Conductors and Insulators :The substances, which allow the passage of electricity, are called conductors whereas those,

which do not allow the

passage of electricity through them, are called insulators. Conductors are of two types :
(1) Metallic conductors : These are the metallic substance which allow the passage of electricity through them with out undergoing any
chemical change. The conduction through metals is due to the movement of electrons in the metallic crystals. Resistance increases with increase of
temperature .examples - Metals, alloys, graphite etc
(2) Electrolytic conductors : These are the substance which allow the passage of electricity through their molten state or through their
aqueous solutions and also undergo chemical decomposition at the same time. The conduction through the electrolytes is due to the movement of
ions. It is generally referred to as electrolytic conduction. The substances, which do not conduct electricity, through their molten state or aqueous
solution, are called non-electrolytes , Resistance decreases with increase of temperature. Examples – H2O, NaCl, AgNO3.

Difference between metallic and electrolytic conductors :

S.N Metallic conductors Electrolytic conductors
1 Flow of current due to movement of free electrons Flow of current due to movement of ions
2 Does not involve transfer of matter involves transfer of matter
3 Does not involve any chemical change involve any chemical change
4 Conducting power usually very high Conducting power is comparatively less
5 Does not follow faraday’s law of electrolysis follow faraday’s law of electrolysis
6 On increasing temperature resistance increases , conductivity On increasing temperature resistance increases ,
decreases conductivity increases

ELECTROLYTES
(a) Substances whose aqueous solutions allow the conduction of electric current and are chemically decomposed are called as electrolytes.
(b) The positive charged ion furnished by electrolyte is called cation while the negative charged ion furnished by electrolyte is called anion.
Types of Electrolytes
(a) Strong Electrolyte - Electrolytes which are highly decomposable in aqueous solution and conduct electricity frequently are called strong
electrolytes eg. Salts of strong acid and bases, mineral acid.
(b)Weak Electrolyte - Electrolytes which are decomposable to a very small extent in their dilute solutions are called weak electrolytes eg.
Organic acids, inorganic acids(H3PO4, HCN) and) bases (Fe(OH)3, NH4OH) etc.
Factors affecting electrolytic conductance :
(1) Nature of electrolyte : Conductance of strong electrolyte is higher than weak electrolyte
Strong electrolyte > Weak electrolyte
(2) Nature of solvent : more polar solvent > less polar solvent
(3) Concentration : conductance decreases with increasing the concentration
(4) Temperature : conductance increases with increasing the temperature because mobility of ions increases
(5) Solvation or hydration : conductance decreases with increasing the hydration of ions
Li+ < Na+ < K+ < Rb+ < Cs +
(6) Viscosity : conductance decreases with increasing the viscosity

Terms related electro chemistry :

(1) Ohm's law : This law states that the current flowing through a conductor is directly proportional to the potential difference across it, i.e.,
I V
where I is the current strength (In Amperes) and V is the potential difference applied across the conductor (In Volts)
V
or I  or V  IR
R

where R is the constant of proportionality and is known as resistance of the conductor. It is expressed in Ohm's and is represented as . The above
equation is known as Ohm's law. Ohm's law may also be stated as,
“the strength of current flowing through a conductor is directly proportional to the potential difference applied across the conductor and inversely
proportional to the resistance of the conductor.”
(2) Resistance : It measures the obstruction to the flow of current. The resistance of any conductor is directly proportional to the length (l) and
inversely proportional to the area of cross-section (a) so that
l l
R  or R  ρ
a a
where  (rho) is the constant of proportionality and is called specific resistance or resistivity. The resistance depends upon the nature of the
material.
l = distance between two electrode
a = area of electrode or dipped surface area ( if area of both electrode is different then we have to take common area of both )
Units : The unit of resistance is ohm ( ).
(3) Resistivity or specific resistance : We know that resistance R is
l
R  ; Now, if l  1 cm , a  1 cm
2
then R  
a
 2
Thus, resistivity is defined as the resistance of a conductor of 1 cm length and having area of cross-section equal to 1 cm . or
Resistance of 1 cm3 of solution will be it's resistivity.
Or
It is the resistance offered by the all the ions present in 1cm3 of an electrolytic solution and denoted by 
2
a cm
Units : The units of resistivity are   R.  Ohm  Ohm . cm
l cm

Its SI units are Ohm metre (  m ). But quite often Ohm centimetre (  cm ) is also used.

