anode and a pure metal sheet as the cathode in a large electrolytic cell. The soluble salt to the pure
metal is used as electrolyte. When current is passed, pure metal out of anode dissolves in to
electrolyte and gets deposited on the cathode. Blister copper is purified in this manner.
(iv) Manufacture of chemicals: Caustic soda is prepared by the electrolysis of sodium chloride solution.
(v) Electrotyping: The exact copies of the metallic type, used in the printing work and the engraved
blocks on the metals, can be prepared by the process of electrolysis; A sheet of wax is first pressed
against the type set or block. The impression obtained on wax is made conducting by coating it with
graphite powder Then it is copper plated by the process of electrolysis. The sheet so obtained is a
copy of the type of the block. It is also used for the manufacture of gramophone records.
(vi) Andolising: It is the process of coating aluminium with its oxide electrochemically to protect it
against corrosion. In dilute sulphuric acid as electrolyte, the aluminium article is made the anode.To
give the surface of the article beautiful coluors, dyes are mixed in the electrolyte.
(vii) Production of oxygen and hydrogen: Oxygen and hydrogen are obtained commercially, by the
electrolysis of acidulated water.
(viii) Medical applications: Electrolysis is used for nerve stimulation especially for polio, for removing
unwanted hairs on any part of the body etc.

11. Electro Chemical cell:

Electro-chemical cell is a seat of electrical power. Infact, the electro chemical cell is device by which
electric current energy is generated at the cost of chemical energy, due to chemical action taking place in the
cell .Electro- Chemical cells are of two types.

(i)Primary cells

(ii) Secondary cells

Primary cell is that cell in which electrical energy is produced due to chemical energy. The chemical reaction in
the cell is irreversible. For example; Voltaic cell, Daniel cell, Leclanche cell, Dry cell etc.

Secondary cell is that cell in which the electrical energy is first stored up as chemical energy and when current
is drawn from the cell, then the chemical energy is reconverted into electrical energy. The chemical reaction is
reversible in this cell. These cells are also known as storage cells or accumulators. Examples; Acid or Lead
accumulators and Alkali or Edison cells.
The initial cost of a primary cell is relatively low compared to a secondary cell, but its operating cost is quite
high. In contrast the running cost of a secondary cell is very low in the long run.
12.Voltaic Cell
Voltaic cell was invented by Allexandro de Volta in 1800. It consists of two rods (called
electrodes) one of copper and another of zinc, partly immersed in dilute sulphuric acid (called electrolyte)
contained in a glass vessel Fig. 2(d).7. The copper rod acts as positive electrode and zinc rod acts as negative
electrode.

FIGURE 2(d) 7

Action of voltaic cell. In electrolyte (i.e., dilute H2SO4) due to dissociation, there exist positively charged
hydrogen ions (H+) and negatively charged sulphate ions (SO4 ) as represented below

H2SO4 2 H+ + SO4- -
When the copper and zinc rods are immersed into the electrolyte, some of the zinc atoms from zinc rod go
into the solution as zinc ions (Zn++).
Zn Zn++ + 2e-
For each zinc ion so produced, two electrons are left on the zinc rod. Due to it, the zinc rod attains negative
charge and goes at lower potential w.r.t, to electrolyte. The positively charged zinc ions which enter the
solution repel the positively charged hydrogen ions on to the copper. These hydrogen ions (H + ), on
reaching the copper rod, extract electrons from there and become neutral hydrogen atoms which escape
from the solution as hydrogen gas, leaving the copper rod positively charged. Due to it, the copper rod attains
higher potential w.r.t.to electrolyte. Inside the solution, the Zn ++ combine with SO4-- forming ZnS 04 i.e.

Zn+ + + SO- - ZnSO4

This process continues till the positive charge, acquired by the copper rod is sufficient to repel the positively
charged hydrogen ions with a force equal in magnitude but opposite in direction to the force exerted by the
positive zinc ions on them. Thus a maximum potential difference is set up between copper and zinc rods,
copper being at higher potential than zinc rod. The maximum potential of zinc rod w.r.t. electrolyte is

-0 . 62 V. The maximum potential of copper rod w.r.t. electrolyte is + 0.46 V. This maximum potential
difference between the two electrodes of a cell in open circuit is called its electromotive force. The e.m.f. of a
voltaic cell.

