Chapter -1

Electrolytic solution
Electrolytes are substances that form ions in
solutions, conduct the electric current.

 Electrolytes may be subdivided further into strong electrolytes

(hydrochloric acid, sodium sulphate) and weak electrolytes
(acetic acid , Barium sulphate).

 Strong electrolytes are completely ionized when they are

dissolved in water. They conduct electrical currents very
efficiently. The classes of strong electrolytes include: (a) soluble
salts e.g. BaCl2, (b) strong acids e.g. HCl, HNO3, H2SO4, (c) strong
bases e.g. NaOH, KOH

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 Weak electrolytes are substances that exhibit a small
degree of ionization in water. That is, they produce
relatively few ions when dissolved in water.

 Their solutions produce a small current.

 The most common weak electrolytes are weak acids

(e.g. acetic acid) and weak bases (ammonium hydroxide –

NH4OH).

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 Conductivity of Electrolyte Solution

 Ions in solution can be set in motion by applying a potential

difference between two electrodes.
 The conductance (G) of a solution is defined as the inverse of the
resistance (R): 1
G  , in units of  1
R

 For parallel plate electrodes with area A,

it follows: A
G
L

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 Conductivity of Electrolyte Solution
 The conductivity of a solution depends on the number of ions present.
Consequently, the molar conductivity Λm is used

m 
C

C is molar concentration of electrolyte and unit of Λm is S m2 mol-1

 In real solutions, Λm depends on the concentration.

The concentration dependence of conductance
indicates that there are 2 classes of electrolyte

Strong electrolyte: molar conductivity

depends slightly on the molar concentration

Weak electrolyte: molar concentration falls

sharply as the concentration increases

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 Strong Electrolyte

• Strong electrolyte are highly ionized in the solution.

• Examples are HCl, H2SO4, NaOH, KOH etc

 Fully ionized in solution
 Kohlrausch’s law  m  0 m  KC 1/ 2

 Λ0m is the limiting molar conductivity

 K is a constant which typically depends on the stoichiometry
of the electrolyte

 C1/2 arises from ion-ion interactions as estimated by the Debye-

Hückel theory.

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 Strong electrolytes - Kohlrausch’s law

            K c
Kohlrausch‟s law

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 Weak Electrolyte

 Not fully ionized in solution

HA(aq )  H2 O(l ) H3 O  (aq )  A  (aq )
(1   ) c c c

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Weak electrolytes are only feebly ionized in the solution.
Examples are H2CO3, CH3COOH, NH4OH etc

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 Transport properties
“It is evident from the Hittorf‟s theoretical device that the number of
ions discharged at each electrode depends upon the sum of the
speeds or mobilities of the two ions”.

Example:-

a) When only two cations could move in a given time, the number of
ions discharged at each electrode was also two.

b) When two cations and three anions moved in a given time, the
number of ions discharged at each electrode was also equal to five.

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DETERMINATION OF TRANSPORT NUMBER: -
a) HITTORF‟S METHOD

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 b) THE MOVING BOUNDARY METHOD:

• This method is based on the direct observation of migration of ions in an

electric field.

• The principle may be explained with reference to determination of

transport number of H+ ions in hydrochloric acid.

• The conductivity cell in this method consists of a vertical tube of uniform

bore filled with Cadmium chloride and hydrochloric acid.

• Hydrochloric acid is the principle electrolyte while Cadmium chloride

serves as the indicator electrolyte to enable formation of boundary.

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• The concentrations are so adjusted that hydrochloric acid
solution is lighter than the Cadmium chloride solution and
therefore floats over the Cadmium chloride solution.

• A sharp boundary appears between the two solutions

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 The selection of the indicator electrolyte has to be made carefully.
Its cation should not move faster than the cation whose transport
number is to be determined and should have the same anion as
the principle electrolyte.
 Cadmium chloride fulfils these conditions, Mobility of Cd+2 are less
than H+ has a common anion.
 The anode inserted at the bottom is a stick of Cadmium metal,
while the cathode at the top is a platinum foil.
 When the small current is made to flow through the conductivity
cell, the chloride ions move towards the anode while hydrogen ion
followed by cadmium ion move towards cathode.

