Electrolytic Conductance: Conductors: Are two types

Metallic Conductor
Electrolytic Conductors
1. Charge carriers are Electrons
Charge carriers are Ions
2.No Chemical Change
Decomposition of electrolyte can the
place
3. No transfer of mass
transfer of mass
4.Resistance is because of Collision of Resistance is because of Collision of
electrons with fixed metal atoms
ions with fixed Solvent molecules and
inter ionic force of attraction
5. With increase in Temp, Resistance
With increase in Temp, Resistance
increases
decreases
6.Low resistance generally good
High resistance generally good
conduct
conduct
Conductivity depends upon:
Conductivity depends upon: Density,
Concentration, Temperature, nature
Temperature, no of valence electrons,
of electrolyte, Speed of ions, Size of
nature of metal and its structure
the ions, nature of Solvent
Influencing factors of Electrolytic conductance and Resistance
1. Solute Solute interactions: as force of attraction increases, resistance increases
Force Charge
2. Solute Solvent interactions : Greater the salvation, greater will be the resistance
Force Charge 1/ Size
Li+ (hydrate more) > Cs+ (hydrate less)
Resistance of LiCl > Resistance of CsCl
3. Solvent Solvent interactions (Viscosity ): greater the viscosity greater will be resistance
4. With increase in Temperature resistance decreases
5. Nature of electrolyte: weak electrolyte high resistance
Resistance ( R ): Units : Ohm ( ) , SI unit: Kg.m2 / S3. A2
The resistance of a conductor ( Metallic or Electrolytic ) is directly related to length (l) and
inversely to its Cross sectional area (A)

R l,

l
,
A

R=

.l
,
A

= rho= Resistivity or Specific Resistance

Units of ( rho ) : Ohm.meter ( .m ) , When l = 1cm, and A = 1 Cm2 , R =

Resistivity of a solution : the resistance of the solution between two electrodes of 1 cm 2 area
of cross section and 1 cm apart Or Resistance of 1cm3 of solution will be its Resistivity.
Conductance ( G ): The Power of Conductor

1
l
A 1
k.A
G=
,
G=
,
G=
= k (Kappa) , G =
, k= Conductivity or specific conductance

.l
R
.l
l

A
Units of G: Ohm-1 or mho or Siemann ( S ) ( 1 Ohm -1 = 1 S ), Siemann is equal to ohm-1 and
it is also called mho.

Conductivity (k) : The conductance of any solution held between two electrodes of one unit
area each and separated by a distance of one unit
Units of k : S.m-1 ( -1 is known as Siemanns )

k=

G.l
A

but G =

1
,
R

k=

l l

= Cell constant (G ) ,

R.A A

Kappa directly related to no of ions or no of charge carriers

Conductivity or Resistivity of the solution is dependent on its concentration, so two more
type of conductivities are defined for the solution.
Molar conductivity or molar conductance ( m or m )
Conductivity (k ) of all the ions produced by one mole of an electrolyte, when
dissolved in V ml of water or any solution. ( or ) Conductance of a solution
containing 1 mole of an electrolyte between two electrodes which are 1 cm
apart

1
m = k . V V =

C (Molarity)

m =

k. 1000
,
C

Units of m Ohm 1.cm 2 .mol 1

Equivalent Conductivity or Conductance: eq :

Conductivity (k ) of all the ions produced by one Equivalent of an electrolyte,
when dissolved in V ml of water or any solution. ( or ) Conductance of a
solution containing 1gm Equivalnt of an electrolyte between two electrodes
which are 1 cm apart

eq = k. V,

m =

k. 1000
,
N

Units of eq Ohm 1.cm 2 .eq 1

Relation between Molar and Equivalent Conductance:

m = n f . eq

Variation of Conductivity and molar conductivity with Concentration:

1. Conductivity always decreases with the decrease in concentration both for weak and
strong electrolytes.
2. The number of ions per unit volume that carry the current in a solution decreases on
dilution.
3. Molar conductivity increases with decrease in concentration. This is because the total
volume , V of solution containing one mole of electrolyte also increases.
4. Molar conductivity is the conductance of the solution
5. When concentration approaches Zero, the molar conductivity is know as limiting molar
0
conductivity and is represented by the symbol - m

1.

Sol:
2.

Sol:

Specific conductance of a decimolar solution of potassium chloride at 180 C is

1.12 S m-1. The resistance of a cell containing the solution at 180 C was found to
be 55 ohm. What is the cell constant?
R 55 ,
C 1/ 55 S , k 1.12 S m 1
K cell k / C 1.12 /1/ 55 S 61.6 m 1 0.616 cm 1 .
The resistance of 0.01 M solution of an electrolyte was found to be 210 ohm at
250 C . Calculate the molar conductance of the solution at 250 C . Cell constant
0.88cm 1 .
R 210 , C 1/ 210 S , K cell 0.88 cm 1
k cell cons tan t conduc tan ce 0.88 cm 1 1/ 210 S

0.00419 S cm 1 0.419 S cm 1 .
Concentration of the solution, c 0.01 mol dm 3 10 mol m 3
m k / c 0.419 S m 1 /10 mol m 3 , 0.0419 S m 2 mol 1 .
3.