= 0.46 - (-0.62) = 1. 08 V.
When the electrodes are connected to an external resistor, the circuit is completed. There will be flow
of electrons from the negatively charged zinc rod to the positively charged copper rod through the external
resistor. Now the conventional electric current is said to flow from copper to zinc. As the electric current is
drawn from the cell, the potential difference between the electrodes is reduced to some extent. Now
more zinc goes into solution and the original potential difference is again built up. Thus the electric current
can be continuously drawn from the cell till the whole zinc is dissolved or the sulphuric acid is consumed.
Inside the cell, the electric current (i.e. the motion of positive charge) is from zinc electrode to copper
electrode, hence the zinc rod is the anode and the copper rod is the cathode.
13:: Defects of a Voltaic Cell
There are two main defects of voltaic cell.
(i) Local action
(ii) Polarisation

(i) Local Action. It arises due to the presence of impurities of iron, carbon etc. or, the surface of
commercial zinc rod used as anode or a negative electrode. The particles of these impurities and zinc
in contact with sulphuric acid form minute voltaic cells in which small local electric currents are
set up, resulting in the wastage of zinc even when the cell is not sending the external current. This
defect is called local action.
Local action can be removed by amalgamating the zinc rod with mercury i.e., the surface of zinc rod is
rubbed with mercury. Due to it, the impurities in zinc rod are covered with a layer of mercury because they
are insoluble in mercury. However, the zinc in amalgamated zinc rod is exposed only to the acid. Thus, the
local action does not take place on the amalgamated zinc rod but when the cell is supplying the current, the
zinc is being chemically acted upon. The fresh zinc continues to come to the surface. As a result of it, the
chemical action is sustained without any local action.
(ii) Polarisation. It arises when the positive hydrogen ions which are formed by the action of zinc on
sulphuric acid, travel towards the copper rod and after transferring the positive charge are converted into
hydrogen gas atoms and get deposited in the form of a neutral layer of a gas on the surface of copper rod.
This weakens the action of cell in two ways:

(a) The internal resistance of the cell increases because the layer of hydrogen gas is a bad conductor
of electricity.
(b) The hydrogen ions moving towards the copper plate are unable to reach it and hand over the charge
to the hydrogen layer present on the surface of copper rod.
Due to above facts, the positively charged ions set up a field from the layer of hydrogen to zinc, resulting in back
electromotive force which sends the current in the opposite direction and weakens the action of the cell. This is
called polarisation defect.
This defect can be removed either by brushing off the hydrogen layer from the positive electrode i.e. copper
rod (or cathode) from time to time or by using a depolariser i.e. some oxidising agent (e.g. Mn02, CuSO4 etc.)
which may oxidise hydrogen into water.
14. Daniel Cell :
It consists of a copper vessel containing saturated copper sulphate (CuSO4) solution. The copper vessel
itself acts as the positive electrode or cathode. A porous pot containing 10% dilute s u l p h u r i c a c i d
( c a l l e d e l e c t r o l yt e ) a n d amalgamated zinc rod (called anode), is placed in the copper vessel and is
partly immersed in a copper sulphate solution. The porous pot prevents the solution from mixing, but
allows the hydrogen ions to pass through it. A perforated shelf containing the copper sulphate crystals
is placed at the top of t he vessel i n order to keep the concentration of the copper sulphate
solution same, Fig. 2(d).8.

FIGURE 2(d) 8

Zn Zn + + + 2e-
H2S O4 2H+ + SO-4- -
Zn++ + SO4- - ZnSO4
Zn + H2SO4 ZnSO4 + 2H+ + 2e -
The electrons so released are connected by zinc rod making it at negative potential w.r.t. electrolyte. The
hydrogen ions (H + ) so formed diffuse through the pores of porous pot and interact with copper sulphate,
forming thereby sulphuric acid and releasing copper ions (Cu++).
2H+ + CuSO4 H2SO4 + Cu+ +
These positive copper ions extract electrons from copper vessel, thereby making it at positive potential w.r.t. to
electrolyte, convert into copper atoms and are deposited on the copper vessel so that there is no
polatisation. Thus the copper sulphate acts as the depolariser. The use of the amalgamated zinc rod avoids
the local action in the cell. In this cell, as the reaction continues, the concent rat ion of copper sul phat e
s ol ut ion decreases. Some CuSO4 crystals get dissolved immediately from the performated shelf into
CuSO4 solution. Thus the concentration of CuSO4 is maintained. As the concentration of the copper sulphate
solution remains constant, when Daniel cell is in use, therefore, its e.m.f. remains constant.
The e.m.f. of Daniel cell is
 = 0.76 V- (-0.34 V) = 1.1 V
15 Leclanehe Cell
A Leclanche cell consists of a vessel of glass containing strong solution of ammonium chloride which acts as
electrolyte. An amalgamated zinc rod dipping in ammonium chloride acts as negative electrode or anode. A
porous pot is placed inside the glass vessel. The carbon rod placed inside the porous pot acts as positive electrode or
cathode. The space in the porous pot is filled with manganese dioxide and charcoal powder, Fig. 2(d). 9. The
charcoal powder makes the manganese dioxide electrically conducting and manganese dioxide acts as depolariser.
The inner side of glass vessel near the open end is coated with black paint which works as a reflector for the ammonium
chloride crystals as they have the tendency to creap along the glass wall. This helps in maintaining the proper
concentration of ammonium chloride solution.

