www.sakshieducation.

com
www.sakshieducation.com
TOPIC-4
ELECTRO CHEMISTRY
Faradays laws of electrolysis and applications
VERY SHORT !S"ER #$ESTIO!S
%&E'plain Faradays First law of elelctrolysis(
ns) Faraday*s First +aw) When an electric current is passed through an electrolyte,
the amount of substance deposited is proportional to the quantity of electric charge
passed through the electrolyte.
If W be the mass of the substance deposited by passing Q coulomb of charge, then
according to the law, we have the relation:
W Q
A coulomb is the quantity of charge when a current of one ampere is passed for one
second. hus, amount of charge in coulombs,
Q ! current in amperes " time in seconds
! I " t
#o W I " t
or W ! $ " I " t
where $ is a constant, known as electro%chemical equivalent, and is characteristic of the
substance deposited.
&. E'plain faradays Second law of elelctrolysis(
ns) When the same quantity of charge is passed through different electrolytes, then the
masses of different substances deposited at the respective electrodes will be in the ratio of
their equivalent masses.
Again according to first law,
W ! '"Q
hen Q ! ()*++ coulomb, W becomes gram equivalent mass ,-..
hus, - ! '"()*++
or ' ! -/()*++
$
0
/$
&
! -
0
/-
&
1. E'plain ,ow f-nda.ental -nit of c,ar/e can 0e fo-nd o-t(
ns) F-nda.ental -nit of c,ar/e) As one g%equivalent of an ion is liberated by ()*++
coulomb, it follows that charge carried by one g%equivalent of an ion is ()*++ coulomb.
If the valency of an ion is 2n2, then one mole of these ions will carry a charge of n3
coulomb. 4ne g%mole of an ion contains ).+& " 0+
&1
ions.
hen,
he charge carried by an ion ! n3/,).+& " 0+
&1
. coulomb
3or n ! 0,
he fundamental unit of charge ! 3/,).+& " 0+
&1
.
i.e., ()*++/,).+& " 0+&1 . ! 0.) " 0+
%0(
coulomb
or 0 coulomb5!).&6 " 0+
07
electrons
he rate of following of electric charge through a conductor is called the electric current.
4& Find t,e c,ar/e in co-lo.0 on % /-ion of(
Sol-tion) 8harge on one ion of 9
1%
! 1 " 0.) " 0+
%0(
coulomb
hus, charge on one g%ion of 9
1%
! 1 " 0.) 0+
%0(
" ).+& " 0+
&1
! &.7( " 0+
*
coulomb
1& How .-c, c,ar/e is re2-ired to red-ce 3a4 % .ole of l
56
to l and 304% .ole
of to 7n
86
(
Sol-tion) ,a. he reduction reaction is
Al
1:
: 1e
%
%%; Al
0 mole 1 mole
hus, 1 mole of electrons are needed to reduce 0 mole of Al
1:
.
Q ! 1 " 3
! 1 " ()*++ ! &7(*++ coulomb
,b. he reduction is
<n
6
%
: 7= : *e
%
%%; <9
&:
: 6=
&
4
0 mole * mole
Q ! * " 3
! * " ()*++ ! 67*++ coulomb
+O!9 !S"ER #$ESTIO!S
%& E'plain t,e Faradays +aw of Electrolysis(
ns) he relationship between the quantity of electric charge passed through an
electrolyte and the amount of the substance deposited at the electrodes was presented by
3araday in 0716, in the form of laws of electrolysis.
3i4 Faraday*s First +aw
When an electric current is passed through an electrolyte, the amount of substance
deposited is proportional to the quantity of electric charge passed through the electrolyte.
If W be the mass of the substance deposited by passing Q coulomb of charge, then
according to the law, we have the relation:
W Q
A coulomb is the quantity of charge when a current of one ampere is passed for one
second. hus, amount of charge in coulombs,
Q ! current in amperes " time in seconds
! I " t
#o W I " t
or W ! $ " I " t
where $ is a constant, known as electro%chemical equivalent, and is characteristic of the
substance deposited.
When a current of one ampere is passed for one second, i.e., one coulomb ,Q ! 0., then
W ! '
hus, electrochemical equivalent can be defined as the mass of the substance deposited
by one coulomb of charge or by one ampere of current passed for one second. 3or
e>ample, when a charge of one coulomb is passed through silver nitrate solution, the
amount of silver deposited is +.++0007 g. this is the value of electrochemical equivalent
of silver.
Faraday*s Second +aw
When the same quantity of charge is passed through different electrolytes, then the
masses of different substances deposited at the respective electrodes will be in the ratio of
their equivalent masses.
he law can be illustrated by passing same quantity of electric current through three
voltametres containing solutions of =
&
#4
6
, 8u#4
6
and Ag94
1
respectively as shown in
3ig.0&.0. In the first voltameter, hydrogen and o>ygen will be liberated? in the second,
copper will be deposited and in the third, silver will be deposited.
,<ass of hydrogen./,<ass of copper. ! ,-quivalent mass of hydrogen./
,-quivalent mass of copper.
or ,<ass of copper./,<ass of silver. ! ,-quivalent mass of copper./
,-quivalent mass of silver.
or ,<ass of silver./,<ass of hydrogen. ! ,-quivalent mass of silver./
,-quivalent mass of hydrogen.