Sol:

The resistance of 10.5 M solution of an electrolyte in a cell was found to be 45 .

Calculate the molar conductance of the solution if the electrodes in the cell are 2.2
cm apart and have an are of 3 3.8 cm3 ?
R 45 , C 1/ 45 S , K cell 1/ a 2.2 cm / 3.8 cm 2 0.5789 cm 1 57.89 m 1
k 57.89 m 1 1/ 45 S 1.286 S m 1 ,

c 0.5 mol dm 3 500 mol m 3

1.286 S m 1
25.72 104 S m 2 mol 1 .
,
500 mol m 3
Calculate the molar conductance of a 0.01 M aqueous solution of an electrolyte if
its resistance at room temperature is 210 and cell constant is 0.88cm 1 ?
m k / c

4.

Sol:

R 210 ; kcell 0.88 cm 1 88 m 1

k K cell / R 88 m 1 / 210 0.419 S m 1

0.419 S m 1
0.419 S m 1
m k / c

, 419 104 S m 2 mol 1 .

0.01 mol dm 3 0.01 103 mol m 3
5.

When a conductance cell was filled with a 0.02 mol dm 3 aqueous solution of KCl
which had a specific conductance of 0.2767 S m 1 , it had a resistance of 82.39
at room temperature. When the same cell was filled with a 2.5 103 mol dm 3
solution of K 2 SO4 , its resistance was 325 . Calculate the cell constant and the
specific conductance of K 2 SO4 solution?

Sol.

For KCl,
Since

c 0.02 mol dm 3 0.02 103 mol m 3

R 82.39 ; k 0.2767 S m 1 0.2767 1 m 1
k K cell / R,

K cell kR 0.2767 1 m 1 82.39

22.80 m 1 0.2280 cm 1 .

For K 2 SO4 solution, k K cell / R

6.

Sol.

22.80 m 1
, 7.01102 S m 1 .
325

The specific conductance of water is 7.6 102 S m 1 and the specific conductance
of a 0.1 M aqueous solution of KCl is 1.1639 S m 1 . A cell had a resistance of
33.20 when filled with a 0.1 M KCl solution and 300 when filled with a 0.1
M acetic acid solution. Calculate the molar conductance of acetic acid?
k K cell / R , i.e, k 1/ R . Thus we have
k CH 3COOH
R KCl

k KCl
R CH 3COOH

1
Now, R KCl 33.20 ; R CH 3COOH 300 and k KCl 1.1639 S m

k CH 3COOH

33.20 1.1639 S m1
300

0.129 S m 1 .

It should be noted that k CH 3COOH contains a contribution of 7.6 102 S m 1

due to water. Hence specific conductance due to
CH 3COOH 0.129 S m 1 7.6 102 S m 1 , 5.3 102 S m 1 .

7.

Sol.

k
5.3 102 S m 1
m CH 3COOH
5.3 104 S m 2 mol 1 .
3
3
c 0.110 mol m
The specific conductance of 0.01 M solution of acetic acid was found to be
0.0163 S m 1 at 250 C . Calculate the degree of dissociation of the acid. Molar
conductance of acetic acid at infinite dilution is 390.7 104 S m 2 mol 1 at 250 C .
k 0.0163 S m 1 ,
c 0.01 mol dm 3 10 mol dm 3
k 0.0163 S m 1
m
16.3 104 S m 2 mol 1
3
c
10 mol m
om 390.7 104 S m 2 mol 1 (given)
Degree of dissociation,

m
16.3 104 S m 2 mol 1

0.0472 .
om 390.7 104 S m 2 mol 1

Kohlrausch law: Limiting molar conductivity of an electrolyte (molar conductivity at

infinite diution) is sum of limiting ionic conductivities of cation & anion each multiplied with
no. of ions present in one formula unit of electrolyte .
eg.

for AxBy =
or

Eq. conductivity of an electrolyte at infinite dilution is sum of two values one depending
upon cation & other upon anion.
eq

&

Ionic conductivities at infinite dilution

Kohlrausch law Applications:

(1) Calculation of Molar Conductivity at infinite dilution (

) for weak electrolytes:

Illustration: Calculate molar conductance at infinite dilution for CH 3COOH.

(HCl) = 425

-1

cm2 mol-1

(NaCl) = 188

(CH3COONa) = 96
Ans:

(CH3COOH) =
+

(HCl) =

(H ) +

(NaCl) =

(Na+) +

-1

-1

cm2 mol-1

cm2 mol-1

(CH3COO-) +

(H+)

Required.

(Cl) ....................................... (i)

(Cl) .................................... (ii)

(CH3COONa) =
(CH3COO-) +
(Na+) .................. (iii)
By (i) + (iii) - (ii), we get required
(CH3COO-) +
= 333

-1

(H+) = 425 + 96 - 188

cm2 mol-1

(2) Calculation of deg. of dissociation:

in molar conductivity with dilution is due to increase in dissociation of electrolyte.
Deg. of dissociction ( ) =
(3) Calculation of dissociation constant:

Kc =

K can be calculated if

is known.