The action of the cell can be described as follows.

Zn Zn++ + 2e-

2NH4Cl 2NH3 +2H+ +2Cl-

Zn++ +2Cl- ZnCl2

Zn+ 2NH4Cl 2NH3 +ZnCl2 +2H++2e-

The electrons so released are collected by zinc rod, making it at negative potential w.r.t to electrolyte.
The ammonia gas so produced escapes. The hydrogen ions diffuse through the porous pot and interact with
manganese dioxide according to following reaction
2H+ + 2MnO2 Mn2O3 +H2O
+ 2 units of positive charge.
This positive charge is transferred to the carbon rod which attains the positive potential w.r.t. electrolyte. The
depolariser (MnO2) in Leclanche cell is in solid form and is slow in action. Therefore, when the current is drawn from
the Leclanche cell, the hydrogen is liberated quickly than MnO2 can use it up. So, after some time, a partial
polarisation sets in due to accumulation of hydrogen on cathode and thereby, the current falls off. When the circuit is
switched off, the hydrogen gas escapes. The cell regains its original e.m.f. When the cell is allowed to rest for some
time, Mn2O3 changes back to MnO2 by taking O2 from the atmosphere and cell is again ready for use. Thus Leclance
cell is useful in those experiments where intermittent supply of current in needed.
 FIGURE 2(d) 9

The e.m.f of Leclanche cell is 1.45V and its internal resistance can vary from 0.1 to 10.
A dry cells is a portable form of a Leclanche cell. It consists of zinc vessel which acts as a negative electrode or anode.
The vessel contains a moist paste of saw dust saturated with a solution of ammonia chloride and zinc chloride.
16. Dry Cell :
The ammonium chloride acts as an electrolyte and the purpose of zinc chloride is to maintain the moistness of
the paste being highly hygroscopic. The carbon rod covered with a brass cap is placed in the middle of vessel. It acts
as positive electrode or cathode. It is surrounded by a closely packed mixture of charcoal and manganese dioxide
(MnO2) in a muslin bag. Here Mn02 acts as depolariser. The zinc vessel is scaled at the top with pitch or shellac. A
small hole is provided in it to allow the gases formed by the chemical action to escape. Fig. 2(d).10. The chemical
action inside the cell is the same as in Leclanehe cell.
The e.m.f. of dry cell is 1.5 V. If this cell is used continuously, the polarisation defect may develope in this cell but it
regains its e.m.f. if allowed to rest for a while.
End point voltage of a cell. It is the lowest voltage a cell can tolerate and still be functional. The end point
voltage of dry cell is 0.8 V.

FIGURE 2(d) 10
17: Standard Cell
Standard cell is that cell which can provide nearly a constant e.m.f. over a very long periods of time. The
Daniel cell and Leclanche cell as discussed above do not have constant e.m.f. with time due to change
in the ionic concentration of their electrolytes. The commonly used standard cell is the weston cadmium cell
as shown in Fig. 2(d).11.

FIGURE 2(d) 11
\

It consists of H-shaped glass vessel whose two vertical limbs A and B are 3" long and (1/2)" diameter.
The positive electrode or cathode of the cell is pure mercury at the bottom of limb A. Above which there is a
paste of mercurous sulphate (Hg2S0 4) which acts as a depolariser. Over this paste , cadmium sulphate
(CdSO 4 ) crystals are placed.
The negative electrode or anode of the cell is cadmium-mercury (Cd Hg) amalgam placed at the bottom
of the other tube B. Over this amalgam, cadmium sulphate crystals are placed.
The electrolyte is a saturated solution of cadmium sulphate which is filled in both the limbs of the tube.
Platinum wires are sealed at the bottom of each limb of the tube which are connected to the terminals on the
insulated box in which H-shaped vessel is kept. The cell can be connected to the external circuit through
the terminals on the box.

