Electrical Conductance of Electrolytic Solutions

Classification of Conductors:
1) Non-conducting bodies or Insulators:
- Do not allow flow of current even at high electric fields.
- Specific Resistance/Resistivity (ρ) is greater than 108 ohm cm
- Example: Dry Wood, Bone China, etc. Temperature Coefficient of conductivity is zero.
2) First- Class Conductors or electron conducting materials:
- Flow of current is due to electrons
- Specific Resistance/Resistivity (ρ) is between 10-6 to 10-3 ohm cm.
- Example: metals, metal-oxides. Temperature Coefficient conductivity is negative.

3) Semiconductors:
- Flow of current is due to electrons and holes. Temperature Coefficient conductivity is positive.
- Specific Resistance/Resistivity (ρ) is between 10-5 to 105 ohm cm.
- Example: semi-metals, intermetallic compounds salts, organic compounds.
4) Second- Class Conductors or ionic conductors:
- Flow of current is due to IONS. Temperature Coefficient conductivity is positive.
- Specific Resistance/Resistivity (ρ) is between 10-1 to 108 ohm cm.
- Example: solid salts, ionic melts, electrolyte solutions.

5) Mixed Conductors :
- Flow of current is due to electrons + ions. Temperature Coefficient depends upon composition.
- Specific Resistance/Resistivity (ρ) – depends upon composition.
- Example: solutions of alkali and alkaline earth metals in ammonia.
 Electrical Conductance of Electrolytic Solutions
 The ionic conduction in an electrolyte is expressed as:
1) Specific Conductance or conductivity (κ) = 1/ρ
- defined as the conduction in an electrolyte layer placed between two oppositely
charged electrodes, each having a surface area of 1 cm2 and distance between the
two being 1 cm.
- can also be considered as the conduction of an electrolyte layer place between two
opposite face of an cube of edges 1cm.
- units are ohm-1cm-1, mho cm-1, S cm-1

1 cm
 Electrical Conductance of Electrolytic Solutions
2) Equivalent Conductance (λ) = κ/(zc) = κ V/(z)
- defined as the conduction in one equivalent
electrolyte layer placed between two oppositely
One
charged electrodes, each having a surface area of 1 Equivalent
cm2 and distance between the two being 1 cm. Electrolyte
- can also be considered as the conduction of one
equivalent electrolyte layer place between two
opposite face of an cube of edges 1cm. 1 cm
- units are ohm-1cm-1 equiv-1

3) Molar Conductance (λm) = z λ

- defined as the conduction in one molar electrolyte
layer placed between two oppositely charged
One
electrodes, each having a surface area of 1 cm2 and Molar
distance between the two being 1 cm. Electrolyte
- can also be considered as the conduction of one
molar electrolyte layer place between two opposite
face of an cube of edges 1cm. 1 cm
- units are ohm-1cm-1 M-1
Effect of Concentration on the conductance of electrolyte solutions
Effect of Concentration on the conductance of electrolyte solutions
Debye – Onsager Theory of Conductance

λc = λ0 - (λII + λI)
Effect of Concentration on the conductance of electrolyte solutions
 Effect of temperature on the conductance of electrolyte solutions

At narrow temperature range: λt = λt0 (1+αt)

At wider temperature range: λt = λt0 (1 + αt – βt2)

Kohlrausch’s Formula: κt = κt=25 [1 + α’(t-25) – β’(t-25)2]

 Electrical Conductance of Electrolytic Solutions
Walden Rule

This rule was concluded by Walden during the course of his investigation of the
conductance of tetraethylammonium iodide in various solvents. The values of Λ0η0 for
tetraethylammonium iodide in various solvents are given in the table.

Solvent CH3OH CH3OCH3 CH3CN C2H4Cl2 CH3NO2 C6H5NO2 C6H5OH

Λ0η0 0.63 0.66 0.64 0.60 0.69 0.67 0.63

According to Walden’s rule, the product of the equivalent conductance at infinite dilution
and the viscosity of the solvent are approximately constant and independent of the nature
of the solvent.
Λ0η0 ≈ constant for a given electrolyte in any solvent.

A major advantage of this rule is that the ion conductance at infinite dilution can be
calculated on knowing the viscosity of the solvent.
 Abnormal Ion Conductances
 An inspection of the conductance- viscosity products for the hydrogen reveals the fact that
the values in the hydroxylic solvents, and particularly in water, are abnormally high.

 The high conductance-viscosity product of the hydrogen ion in water could not be
explained by its small size.

H+ + H2O = H3O+
 The hydrogen ion in water must be combined with at least one molecule of water and thus
represented by H3O+.

 Hence its effective size and conducting power should be approximately the same as that
of the sodium ion. But it is actually many times greater.

