ELECTROCHEMISTRY

[PART-2]
OHM’S LAW
 Ohms law is applicable for electrolytic
conductors also.
 It states that the current passing through a
conductor is directly proportional to the potential
difference applied.
 That is; V I
Or V = IR
 Where R is the resistance of the conductor
and its unit is ohm (W)
 The resistance of a conductor is directly
proportional to its length (l) and inversely
proportional to its area of cross section (a) .
 That is; R  l and R  1/a
 Hence Rl/a
R = ρ (l / a)
 Where ‘ρ’ is called resistivity or specific resistance.
 In the case of electrolytic cells, ‘l’ represents the
distance between the electrodes and ‘a’ represents
the area of cross section of the electrodes.
 We know that, R = ρ (l / a)
⸫ ρ = Ra/l
 If a = 1 cm2, l = 1 cm, then, ρ = R
 Thus resistivity is defined as the resistance
offered by the conductor of 1 cm length and
area of cross section to 1 cm2.
 The unit of ris W cm or Wm
CONDUCTANCE (G)
 Conductance is the measure of ease with which
current flows through the conductor.
 Conductance is the reciprocal of resistance.
 That is; G = 1/R
 G = 1/ρ (l / a)
 G = κ (a / l)
 Where ‘κ’ is called specific conductance or
conductivity.
 It is the reciprocal of resistivity.
That is κ = 1/ρ .
 κ = G (l / a)
 Unit of conductance is ohm–1 or mho or
Siemens (s)
 The SI unit of conductance is Siemens (S)
 Unit of conductivity is ohm–1 cm–1 or S m–1
Cell constant ( G* )
Distance between the electrodes
 Cell constant=
Area of cross section of electrode

 That is; G* = l/a

 Unit of cell constant is cm-1
 SI unit of cell constant is m-1
Relation between conductivity and cell
constant

We have; G*= l / a…………………..(1)

κ = G (l / a)……………….(2)
Therefor, κ = G G*
Or κ = G*/R
Equivalent conductivity ( Λeq )
 Equivalent conductivity of a solution at a given
concentration is defined as the conductance
offered by all the ions formed by dissolving 1 gram
equivalent of electrolyte in solution.
 Λeq= 1000 κ /normality ( If ‘κ is in ohm-1 cm-1)
 Λeq= κ / 1000 normality ( If ‘κ is in ohm-1 m-1)
 Unit of equivalent conductance is ohm–1 cm2 eq–1
or S m2 eq–1
Molar conductivity ( Λm)
 Molar conductivity of a solution at a given
concentration is defined as the conductance
offered by all the ions formed by dissolving 1 mol
of an electrolyte in solution.
 Λm = 1000 κ /Molarity ( If ‘κ is in ohm-1 cm-1)
 Λm= κ / 1000 Molarity ( If ‘κ is in ohm-1 m-1)
 Unit of molar conductivity is ohm–1 cm2 mol–1 or
S m2 mol–1
Relation between Λm and Λeq
Λm = n × Λeq
Where n is the total charge of the cation
or anion of a single molecule of the
electrolyte
Eg: NaCl Na+ + Cl– n=1
CaSO4 Ca2+ + SO42– n=2
Al2(SO4)3 Al3+ + 3SO42– n=6
 Variation of conductivity and molar
conductivity with dilution
 Conductivity of an electrolytes decreases
with decrease of concentration or increase
of dilution.
 Because when the solution becomes dilute,
the number of current carrying particles
present per mL of the solutions becomes
decreases.
 The Λm increases with increase of dilution.
 Strong electrolytes are almost completely ionised in
solution. The molar conductance of such a solution
increases on further dilution due to the increase in the
mobility or speed of ions since other interacting forces
are minimized on dilution.
 In the case of weak electrolytes, they have low degree
of dissociation, as the dilution increases, the degree of
dissociation increases which increases the number of
ions in the solution. Hence Λm increases with dilution.
 The molar conductivity at zero concentration
or infinite dilution is called limiting molar
conductivity.
 It is represented as Λm0 or Λm∞.
 The mathematical relationship between m
and m0 for strong electrolytes was developed
by Debye, Huckel and Onsagar and the
equation is known as Debye-Huckel-
Onsagar equation.
 The simplified form is
Λm = Λm0 - A√C
 Strong electrolyte