When the cell is in use the chemical reactions involved in this cell are given below

(i) At the negative electrode

Cd = Cd++ + 2e-
Thus the cadmium atoms give the negative charges.
 (ii) At the positive electrode

Cd ++ +CdSO 4 + HgSO 4 = 2CdSO 4 +2Hg +

The mercury ions acquire negative charge from the positive electrode, get neutralised and deposit
there i.e. 2e + 2 Hg+ = 2 Hg

Due to these reactions a constant potential difference is developed between two electrodes of the cell and a
constant electronic current is maintained in the external circuit. The e.m.f. of this cell is 1.0183 V at 20C,
which is independent of temperature over a considerable range.

18.Secondary cell

A secondary cell is that cell in which the electrical energy is first stored up as a chemical energy and when
the outside circuit is closed to draw the current from the cell, the chemical energy is reconverted into
electrical energy. The chemical reactions are reversible in this cell.
The secondary cells are also called storage cells or accumulators because they act in such a way as if they
were reservoir of electricity i.e., the current can be drawn from them whenever required and when they
are discharged, they can be recharged. The commonly used secondary cells are Lead-Acid Accumulator
and Edison cell.

2(e) Thermoelectric Effects of current

2(e).1. Seebeck Effect
Seebeck in 1821 found that if two wires of different metals, say copper and iron, are joined at their ends A and
B, through a low resistance galvanometer G to form a closed circuit, and if one of the junctions, say A, is
heated and the other junction B is kept cold, the galvanometer shows a deflection. Fig. 2(e).1. This must be
due to a current in the circuit called thermo electric current. The current must further be due to certain e.m.f.
called thermo e.m.f. The assembly of two different metals joined at their ends to have two junctions in a
circuit, is called a thermocouple. This phenomenon is known as thermo-electric effect as electricity has been
produced from heat. As this phenomenon of thermo-electricity was discovered first of all by Seebeck, hence it
is also called Seebeck effect.

FIGURE 2(e) 1

Thus Seebeck effect is the phenomenon of generation of an electric current in a thermocouple by keeping its
two junctions at different temperatures.
T h e d i r e c t i o n o f c u r r e n t i n C u F e thermocouple is from Cu to Fe through hot junction and
can be remembered by the word chi. In Sb Bi thermocouple the direction of current is Sb to Bi through cold
junction. It can be recollected by ABC.
Seebeck found that the magnitude and direction of thermo e.m.f. devel oped in a thermocouple
depends upon :
(i) the nature of met als forming the thermocouple.

(ii) difference in temperatures of the two junctions.

The Seebeck effect is reversible. It means if the hot and the cold junctions are interchanged, the direction of
thermoelectric current is reversed. Thus seebeck effect is a reversible effect.

Seebeck from his experimental investigations, arranged a number of metals in a series known as Seebeck
series. Some of the metals of this series, in the order Seebeck arranged them, are given below.
Bismuth, constant, nickel, platinum, mercury, aluminium, lead, silver, gold, copper, zinc, iron, nichrome and
antimony.

When any two of these metals form a thermocouple, current flows through the hot junction from a metal
occurring earlier; to a metal occurring later; in the series.
Seebeck also found that for a given difference of temperatures of two junctions, the larger is the gap in Seebeck
series between the metals forming the thermocouple, the greater will be the thermo e.m.f. generated. That is
why, the thermo e.m.f. developed is maximum in a thermo-couple of antimony and bismuth for a given
difference in temperatures of the two junctions. The thermo e.m.f. is of the order of 10-3 V or less.
For a temperature difference of 100C between the two junctions, the thermo e.m.f. produced
in CuFe thermocouple is only 0.0013 V . and in SbBi thermocouple is 0.008 V.
2(e).2. Origin of Thermo E.M.F

We know that number of electrons per unit volume (i.e. electron density) of a conductor depends on
material of the conductor. In general, it is different for different conductors.
When two different metals are brought into contact, at the junction, the free electrons tend to diffuse from
the metal with greater free electron density to the other with lower free electron density. Due to this diffusion,
a potential difference is developed at the junction of the two metals called contact potential. When both the
junctions are at the same temperature, the contact potentials at the two junctions will be the same. Hence no
current flows in the thermocouple. But if one junction is heated up, the rate of diffusion of fre_ electrons at that
junction will change. As a result of it, the contact potentials at the two junctions will become different and
there will be an effective potential difference (e.m.f.) in the circuit, called thermo e.m.f.
Thus the thermo e.m.f. produced in a thermocouple is equal to the difference in contact potentials at
the two junctions A. and B and is given by
VAB = VA - VB
2(e).3.Effect of temperature on Thermo E.M.F
To study the effect of temperature on thermo e.m.f. let us take Cu- Fe thermocouple with a sensitive
galvanometer G connected in the circuit as shown in Fig. 2(e).2 (a).
K e e p i n g t h e j u n c t i o n B a t c o n s t a n t temperature 0C, the temperature of junction.A is iiaduallY-
increased. The deflection m the galvanometer and corresponding temperature of junction A is gradually increased. The.
Deflection in the galvonameter and the corresponding temperature of
the hot junction are recorded.The deflection in the
galvonameter is directly proportional to the thermoelectric current
and hence the thermo e.m.f. The graph showing the variation
between thermo e.m.f. and temperature of hot junction is found
to be parabolic in shape as shown in Fig. 2(e).2 (b).
From these observations, we note that :
(i) w h e n t h e t w o j u n c t i o n s o f t h e thermocouple are
at same temperature (say 0C),galvanometer shows no deflection
i.e. thermo e.m.f. is zero.
HOT JUNCTION
FIGURE .2(e).2