 In acetone, nitromethane, nitrobenzene, liquid ammonia, and probably in other non-

hydroxylic solvents, the conductance-viscosity product and hence the conductance of the
hydrogen ion is almost the same as that of the sodium ion.

 The high conductance is due to a type of Grotthuss conduction.

 Grotthuss Conduction
The Grotthuss mechanism (also known as proton jumping) is the process by which
a proton or proton defect diffuses through the hydrogen bond network of water
molecules or other hydrogen-bonded liquids through the formation and concomitant
cleavage of covalent bonds involving neighboring molecules.
 Debye – Onsager Theory of Conductance
In Debye-Huckel theory it is assumed that a given ion (such as
a cation) is surrounded by neighbouring ions of opposite
charge (anions). These surrounding counter-ions are said to
form an ionic atmosphere which can be visualized as a
charged cloud surrounding the central ion of interest. In the
absence of an electric field the ionic atmosphere is
spherically distributed around the central ion.

When an electric field is present the central ion migrates through the
solution and so the ionic atmosphere is no longer spherically
symmetric. Because the ions forming the atmosphere do not adjust
to the moving ion immediately, the atmosphere is incompletely
formed in front of the moving ion, and incompletely decayed behind
the moving ion. The net result is the displacement of the center of
charge of the atmosphere behind the moving ion.
 Debye – Onsager Theory of Conductance

 The moving ion also experiences an enhanced viscous drag force. This arises because the
ionic atmosphere moves in a direction opposite to that of the ion thereby reducing the
mobility and hence the conductivity of the latter.
 This is called the electrophoretic effect. The electrophoretic effect (occurring also in the
case of the electrophoretic motion of charged colloidal particles in an electric field) is
caused by the simultaneous movement of the ion in the direction of the applied electric
field and of the ionic atmosphere in the opposite direction.
 Both the central ion and the ions of the ionic atmosphere take the neighbouring solvent
molecules with them, which results in a retardation of the movement of the central ion.
λc = λ0 - λI
 Debye – Onsager Theory of Conductance
 The charge on the ion and the atmosphere are opposite,
the result is retardation in the motion of the moving
central ion. This reduction in the mobility of the ion is
called the relaxation effect. λ = λ - λ
c 0 II

 The time-of-relaxation effect originates in a certain time delay (relaxation) required for
the renewal of the spherical symmetry of the ionic atmosphere around the central ion
moving under the influence of an applied electric field. The disappearance of the ionic
atmosphere after removal of the central ion, similar to its formation, is an exponential
function of time; in fact, both of these processes are complete after twice the relaxation
time, which is of the order of 10-7 to 10-9 s, depending on the electrolyte concentration.
 If the central ion moves under the influence of an external electric field, it becomes
asymmetrically located with respect to the centre of the ionic atmosphere. Thus the time
average of the forces of interaction of the ionic atmosphere with the central ion is not
equal to zero. The external electric field is decreased by the relaxation electric field, as it
is oriented in the opposite direction to the external force.
 Although the relaxation time is several orders of magnitude smaller than the time
required for the central ion to pass through the ionic atmosphere(about10-3 s), its effect is
important because the strength of the electric field formed by the ionic atmosphere (~105
V/ cm) is greater than the strength of the external electric field. Thus, even small changes
in the symmetry of the ionic atmosphere have measurable effect acting against that of the
external electric field.
Debye – Onsager Theory of Conductance

λc = λ0 - (λII + λI)
Wien Effect

 The Wien effect is the experimentally-observed increase in ionic mobility or conductivity

of electrolytes at very high gradient of electrical potential.

 The conductivities of strong electrolytes do not depend on the strength of the electric
field for weak fields (of the order of 104 V/m).

 At high electric field strengths (of about 107 V/m), Wien observed a significant increase
in the conductivity. This effect increases at higher concentrations and at a higher charge
number of the electrolyte ions and approaches a limiting value with increasing electric
field.

 This phenomenon is a result of the high ion velocities, preventing rearrangement of the
ionic atmospheres during motion. Thus an ionic atmosphere is not formed at all and both
the electrophoretic and relaxation effects disappear.
Debye–Falkenhagen Effect
 The increase in the conductivity of an electrolyte solution when the applied voltage has a
very high frequency is known as Debye–Falkenhagen effect.

 Debye and Falkenhagen predicted that the ionic atmosphere would not be able to adopt
an asymmetric configuration corresponding to a moving central ion if the ion were
oscillating in response to an applied electrical field and if the frequency of the applied
field were comparable to the reciprocal of the relaxation time of the ionic atmosphere.

 This was found to be the case at frequencies over 5 MHz where the molar conductivity
approaches a value which is somewhat higher. This increase of conductivity is caused by
the disappearance of the time-of-relaxation effect, while the electrophoretic effect
remains in full force.