It is observed that by passing one coulomb of electric charge.
=ydrogen evolved ! +.++++0+1) g.
8opper deposited ! +.+++1&(& g.
and #ilver deposited ! +.++0007 g
hese masses are in the ratio of their equivalent masses. 3rom these masses, the
amount of electric charge required to deposit one equivalent of hydrogen or copper or
silver can be calculated.
3or hydrogen ! 0/+.+++0+1)! ()*++ coulomb
3or copper ! 10.@7/+.+++1&(&! ()*++ coulomb
3or silver ! 0+@.77/+.++0007 ! ()*++ coulomb
his follows that ()*++ coulomb at electric charge will deposit one g equivalent of any
substance. ()*++ coulomb us termed as one 3araday and is denoted by 3.
Again according to first law,
W ! '"Q
hen Q ! ()*++ coulomb, W becomes gram equivalent mass ,-..
hus, - ! '"()*++
or ' ! -/()*++
$
0
/$
&
! -
0
/-
&
8& E'plain t,e applications of Faradays +aws of electrolysis(
ns)
pplications of Electrolysis
he phenomenon of electrolysis has wide application. he important ones are:
3%4 :eter.ination of e2-i;alent .asses of ele.ents)
According to second law of electrolysis when the same quantity of electronic current is
passed through solutions of salts of two different cells, the amounts of the metals
deposited on the cathodes of the two cells are proportional to their equivalent masses of
the respective metals. If the amounts of the metals deposited on the cathodes be W
A
and
W
A
respectively, then
"

<"
=
> 3E2-i;alent .ass of 4<3E2-i;alent .ass of =4
Bnowing the equivalent mass of one metal, the equivalent mass of the other metal can be
calculated from the above relationship. he equivalent masses of those non%metals which
are evolved at anodes can also be determined by this method.
384 Electron .etall-r/y)
he metals like sodium, potassium, magnesium, calcium aluminum, etc., are obtained by
electrolytes of fused electrolytes.
F-sed electrolyte 7etal isolated
9a8l : 8a8l
&
: B3 9a
8a8l
&
: 8a3
&
8a
Al
&
4
1
: cryolite Al
<g8i
&
,1*C. : 9a8l ,*+C. : 8a8l
&
,0*C. <g
9a4= 9a
B8l : 8a8l
&
B
354 7an-fact-re of non-.etals)
9on%metals like hydrogen, fluorine, chlorine are obtained by electrolysis.
344 Electro-refinin/ of .etals)
he metals like copper, silver, gold, aluminum, tin, etc., are refined by electrolysis.
314 7an-fact-re of co.po-nds)
8ompounds like 9a4=, B4=, 9a
&
84
1
B8I4
1
, white lead, B<n4
6
, etc., are
manufactured by electrolysis.
3?4 Electroplatin/)
he process of coating an inferior metal with a superior metal by electrolysis is known as
electroplating.
he aims of electroplating are:
,i. o prevent the inferior metal from corrosion.
,ii. o make it more attractive in appearance.
he obDect to be electroplated is made the cathode and block of the metal to be deposited
is made the anode in an electrolytic bath containing a solution of a salt of the anodic
metal. 4n passing electric current in the cell, the metal of the anode dissolves out and is
deposited on the cathode%article in the form of a thin film. he following are the
requirements for fine coating:
,i. he surface of the article should be free from greasy matter and its o>ide layer. he
surface is cleaned with chromic acid or detergents.
,ii. he surface of the article should be rough so that the metal deposited sticks
permanently.
,iii. he concentration of the electrolyte should be so adDusted as to get smooth coating.
,iv. 8urrent density must be the same throughout.
For
electroplatin/
node Cat,ode Electrolyte
With copper
With silver
With nickel
With gold
With $inc
With thin
8u
Ag
9i
Au
'n
#n
4bDect
4bDect
4bDect
4bDect
Iron obDects
Iron obDects
8u#o
6
: dilute =
&
#o
6
BAg,89.
&
9ickel ammonium sulphate
BAu,89.
&
'n#4
6
#n#4
6
T,ic@ness of coated layer
Eet the dimensions of metal sheet to be coated be ,a cm " b cm..
hickness of coated layer ! c cm
Folume of coated layer ! ,a " b " c. cm
1
<ass of the deposited substance ! Folume " density
! ,a " b " c. " d g
!; ,a " b " c. " d ! ,I"t"-./()*++
Gsing above relation we may calculate the thickness of coated layer.
Sol;ed E'a.ples on Faradays +aws of Electrolysis
So.e Sol;ed E'a.ples
E'a.ple %& 3ind the charge in coulomb on 0 g%ion of
Sol-tion) 8harge on one ion of 9
1%
! 1 " 0.) " 0+
%0(
coulomb
hus, charge on one g%ion of 9
1%
! 1 " 0.) 0+
%0(
" ).+& " 0+
&1
! &.7( " 0+
*
coulomb
E'a.ple 8& =ow much charge is required to reduce ,a. 0 mole of Al
1:
to Al and
,b.0 mole of to <n
&:
H
Sol-tion) ,a. he reduction reaction is
Al
1:
: 1e
%
%%; Al
0 mole 1 mole
hus, 1 mole of electrons are needed to reduce 0 mole of Al
1:
.