(ii) As the temperature of the hot junction increases, keeping the cold junction at constant temperature 0C,
the thermo e.m.f. increases with the increase in temperature till it becomes maximum at a certain
temperature.

The temperature of the hot junction at which thermo e.m.f in a thermocouple is maximum is called
neutral temperature. It is represented by Fn in the graph.
The value of neutral temperature.
(a) is constant for a thermocouple.
(b) depends upon the nature of materials forming the thermocouple:
(c) is independent of the temperature of cold junction.
F o r C u F e t h e r m o c o u p l e , n e u t r a l temperature is 270C, whatever may be the temperature
of cold junction.
(iii) When hot junction is heated beyond ne ut r al t em p e r at u r e, t he rm o e.m . f s t a rt s decreasing
instead of increasing.
(vi) At another particular temperature of hot junction, the value of thermo e.m.f. becomes zero. On
heating slightly further, the direction of thermo e.m.f. is reversed. It is due to the number densities and rates of
diffusion of electrons in the two metals used are reversed.
The temperature of the hot junction at which the therrno e.m.f in a thermocouple becomes zero and just beyond it
reverses its direction is called Temperature of Inversion. It is represented by T1.
The value on temperature of inversion depends
(a) the temperature of the cold junction and
 (b) the nature of materials forming the Thermo-couple.
Thus for a given thermocouple, there will be different values of temperature of inversion corresponding to
different values of temperature of cold junction.
2(e).4. Relation between Tn and 'T1;
It is found that temperature of inversion T1 is as much above the neutral temperature (T) as much above the
neutral temperature is above the temperature of the cold junction (T0, say) i.e.
Ti Tn = Tn T0 or Ti =2 Tn T0
Ti T0
Or Tn =
2
Here, Ti , Tn and T1 are in and not in Zkelvin or absolute temperature.
The temperature of inversion of a thermocouple is 620C and the neutral temperdture is 300CFind.temparature
of cold junction.
Sol. Ti Tn = Tn T0
or T0 = 2 Tn Ti = 2 x 300 620 = - 20C.

2(e).5. Thermo-Electric Power

Thermo electric power is defined as the rate of change of themro e.m.f with temperature. It is also called Seebeck
coefficient and is denoted by S.
From experimental study, it was concluded that the variation of therm e.m.f. E with the temperature T C
of the hot junction, when cold junction is at 0C is a parabolic curve represented by the equation
1
E = T +2 T2

where and are constants which depend upon the nature of the metals forming the
thermocouple and the temperature difference of the two junctions.
The thermoelectric power (called Seebeck coefficient) is given by
dE
S T 2 . (i)
dT
It means, S T
dE
Hence the graph between S = and T will be a straight line AB as shown in Fig. 2(e).3.
dT

'
dE dT
FIGURE 2(e).3

[Note. The shape of graph is due to the fact that the value of dE/dT (i.e. the slope of tangent). at various
locations on parabolic curve representing the variation of E and T for a thermocouple, decreases with
the increase in T and becomes zero when T = T n ]
When T=0, from (ii),
dE
S= = = OA (the intercept)
dT
It shows the thermoelectric power is independent of the temperature of cold junction.
Since neutral temperature (T n) is that temperature of the hot junction at which thermo e.m.f. in a thermocouple is
dE
maximum, therefore at neutral temperature = 0 and T = T n
dT
From (ii), 0 = = + Tn
or Tn = - /
If cold junction is at 0 then T1 = -2/
Do you know?
In a thermocouple, the thermoelectric power at neutral temperature is zero.
In a thermocouple, the thermoelectric power is independent of temperature of cold junction.
Thermoelectric power is positive if temperature of the hot junction lies in between temperature of cold junction
and neutral temperature and is negative for temperature between neutral temperature and temperature of
inversion.
For a given thermocouple if the values of a and b are positive and temperature of cold junction is 0Cor more,
then there will be no detection of neutral temperature and temperature of inversion for this thermocouple.