(4) Conductance : It is a measure of the ease with which current flows through a conductor. It is an additive property. It is expressed as G. It is
reciprocal of the resistance, i.e.,
1
G 
R

1 1 1
Units : The units of conductance are reciprocal Ohm ( ohm ) or mho. Ohm is also abbreviated as  so that Ohm may be written as  .
1
According to SI system, the units of electrical conductance is Siemens, S (i.e., 1 S  1  ).

(5) Conductivity or specific conductance : It is the conducting power of all ions present in 1 cm3 of an electrolytic solution and it is
reciprocal of specific resistance and is denoted by the symbol,  (Greek kappa).
1  
Thus, K   
 RA A
Units : The units of conductivity are
1 1 1
  Ohm 1
cm–1 or  cm
Ohm . cm

2 1
In SI units, l is expressed in m area of cross-section in m so that the units of conductivity are S m .

(6) Cell constant ; For a given cell l/a is constant called a cell constant and denoted by x
Cell constant (x) = l / a
Unit - unit of cell constant is cm-1
Relation between cell constant and conductivity :
Conductivity = cell constant x conductance
(7) Molar conductivity or molar conductance : Molar conductivity is defined as the conducting power of all the ions produced by
dissolving one mole of an electrolyte in V ml of solution. It is denoted by m (lambda).

K  1000 K  1000
 m  KV m   m 
C molarity

where, C = M is the molar concentration.

V= Volume ( in ml ) of solution which contain 1mole electrolyte
[ derivation:
3
If M is the concentration of the solution in mole per litre, then M mole of electrolyte is present in 1000 cm

1000
1 mole of electrolyte is present in 
3
cm of solution
M

Thus,     Volume
3
in cm containing 1 mole of electrolyte.
  1000
or 
M

Units of Molar Conductance : The units of molar conductance can be derived from the formula ,
  1000

M

3
cm
The units of  are S cm
1
and units of  are, Λ  S cm
1
 S cm
2
mol
1
 S cm 2
mol
1
mol
2 1 3
According to SI system, molar conductance is expressed as S m mol , if concentration is expressed as mol m .

(8) Equivalent conductivity : It is defined as the conducting power of all the ions produced by dissolving one gram equivalent of an electrolyte
in V ml solution. It is expressed as eq and is related to specific conductance as
K  1000
eq = k xV , eq 
Normality
where N= Normality .

2
 1 1
Units of Equivalent Conductance : The units of equivalent conductance are Ohm
2
cm ( gm equiv ) .
= Sm2eq-1
Relation between eq and m :
K  1000 K  1000
We know , m  eq 
molarity Normality

m / eq = N/M = nf , m = N/M = nf x eq

Molar Conductance = valence factor x Equivalent Conductance

Some important unit conversion :

1Sm2mole-1 = 10 4Scm2mole-1 , 1Scm2mole-1 = 10 - 4Sm2mole-1
-1 2 -1 ,
1Scm = 10 Sm 1Sm-1 = 10 - 2Scm-1

Experimental measurement of conductance : (wheat stone bridge ) :

(i) The conductance of a solution is reciprocal of the resistance, therefore, the experimental determination of the conductance of a solution involves
the measurement of its resistance.