Illustration: Conductivity of 0.001 M CH3COOH is 4.95 x 10-5 S cm-1. Calculate its dissociation
constant. Gijven for acetic acid, 0 is 390.5 S cm2 mol-1.

Ans:

=
K=

= 49.5 S cm2 mol-1

=
=

= 0.127
= 1.85 x 10-5

(4) Calculation of solubility of sparingly soluble salt:

Solubility =

Illustration: Conductivity of solurated sol. of Agcl at 288 K is found to be 1.382 x 10 -6

Find its solubility
(Ag+) = 61.9
Ans:

(AgCl) =

-1

cm2 mol-1 &

0

Ag

++

(Cl-) = 76.3

-1

- = 61.9 + 76.3 = 138.2

Cl

Solubility =
=
= 10-5 mol L-1 = 10-5 x 143.5 g/L
= 1.435 x 10-3 g/L
(5) Calculation of Ionic product of H2O:
Ionic conductance of H+ & on- at infinite dil.
0
-1
cm2 & 0OH- = 198.5 -1 cm2
n+ = 349.8
= 0H+ + 0OH= 349.8 + 198.5 = 548.7 -1 cm2
Sp. conductance of pure water at 298 K is found to be
K = 5.54 x 10-8 -1 cm-1
= K x 1000/C
Molarity i.e. [H-1] or [on-] =

cm2 mol-1
-1

cm2 mol-1

-1

cm-1.

= 1.01 x 10-7 mol/L

Kw = [H-1] [OH-] = 1.01 x 10-7 x 1.01 x 10-7 = 1.02 x 10-14 mol/L

6.

o
At 250 C , m for potassium picrate is 103.97 104 S m 2 mol 1 and K is

73.58 104 S m 2 mol 1 . Calculate o for the picrate ion and the transport number of the
Sol.

picrate ion at infinite dilution.

o
0
o
From Kohlarauchs law, m

o picrate om o K 103.97 73.58 104 S m 2 mol 1

30.39 104 S m 2 mol 1 .
Hence, the transport number of the picrate ion at infinite dilution.

7.

o
30.39 104 S m 2 mol 1

0.292 .
om 103.97 104 S m2 mol 1
For the strong electrolytes NaOH, NaCl and BaCl2 , the molar ionic conductances at
infinite dilution are 248.104 ,126.5 104 and 280.0 104 S m 2 mol 1 , respectively.
o
Calculate m for Ba OH 2 .

Sol.

BaCl2 2 NaOH

to

Ba OH

2 NaCl

Thus, according to the Kohlrausch law of independent migration of ions,

o
o
omBa OH omBaCl2 2 mNaOH
2 mNaCl
2

280 2 248.1 2 126.5 104 S m 2 mol 1

523.2 104 S m 2 mol 1 .

8.

Sol.

At 250 C , a 0.1 M solution of lithium halide (LiX) has a specific conductance equal to
0.9 104 S m 1 . (a) Calculate the molar conductance of the solution. (b) If the molar
ionic conductance of Li is 39.5 104 S m 2 mol 1 , what is the molar ionic conductance
of the halide ion, X ?
(a) Specific conductance, k 0.9 104 S m 1 .

4
1
k 0.9 10 S m
c 0.1 mol dm 100 mol m . m
90 104 S m 2 mol 1 .
3
c
100 mol m
3

(b)

According to Kohlrauschs law,

om o o m0 = +0 + _0

o om o

90 39.5 104 50.5 10 4 S m 2 mol 1 .

9.

The molar ionic conductances at infinite dilution for H and OH ions are 349.8 104
and 196.7 104 S m 2 mol 1 , respectively. At 250 C , the specific conductance of water
o
is 5.7 106 S m 1 . Assuming that m differs very slightly from m , calculate the ionic

product of water at 250 C .

Sol.

From Kohlrauschs law,

om o o 349.8 196.7 104 S m 2 mol 1 , 546.5 104 S m 2 mol 1 .

om m given

From Eq.14,

5.7 106 S m 1

K
c

m 546.5 104 S m 2 mol 1

1.04 104 mol m3 1.04 107 mol dm 3 . K w H OH
1.04 107 mol dm 3 1.04 107 mol dm 3 , 1.08 1014 mol 2 dm 3 .

10.

The molar conductance at infinite dilution for sodium acetate and hydrogen chloride at
4
2
1
300 C are 91.0 104 and 426.16 10 S m mol , respectively. Also for H in HCl,

t is 0.821 and for CH 3COO in CH 3COONa , t is 0.556. Assuming that t t o ,

Sol.

o
calculate m for CH 3COOH .
We know that

0 t 0 0m and 0m t0 om

Assuming that t0 t and t0 t , from the data on HCl, we have

0 0.821 426.16 104 349.88 104 S m 2 mol 1 .

From the data on CH 3COONa ,
o 0.556 91.0 104 50.60 104 S m 2 mol 1 .
Hence, for CH 3COOH ,
om 0 0 349.88 50.60 104 S m 2 mol 1 .