For copper - iron couple, the thermo e.m.f. (temperature of cold junction at 0C) is given by E = (14 -
0.022) V. Find
(i) them electric power at 0 = 50C and
(ii) neutral temperature.
Sol. (i) Thermo electric power,
dE d
(14 0.02 2 )
S = d d
= 14 0.02 x 2
 = 14 0.02 x 2x50
= 12V -1
(iii) When = n,
dE
d = 0;
14
So, n = 0.02 2 = 350C
Peltier in 1834 found that if a current is passed through a junction of two different metalS, the heat is either
evolved or absorbed at that junction. This effect is known as Peltier effect. The quantity of heat absorbed or
evolved at a junction is proportional to the quantity of charge crossing that junction. If the direction of current
is reversed, the heating effect at that junction is also reversed. Thus Peltier effect is reversible effect. It is also
complementary to Seekbeck effect.
In an Sb - Bi thermocouple, when the junction A is heated and B is kept cold, according to Seebeck effect,
thermo- electric current flows from Sb to Bi at the junction B and Bi to Sb at the junction A Fig. 2(e).4 (a).
When battery is inserted in the circuit so that current flows from Sb to Bi through junction B. k e e p i n g b o t h
t h e j u n c t i o n s a t t h e s a m e temperature, the Peltier heat is evolved at the junctio n B and is
absorbed at junction A, Fig. 2(e) .4(h). When the direction of current is reversed, heat is evolved at
junction A and is absorbed at junction B. This shows that Peltier effect is also reversible like seebeck
effect.

FIGURE 2(e).4

From above we note that the Peltier heat is evolved at a junction of a thermocouple which is kept cold for
Seebeck effect and the Peltier heat is absorbed at a junction of a thermocouple which is kept hot for Seebeck
effect. Thus outcome of Peltier effect and Seebeck effect is complementary to each other. Hence, Peltier effect
is complimentary to Seebeck effect.
Peltier co-efficient. Peltier co-efficient is defined as the amount of heat energy absorbed or
fit a junction of two different metals when one coulomb charge passes through that junction. It is denoted by
and is given by
 Peltier heat
= charge flowing

S. I. unit ofr is JC-1

Peltier co-efficient depends upon (i) the nature of the two metals forming the junction and (ii)
temperature of the junction. Peltier effect has different values for hot and cold junctions.
2(e).7. Difference between Peltier Effect and Joule's Heating Effect
PELTIERS EFFECT JOULES EFFECT
1 . It is reversible effect. 1. It is reversible effect.
2 It takes place only at
2.It occurs throughout the conductor.
the junction of twodifferent metals.
3. It may be heating or cooling effect. 3.It is always aa heating effect.
4. Heat evolved or absorbed at a junction
4. Heat produced is proportional to the square of
is proportional to thefirst power of current
through the junction. current through the conductor.
5. It depends upondirection of current.
5.It is independent of the direction of current
6. Heat evolved or absorbed depends
upon (i) the nature of the two metals Heat produced depends on the resistance of the
forming the junction
conductor
(ii)temperature ofjunction.

2(d).8: Thomson's Effect

Thomson's effect was discovered by Thomson (later called Kelvin). According to this effect, if two parts of
a single conductor are maintained at different temperatures, an e.ni.f is developed between them. The e.m..1 so
produced is called Thomson's e.m.f. If the steady current is passed through an unequally heated conductor, an
absorption or evolution of heat in excess of Joule's heat, takes place in the conductor.

Thus Thomson's effect is the absorption or evolution of heat in excess of Joule heat when current is passed
through an unequally heated conductor: Thomson effect is reversible effect.
To understand Thomson's effect, consider an unequally heated rod AB of copper. Let the endA of the rod be
at higher temperature than its end On passing the current from A to B in the rod, heat is evolved along the
length of the rod. In case, the current is passed in the rod from end B to A, the heat is absorbed along the
length of the rod. It is accounted due to the fact that in case of copper, the hot end of the rod is at higher
potential and its cold end is at lower potential. When current flows from hot end to cold end of copper rod i.e.
from higher potential to lower potential, the energy is produced which is radiated out in the form of heat.
When current is flowing from cold end to hot end of the copper rod i.e. from lower potential to higher
potential, the energy is required which accounts for the absorption of heat energy. Thomson's effect for copper
is positive. Other substances showing positive Thomson's effect are Sb, Ag, Zn etc.
There are some other substances like Fe, Co, Bi, Pt etc., for which Thomson's effect is negative. It
means for such metals, Thomson's effect is just reverse as that for copper. It means, according to Thomson's
effect for iron rod, heat is absorbed when current is passed from hot end to cold end and heat is evolved
when current is passed from cold end to hot end of the rod.

