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kohlrausch’s law of independent migration of ions:

kohlrausch studied the molar or equivalent conductivities at


infinite dilution o for a number of pairs of strong electrolytes
each having a common cation or anion.

Then, Kohlrausch calculated the differences of o values of


each pair. A few of these results are given in the table below :

Electrolyte o Ω-1.cm2 o electrolyte oΩ-1.cm2 o


KCl 149.86 23.41 KBr 151.92 2.06
NaCl 126.45 KCl 149.86
KBr 151.92 23.41 NaBr 128.51 2.06
NaBr 128.51 NaCl 126.45
144.96 23.41 LiBr 117.09 2.06
121.55 LiCl 115.03

We find that o values for each pair of Na & K salts


having a common anion is same, irrespective of the anion.

Similarly, the o values for each pair of salts having the
same different anions and a common cation is same, irrespective
of the cation.

Based on this, Kohlrausch concluded that :


Each ion makes a definite contribution to the total molar or
an equivalent conductivity of an electrolyte at infinite dilution,
irrespective of the nature of the other ion of the electrolyte.

This individual contribution of an ion towards the total molar


conductivity is called molar ionic conductivity.

Kohlrausch law :

The molar conductivity of an electrolyte at infinite dilution is


the sum of the ionic conductivities of the cation and the anions
each multiplied with the number of ions present in one formula
of the electrolyte.

o  oc  oa

o for NaCl  oNa   oCl 

BaCl2  oBa2  2oCl 

Al2 (SO 4 ) 3  oAl  3  oSO2


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Q : if the molar conductivities at infinite dilution of NaCl, HCl


& CH3COONa are 126.4, 246.1 & 91.0 Ω-1.cm2.mol-1
respectively what will be that of CH3COOH ?
Oslwald dilution law :

According to Arrhenius theory of ionization, when an


electrolyte is dissolved in water, is an equilibrium between the
ions and the undissociated molecules:

For example, a binary electrolyte AB:

Ostwald pointed out the law of chemical equilibrium can be


applied to this ionic equilibrium :

initial concentration

 conc. at equilibrium

or

(law of chemical equilibrium).

(Exact formula) Dstwald dilution law

K = the dissociation constant or ionization constant, so it will be


Kd

Kd is constant only at constant temperature. The unit will be


same as those of the concentration C.
If ( the degree of dissociation is very small,

( ) → can be neglected in comparison to 1 in the


denominator of expression (i).

"Approx. formula" -------------(ii)

depending on the equation (ii) :

for weak binary electrolyte, with a small degree of


dissociation is inversely proportional to the square root of the
initial molar concentration

eq. (i) & (ii) are the two expression of Ostwald’s dilu-law

The validity of Ostwald dilution law:

The degree of dissociation α is determined from conductance

measurements =    at different concentrations for a number


 o 

of electrolytes.

For each electrolyte, the data are fitted in equation (i) to see
whether the value of Kd comes out to be constant or not :

i- The value of Kd comes out to be constant only for weak


electrolytes and that too when the concentration of the
solution is not too high. i.e., for dilute solution only.
ii- The value of Kd does not come out to be constant for
strong electrolytes.

Thus, it may be concluded that Ostwald Dilution law is valid


only for weak electrolytes in dilute solution, (that is why it is
called dilution law) and it does not hold good for strong
electrolytes.

The equation =    can not apply to strong electrolytes, for


 o 

in these the decrease in  with concentration is due to interionic


attraction and not partial dissociation.

In weak electrolytes the variation of with concentration is due


to 2 factors:

1- The partial dissociation of the electrolyte, and

2- The interionic attractions between ions present.

Because of the relatively low degree of dissociation of these


electrolytes, the concentrations of ions present in solution are
quite low, and so are the interionic effects.

Consequently, most of the decrease in eq. is due to decrease in


.

The factors that govern degree of dissociation of an electrolyte :

The degree of dissociation α of an electrolyte in the solution


depends upon the following factors :
1- Nature of the solute :

Some electrolyte like mineral acids, alkalies and most of the


salts are almost completely ionized in water. These are called
"strong electrolytes". On the other hand, some electrolytes like
organic acids and bases and some inorganic acids and bases
ionize only to a small extent. These are called "weak
electrolytes".

2- Nature of solvent :

Every solvent has some definite value of the dielectric


constant which is defined as :"its power to weaken the forces of
attraction present between the ions of the electrolyte". Water has
the highest dielectric constant ( ≈ 80 compared with other). Thus
the dissociation of an electrolyte is maximum in water.

3- Concentration :

Degree of dissociation α of an electrolyte increases with


dilution and becomes maximum at infinite dilution.

4- Temperature :

As the temperature is increased, more of the molecules split


into ions. i.e.,  increases.

5- Presence of common ion :

Α of an electrolyte decreases when another electrolyte is


present which furnishes a common ion. This effect is called
common ion effect. For example, dissociation of
decreases in the presence of .

Determination of degree of ionization:

t( ) (Ω-1.cm-1) * 104
0 0.14
18 0.40
25 0.58
34 0.89
50 1.76

From these results it must be concluded that is a weak


electrolyte and ionizing according to :

to find (degree of dissociation):

V = the volume in cm3 containing 1eq.g of

o

=   
 o 