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• The boundary separating the two solutions also moves upwards as
indicated by an arrow.

• Suppose the boundary moves a distance of l cm then the volume of

the liquid that has moved up is l A cm3 where the „‟A‟‟ is cross-
sectional area of the tube in cm2. Let the concentration of the acid be
“C” gram equivalents per litre.

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Activity and Activity Coefficient

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 Theory of electrolytic conductance
• Flow of electricity through solution of electrolytes is due
to the migration of ions.
• When the potential difference is applied between the
two electrodes the cations which are positively charged
move towards the negatively charged electrodes, known
as Cathode.
• While anions which are negatively charged move
towards the positively charged electrode, known as
anode.

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• “The ease with which electricity flows through a solution is
called the Conductance (G) of the solution”.

• “It is defined as the reciprocal of the resistance (R) of the

solution”.

• It is measured in the unit called reciprocal of Ohm or Ohm- 1.

1. Specific conductance
• The resistance of any conductor varies directly as its length (l)
and inversely as its cross -sectional area, a.

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 The specific resistance is defined as the resistance of the conductor

of 1cm length and 1 cm2 cross-section” Or

 It is the resistance of one cu.cm of the material.

 The reciprocal of specific resistance is called specific conductance”.

 It may be defined as the conductance of one cm3of the material.

 The Unit of specific conductance is Ohm- 1 cm-1.

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 2) Equivalent Conductance:-
 Specific conductance although a suitable property for
characterizing metallic conductance,

 it is not so far characterizing electrolytic conductance.

 While measuring the conductance of electrolytes, the quantity of

greater importance known as equivalent conductance is used.

 Equivalent conductance is defined as the conducting power of all

the ions produced by one gram equivalent of an electrolyte in a
given solution”.

 It is denoted by 

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3) Relation between Specific conductance and equivalent

conductance:-

Equivalent conductance is equal to the product of the specific

conductivity (kv) and the volume „‟V‟‟ in ml, containing one gram

equivalent of the electrolyte

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7) Cell constant:
The specific conductance is the conductance of 1cm3 of the solution.
The conductance measured by using the conductivity cell will be the
specific conductance, if the electrodes are exactly 1 cm2 in area and 1
cm apart. This is not usually the case.
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The conductance obtained will therefore have to be multiplied by a
certain factor in order to get the specific conductance.

This factor is called the cell constant

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 Ionic Equilibria
Ionic Mobility
 Although at infinite dilution, all electrolytes are completely
dissociated.
 The molar conductance of these electrolytes differs vastly from one
another. This difference in molar conductance of the electrolytes is
due to the difference in the speeds of the ions.
Example: The molar conductance at infinite dilution of HCl is more
than that of the NaCl. Since the Cl -1 is common, it follows that the
speed of H+ is more than that of the Na+. Since the speed of an ion
varies with the potential applied, therefore it is better to use the term
ionic mobility.
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 Ionic mobility is defined as the “distance travelled by an ion per second
under a potential gradient of 1 volt per meter”.

a) Ionic mobility is extremely small as compared to the speed of

gaseous molecules. The low ionic mobility is due to the fact that
there are frequent collisions between the ions and the solvent
molecules.

b) Low ionic mobility of lithium and sodium is due to the

i) Smaller radii and

ii) Higher charge density.

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 The higher charge density causes these ions to be more highly hydrated
by ion-dipole interactions than the larger ions, since a hydrated ion has to
drag along a shell of water as it moves through the solution;

 its mobility is naturally less than that of un-hydrated ion.

 The ionic mobility of H+ ion is found to be five to ten times greater than
that of other ions.

 The hydrogen ion because of its smaller size and high charge density is
heavily hydrated to form H9O4+ ion.

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 Because of the large size and shape should predict the mobility of H+ ion to be
low rather than high.

 The high mobility of H+ ions in hydroxylic solvents such as H2O, by Grotthus-

type Mechanism in which proton moves rapidly from H3O+ to a hydrogen bonded
water molecule and is transferred further along a series of hydrogen bonded water
molecules.

 This accounts for high mobility of H+ ions in water.

 Ionic motilities increase with temperature. Ionic motilities increase by

about 2% per degree in the vicinity of 25oC.

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