For lead, Thomson's effect is nil. It means no heat is evolved or absorbed when current is passed through
an unequally heated rod of lead. It is due to this reason that lead is used as a reference metal in
thermoelectricity.
Thomson's coefficient. Thomson's co- efficient is defined as the e.m.f that exists between the two points of a
uniform conductor which has a temperature difference of 1C (or 1K). It is denoted by .

Let dV = Potential difference between two points of a metal rod.

dT = Temperature difference between the same two points of rod.
Then Thomson's co-efficient of the rod is
dV
given by = dT or dV = dT.

Total Thomson's e.m.f between temperature T1 and T 2 of a metal rod is given by

T1
V dT
T2

Thomson's co-efficient is also defined as the. amount of heat energy evolved or absorbed between the two
points of a conductor maintained at a unit temperature lifference when unit current is passed for one second
through the conductor).
If current I flows through a conductor for time t, then the amount of heat energy evolved or absorbed
between the two points of the conductor maintained at a unit temperature difference is given by Q= It.
Relation between Seebeck, Peltier and Thomson's coefficients
If S , and are the Seebeck, Peltier and Thomson's coefficients, then it can be established that

dE
T TS
dT
d 2E d dE dS
T 2 T T
dT dT dT dT

Do you know?
In a thermocouple seebeck e.m.f. is a combination of peltier e.m.fs. and Thomsons e.m.fs.
Seebeck effect, Pelter effect and Thomsons effect are all reversible effects but joule,s heating effect is
irreversable effect.
The thomsons e.m.f for lead is zero.

2(e).9. Two Laws of Thermo tlectricity

The following are the two laws of thermo electricity which were established experimentally.
 1. Law of successive metals (or law of intermediate metals). If a number of metals are in
successive contacts, so as to form a chain, then the effective e.m.f: between extreme metals when placed in direct
contact at a given temperature is equal to the sum of the individual e.m.fs. between adjacent metals provided al l
the junctions are at the same temperature.

If A and D are the extreme metals and B, Care the inlet intermediate metals, then

E AD E AB EBC ECD

2.Law of successive temperature (or law of intermediate temperature). It states that the e.m.f.
for a given thermocouple with junctions at temperature T1 and Tn is equal to the sum of the
e.m.fs. of the thermocouples of the same metals with junctions at temperatures ; T1 and T2, T2 and
T 3, T 3 and T4, ... Tn-1 and T, i.e.,

ETT1n ETT12 ETT23 .........ETTnn1

2(e).10 Applications of Thermoelectric Effects

Important applications of thermo- electric effects are as follows :

(i) T o m e a s u r e t e m p e r at u r e ; u si n g thermoelectric thermometers.
(ii) To detect heat radiation ; using thermopile
(iii) Thermoelectric refrigerator
(iv) Thermoelectric generator.
2(e)11. Thermo Electric Thermometers

A thermoelectric thermometer is used for the measurement of temperatures both low and high.

P r i n c i p l e . I t s w o r k i n g i s b a s e d o n Seebeck-effect. Thermocouples of different metals are

constructed depending upon the temperature to be measured as given below :

Thermocouple Range of temperature

(i) Copper and Gold-Iron alloy 1K to 50K

(ii)Copper and Constantan 50K to 400 K

(iii) Platinum and Platinum- Iridium alloy 400 K to 1300 K

(iv) Platinum and Platinum-
Rhodium alloy 1300 K to 2000K

Cons tru cti on . The wi res formi ng t he thermocouple are welded together at one end and this end
forms the hot junction. The portions of the wires near the hot junction are properly insulated from each other by
enclosing them in a hard-glass capillary tube C.T The wires are passed through mica discs D, which are
fitted one above the other in a porcelain tube T. The ends of these wires are connected to the terminals T1 and
T2. To these terminals are connected compensating leads Li and L2 of the same materials as those forming the
thermocouple itself. By so doing, the cold junction is shifted to a convenient place, where a constant
temperature of 0C is maintained.

FIGURE 2(e).5

By keeping hot junction at different known temperatures, the corresponding values of thermo e.m.fs.
are noted using digital voltmeter in the circuit of thermocouple. The digital voltmeter gives very accurate
reading of the thermo e.m.f. because its internal resistance is very high (about 10 8 to 109 ). A graph is
plotted between the temperature 4 hot junction and thermo e.m.f. as shown in Fig. 2(e).6. The curve so obtained
is called calibration curve.