Weak electrolyte

Λm = Λm0 - A√C
 In the case of strong electrolytes, when the
concentration approaches zero, the molar
conductivity attains a definite value known as
limiting molar conductivity.
 For strong electrolytes, the value of Λm0 is
determined from the graph by extrapolating
it to zero concentration.
 In the case weak electrolytes the limiting value
cannot be obtained because when the
concentration approaches zero, the graph
becomes almost parallel to the Y-axis.
 Thus for weak electrolytes the value of limiting
molar conductivity cannot be obtained by
extrapolating the graph to zero concentration.
 When the concentration approaches zero, the
degree of ionisation approaches unity, ie., the
electrolyte almost undergo complete
dissociation. This causes rise in the value of m
near the infinite dilution.
 In the case of weak electrolytes, the value of m0
can be calculated by Kohlrausch’s law.
 Kohlrausch’s law.
 Kohrlrausch discovered that at infinite dilution,
the ionisation is complete and all forces of
interactions between the ions cease. So each ion
moves independently and contributes a definite
value to the molar conductivity of the electrolyte.
Based on these findings Kohlrausch proposed a
law known as Kohlrausch’s law.
 It states that, “the molar conductance of an
electrolyte at infinite dilution is equal to the sum
of the molar ionic conductance of all the cations
and anions at infinite dilution”.
 Λm0 = n+ λm+ + n- λm-
 Λm0 ------Limiting molar conductivity
 n+ ------number of cations
 λm+ ------limiting molar conductivity of cations
 n- ------number of anions
 λm- ------limiting molar conductivity of anions
 Eg:
Λm0 of Al2(SO4)3= 2 × λm0 of Al3+ + 3 × λm0 of SO42-
 Applications of Kohlrauschs law
1. To calculate the Λm0 of weak electrolytes.
2. To calculate the degree of dissociation
of weak electrolyte [α]
3. Calculation of dissociation constant of
weak electrolyte.
4. Calculation of solubility of sparingly
soluble salt.
QUESTIONS
1. The specific conductance of a 0.1 N KCl
solution at 230C is 0.0112 ohm-1 cm-1. The
resistance of the cell containing the
solution at the same temperature was
found to be 55 ohm. The cell constant will
be :
(A) 0.142 cm-1
(B) 0.918 cm-1
(C) 1.12 cm-1
(D) 0.616 cm-1
2. Resistance of a decimolar solution
between two electrodes 0.02 meter apart
and 0.0004 m2 in area was found to be 50
ohm. Specific conductance (k) is
(A) 0.1 S m–1
(B) 1 S m–1
(C) 10 S m–1
(D) 4 × 10–4 S m–1
3. An electrolytic cell was filled with 0.01 M
KCl solution with a conductivity of 0.015
S cm–1 at 298 K. Its measured resistance
at 298 K was 90 ohm. When the cell was
filled with 0.02 M AgNO3 solution, then
the resistance was 50 ohm. Find the molar
conductivity of 0.02 M AgNO3 solution.
(A) 6.75 Scm2 mol–1
(B) 1.35 Scm2 mol–1
(C) 135 S cm2 mol–1
(D) 1350 Scm2 mol–1
4. The values of limiting ionic conductance of
H+ and HCOO– ions are respectively 347 and
53 S cm2 mol–1 at 298 K. If the molar
conductance of 0.025M methanoic acid at
298 K is 40 S cm2 mol–1, the dissociation
constant of methanoic acid at 298 K is
(a) 1  10–5
(b) 2  10–5
(c) 2.5  10–5
(d) 2.5  10–4
5. A weak electrolyte having the limiting
equivalent conductance of 400 S cm2 g
equiv–1 at 298 K is 2% ionized in its 0.1 N
solution. The resistance of this solution
(in ohms) in an electrolytic cell of cell
constant 0.4 cm–1 at this temperature is
(a) 200
(b) 300
(c) 400
(d) 500
6. The limiting molar conductivities of HCl,
CH3COONa and NaCl are respectively 425,
90 and 125 mho cm2mol-1 at 25oC. The molar
conductivity of 0.1 M CH3COOH solution is
7.8 mho cm2 mol-1 at the same temperature.
The degree of dissociation of 0.1 M acetic acid
solution at the same temperature is
(a) 0.10
(b) 0.02
(c) 0.15
(d) 0.03
7. An increase in molar conductance of a
strong electrolyte with dilution is
mainly due to
(1) Increase in number of ions
(2) Increase in ionic mobility of ions
(3) 100% ionisation of electrolyte at
normal dilution
(4) Increase in both i.e. number of
ions and ionic mobility of ions
8. The molar conductance at infinite
dilution of an aqueous solution of CaCl2,
Na2SO4 and NaCl are a, b and c
respectively. Then molar conductance of
CaSO4 solution at infinite dilution is
given by
(a) a + b + c
(b) a – b + c
(c) a + b – 2c
(d) 2a + b + c
9. The ion having highest limiting molar
conductivity among the following is
(a) SO42–
(b) H+
(c) Ca2+
(d) HO–
10. A weak electrolyte having the limiting
equivalent conductance of 400 S cm2 g eq–1
at 298 K is 2% ionized in its 0.1 N solution.
The resistance of this solution (in ohms)
in an electrolytic cell of cell constant 0.4
cm–1 at this temperature is
(a) 200
(b) 300
(c) 400
(d) 500
THANK YOU