Conductance of cell = 1/R4

D. C can’t be used because it provides two complications
(1) Change in the conc. Of the solution occurs due to electrolysis which will change the resistance
(2) Polarisation at electrodes sets in which also changed the resistance
Conductivity water : the solution are always prepared in conductivity water which has no conductance due to dissolved
impurities , it is prepared by distilling a no of times the distilled water to which a little KMnO4 and KOH have been added
-8 -1
in a hard glass distillation assembly , such water has very low conductance of the order of 4.3 x 10 ohm .
Variation of conductance / conductivity / molar conductivity /equivalent conductance with dilution :
(1) Conductance ; conductance of solution (WE/SE) increases with dilution
Weak Electrolyte - increases due to increases in degree of dissociation
Strong Electrolyte - 100% dissociated at all concentration but conductance increases due to increase the mobility of ions
(2)Conductivity : conductance of solution increases with dilution but conductivity of solution both for weak and strong electrolytes. Decreases due
to number of ions per unit volume that carry the current in a solution decreases on dilution.
(3) Molar conductance and equivalent conductance :
The value of eq and m increase with increasing dilution because specific conductance (K)decreases but KXV
increases on dilution . at infinite dilution ( When concentration approaches zero,) the value of eq and m becomes constant due to
fact that dissociation of electrolyte is completed at infinite dilution . at this point

the molar conductivity is known as m

and equivalent conductivity is known as  eq

Variation of s m with concentration for strong electrolyte (Debye-Huckel -Onsagar (DHO) :

the molar conductivity of strong electrolyte is found to vary with concentration according to equation

cm =  m
-b c .,……………………………………(1)

Where ,
b = constant which depends upon the nature of solvent an temperature , C = molar concentration of solution

 c
m
= molar conductance at concentration C m
 
= molar conductance at concentration at infinite dilution
This equation is called DHO equation and is found hold good at low concentration

3
If cm is plotted against c , a linear graph is obtained for low conc. But

Kohlarausch's Law :
(A) ‘‘At infinite dilution, when dissociation complete(100%,), each ion makes a definite contribution towards equivalent conductance of the
electrolyte irrespective of the nature of the ions of other electrolyte
(B) ‘ At infinite dilution the value of equivalent conductance of an electrolyte is the sum of equivalent conductance of its constituent ions.( cation
and anion)’’

 eq
    
=

 m
=
x 

 y  
Where ,
X = no of cation y = no of anion

Ex
 eq
 m

NaCl
 eq
 ( Na

)


(C l

)
m
 ( Na

)


(C l

)
= =
K2SO4
 eq
 (K

)


2  m
2

(K

)


2
= ( SO 4 ) = ( SO 4 )

Al2(SO4)3
 eq
 
( Al
3
)


2  m
2

( Al
3
)
3 

2
= ( SO 4 ) = ( SO 4 )

(
 )c
m
nf x (   )c
eq
(   )c
eq
= = valence factor x

(
 )a
m
nf x (   )a
eq
(   )a
eq
= = valence factor x

Applications of Kohlrausch's law :

Some typical applications of the Kohlrausch's law are described below,

(i) Determination of m for weak electrolytes : The molar conductivity of a weak electrolyte at infinite dilution (  m )

cannot be

determined by extrapolation method. However,  m values for weak electrolytes can be determined by using the Kohlrausch's equation.

CH 3 COOH
 CH 3 COONa
 HCl  NaCl

(ii) Determination of the degree of ionisation of a weak electrolyte : The Kohlrausch's law can be used for determining the degree of

4
ionisation of a weak electrolyte at any concentration. If cm is the molar conductivity of a weak electrolyte at any concentration C and, m is the

  
c
m
molar conductivity of a electrolyte at infinite dilution. Then, the degree of ionisation is given by, 
m


Thus, knowing the value of  , and  m (From the Kohlrausch's equation), the degree of ionisation at any concentration ( c ) can be
c
m

determined.
(iii) Determination of the ionisation constant of a weak electrolyte : Weak electrolytes in aqueous solutions ionise to a very small
extent. The extent of ionisation is described in terms of the degree of ionisation ( ). In solution, the ions are in dynamic equilibrium with the
unionised molecules. Such an equilibrium can be described by a constant called ionisation constant. For example, for a weak electrolyte AB, the
ionisation equilibrium is, AB ⇌ A

 B  ; If C is the initial concentration of the electrolyte AB in solution, then the equilibrium concentrations of
various species in the solution are, [ AB ]  C (1   ), [ A ]  C  and [ B ]  C 
 