TEMP. OF HOT JUNCTION --11

FIGURE 2(e).6
 To find the unknown temperature of a given bath, the hot junction is placed in the giVen bath. The
thermo e.m.f. so generated is measured. The temperature corresponding to this value of thermo e.m.f. is
determined from the calibration curve.

N o t e . I t i s i m p o r t a n t t o n o t e t h a t thermocouple should not be used to measure the temperature

above the neutral temperature.
Advantages
1. Thermoelectric thermometers can be used over much wider range of temperatures ; ranging from --
200C to 1600C.
2. These thermometers are cheap and can be constructed easily.
3 . Thes e can be used to measure the temperature of small cavity.
4. Their thermal capacity being low, they attain the temperature to be measured very quickly and are,
thus useful for measuring changing temperatures.
Disadvantages
1. Since these thermometers are not direct reading thermometers, so they can not be used for calorimetric
purposes.,
2. There is no common relation connecting thermo e.m.f. and the temperature of a junction in any
thermocouple. Therefore, the given thermocouple has to be calibrated first.
3. For the measurement of temperature over different ranges, different thermocouples are to be used.

2(e).12.Thermopile

A thermopile is a sensitive instrument used for detection of heat radiation and measurement of their
intensity. It is based upon Seebeck effect.
As shown in Fig. 2(e).7, a thermopile consists of a number of thermocouples of Sb Bi, all connected in
series. One set of junctions on one side is coated with lamp black. The other set of junctions on the other
side is well polished. The arrangement is enclosed in a funnel or horn shaped vessel.

Bi
FIGURE 2(e).6
The two ends Ti and T2 of the thermopile are connected to a sensitive galvanometer.
Heat radiations coming from the funnel shaped side of the vessel are made to fall on the set of junctions
coated with lampblack. These are absorbed and consequently the temperature of all the junctions in this
set is raised. The other set of junctions being polished, reflect these radiations and remain cold. Thermo
e.m.f. is developed in each thermocouple. As thermocouples are connected in series, the
thermoelectric current in each flows in the same airection (i.e., from antimony to bismuth at cold
junction). The total current is therefore large and produces deflection in the galvanometer.
The deflection in the galvanometer indicates the existence of heat radiations. The deflection is calibrated to
measure directly the intensity of heat radiations.

This instrument is so sensitive that it can detect heat radiations from a match stick lighted at a distance of
50 metres from the thermopile.
2(e).13 Thermoelectric Refrigerator

The working of thermo-electric refrigerator is based on Peltier effect. According to Peltier effect, if
current is passed through a thermocouple, heat is absorbed at one junction and is evolved at the other junction
of the thermocouple. If on the whole, the heat is absorbed, then the thermocouple acts as thermoelectric
refrigeratof. Such a refrigerator has no motor or compressor. Its efficiency is small in comparison to
conventional refrigerator. Thermo- electric refrigerator is very useful when the region to be cooled is very
small and the noise is not acceptable.
The thermocouple selected for the use of thermoelectric refrigerator should have the following
characteristics :

(i) Low resistivity, so that the loss of energy in the form of Joule heat is minimum.
(ii) Low thermal conductivity. It will help in maintaining large temperature difference between the two
junctions.

(iii)High thermo-electric power

The best material satisfying the above characteristics is the semi-conductor Bi2Te3 (compound of
bismuth and tellurium).
2(e).14 Thermoelectric Generator
Thermocouple can be used to generate electric power using Seekbeck effect in remote areas. It
can be achieved by heating one junction in a flame of kerosene oil lamp and keeping the other junction at room
or atmospheric temperature. The thermo e.m.f. so developed is used to operate radio receivers or even radio
transmitters.
2(e).15.Thermocouple-current meter
It is used to measure accurately both the direct curret and alternating current. Its workig is based on
Seebeck effect. The thermocouple- current meter consists of a resistance R made of tungsten, to the
middle of which one junction of Sb-Bi thermocouple is sealed. The other junction of this thermocouple is
kept at room temperature. A sensitive galvanometer G is connected in series of Sb-Bi thermocouple :

FIGURE 2(e).8

Fi rs t of al l we cal i b rat e t he sc al e of galvanometer by passing different known currents through

resistance R.
Now the current I to be measured is passed through resistance R. It heats up the resistance R. The rate of
heat production H = I2R i.e. H I2. (for given value of R). This heat warms up one junction of Sb-Bi
thermocouple. Due to which a thermoelectric current is set up in a thermocouple. The galvanometer G shows a
reading which is the measure of current. Since the heat produced is proportional t o the square of
current , the instrument can be used both for alternating and direct currents.