Q ! 1 " 3
! 1 " ()*++ ! &7(*++ coulomb
,b. he reduction is
<n
6
%
: 7= : *e
%
%%; <9
&:
: 6=
&
4
0 mole * mole
Q ! * " 3
! * " ()*++ ! 67*++ coulomb
E'a.ple 5& =ow much electric charge is required to o>idise ,a. 0 mole of =
&
4 to 4
&
and ,b.0 mole of 3e4 to 3e
&
4
1
H
Sol-tion) ,a. he o>idation reaction is
=
&
4 %%; 0/& 4
&
: &=
:
: &e
%
0 mole & mole
Q ! & " 3
! & " ()*++!0(1+++ coulomb
,b. he o>idation reaction is
3e4 : 0/& =
&
4 %%; 3e
&
4
1
: =
:
: e
%
Q ! 3 ! ()*++ coulomb
E'a.ple 4 ->actly +.6 faraday electric charge is passed through three electrolytic
cells in series, first containing Ag941, second 8u#46 and third 3e8l1 solution. =ow
many gram of rach metal will be deposited assuming only cathodic reaction in each cellH
Sol-tion) he cathodic reactions in the cells are respectively.
Ag
:
: e
%
%%; Ag
0 mole 0 mole
0+7 g 0 3
8u
&:
: &e
%
%%; 8u
0 mole & mole
)1.* g & 3
and 3e
1:
: 1e
%
%%; 3e
0 mole 1 mole
*) g 1 3
=ence, Ag deposited ! 0+7 " +.6 ! 61.& g
8u deposited ! )1.*/&"+.6 ! 0&.@ g
and 3e deposited ! *)/1"+.6 ! @.6@ g
E'a.ple 1 An electric current of 0++ ampere is passed through a molten liquid of
sodium chloride for * hours. 8alculate the volume of chlorine gas liberated at the
electrode at 9I.
Sol-tion) he reaction taking place at anode is
&8l
%
%%; 8l
&
: &e
%
@0.+ g @0.+ g & " ()*++ coulomb
0 mole
Q ! I " t ! 0++ " * " )++ coulomb
he amount of chlorine liberated by passing 0++ " * " )+ " )+ coulomb of electric
charge.
! 0/,&"()*++."0++"*")+")+ ! (.1&)6 mole
Folume of 8l
&
liberated at 9I ! (.1&)6 " &&.6 ! &+7.(0 E
E'a.ple ?& A 0++ watt, 0++ volt incandescent lamp is connected in series with an
electrolytic cell containing cadmium sulphate solution. What mass of cadmium will be
deposited by the current flowing for 0+ hoursH
Sol-tion) We know that
Watt ! ampere " volt
0++ ! ampere " 00+
Ampere ! 0++/00+
Quantity of charge ! ampere " second
! 0++/00+"0+")+")+ coulomb
he cathodic reaction is
8d
&:
: &e
%
%%; 8d
00&.6 g & " ()*++ 8
<ass of cadmium deposited by passing 0++/00+"0+")+")+
8oulomb charge ! 00&.6/,&"()*++."0++/00+"0+")+")+ ! 0(.+*(7 g
E'a.ple A& In an electrolysis e>periment, a current was passed for * hours through
two cells connected in series. he first cell contains a solution gold salt and the second
cell contains copper sulphate solution. (.7* g of gold was deposited in the first cell. If the
o>idation number of gold is :1, find the amount of copper deposited on the cathode in the
second cell. Also calculate the magnitude of the current in ampere.
Sol-tion) We know that
,<ass of Au deposited./,<ass f 8u deposited.!,-q.mass of Au./,-q.<ass of 8u.
-q. mass of Au ! 0(@/1 ? -q. mass of 8u )1.*/&
<ass of copper deposited
! (.7* " )1.*/&"1/0(@ g ! 6.@)&* g
Eet ' be the electrochemical equivalent of 8u.
- ! ' " ()*++
or ' ! -/()*++ ! )1.*/,&"()*++.
Applying W ! ' " I " t
! * hour ! * " 1)++ second
6.@)&* ! )1.*/,&"()*++. " I " * " 1)++
or I ! ,6.@)&* " & " ()*++./,)1.* " * " 1)++. ! +.+7+6 ampere
E'a.ple B& =ow long has a current of 1 ampere to be applied through a solution of
silver nitrate to coat a metal surface of 7+ cm& with +.++* cm thick layerH Jensity of
silver is 0+.* g/cm
1
.
Sol-tion) <ass of silver to be deposited
! Folume " density
! Area "thickness " density
Kiven: Area ! 7+ cm
&
, thickness ! +.+++* cm and density ! 0+.* g/cm
1
<ass of silver to be deposited ! 7+ " +.+++* " 0+.*
! +.6& g
Applying to silver - ! ' " ()*++
' ! 0+7/()*++ g