[A

][ B

] C  .C  C
2

Then, the ionisation constant of AB is given by, K   

[ AB ] C (1   ) (1   )

We know, that at any concentration C, the degree of ionisation ( ) is given by,   cm / m

C ( m /  m ) C ( m )
c 2 c 2

Then, K   ; Thus, knowing  m and  m at any concentration, the ionisation constant (K) of the electrolyte can
c

[1  ( cm / m )] m ( m  cm )

be determined.
(iv) Determination of the solubility of a sparingly soluble salt : The solubility of a sparingly soluble salt like AgCl . BaSO4 , PbSO4 etc
in a solvent is quite low. Even a saturated solution of such a salt is so dilute that it can be assumed to be at infinite dilution. Then, the molar

conductivity of a sparingly soluble salt at infinite dilution (  m ) can be obtained from the relationship,

m        ........(i)

The conductivity of the saturated solution of the sparingly soluble salt is measured. From this, the conductivity of the salt ( salt ) can be obtained by
using the relationship,  salt   sol   wate r , where,  water is the conductivity of the water used in the preparation of the saturated solution of the salt.
1000  salt
salt  ........(ii)
Cm

From equation (i) and (ii) ;

1000  salt
Cm  , C m is the molar concentration of the sparingly soluble salt in its saturated solution. Thus, C m is equal to the solubility of
(       )
 


the sparingly soluble salt in the mole per litre units. The solubility of the salt in gram per litre units can be obtained by multiplying C m with the molar
mass of the salt.

Ionic Mobility : it is the distance travelled by the per second under potential gradient of the 1 volt per cm and denoted
by 

Ionic Mobility = speed of the ion per unit electrical field

speed speed
 
electrical field potential gradient
–1 2 –1
Unit : Its units are v cm sec
   ,

a
 F  a
,

c
  c

a  F  ,
a  F  a
c  F c
0M 0M
Ionic mobility (  )=u= 
96500 F
 = ionic conductance ,   
a = anionic conductance , c cationic conductance

 n
 a a
  nc x    na x 
 n c c
c a

nc= transport no of cation , na= transport no of anion

5
 Factors affecting mobility :
mobility  Applied voltage
mobility  temperature
mobility  1/ weight of ions
1
Absolute ionic mobility is the mobility with which the ion moves under unit potential gradient. It's unit is cm sec .

Ionic mobility
Absolute ionic mobility 
96,500

Potential gradient ; the ratio of potential difference across the electrode to the distance between them

P. G = V / l

(1)Transport number or Transference number: “The fraction of the total current carried by an ion is known as transport number, transference
number or Hittorf number may be denoted by sets symbols like t+ and t– or tc and ta or nc and na”.
From this definition,
Current carried by an anion Current carried by a cation
ta  , tc 
Total current passed through the solution Total current passed through the solution

evidently, ta  tc  1.

transport number, transference decreases with increasing in concentration

-
Determination of transport number : Transport number can be determined by
(1) Hittorf's method, (2) moving boundary method, (3) emf method
Factors affecting transport number :
A rise in temperature tends to bring the transport number of cation and anion more closer to 0.5
Relation between transport number and Ionic conductance :
 n
 a a
  nc x    na x 
 nc c
c a

nc= transport no of cation , na= transport no of anion

Migration of ions
Electricity is carried out through the solution of an electrolyte by migration of ions. Therefore,
(1) Ions move toward oppositely charged electrodes at different speeds.
(2) During electrolysis, ions are discharged or liberated in equivalent amounts at the two electrodes, no matter what their relative speed is.
(3) Concentration of the electrolyte changes around the electrode due to difference in the speed of the ions.
(4) Loss of concentration around any electrode is proportional to the speed of the ion that moves away from the electrode, so
Loss around anode Speed of cation

Loss around cathode Speed of anion

The relation is valid only when the discharged ions do not react with atoms of the electrodes. But when the ions combine with the material of the
electrode, the concentration around the electrode shows an increase. Transport number or Transference number