Wilhelm Ostwalds dilution law is a relationship between the dissociation constant and the degree of dissociation of a weak electrolyte(acids,

bases).

Kp

constant of protolysis degree of dissociation (or degree of protolysis) c(A ) concentrations of anions c(K+) concentration of cations c0 overall concentration c(KA) concentration of associated electrolyte Concerning conductivity, this results in the following relation:

According to Arrhenius theory of electrolyte dissociation, the molecules of an electrolyte in solution are constantly splitting up into ions and the ions are constantly reuniting to form unionized molecules. Therefore, a dynamic equilibrium exists between ions and unionized molecules of the electrolyte in solution. It was pointed out by Ostwald that like chemical equilibrium, law of mass action can be applied to such systems also. Consider a binary electrolyte AB which dissociates into A+ and B- ions and the equilibrium state is represented by the equation: AB Initially t = o At equilibrium C C(1- ) A+ + B0 0 C C

So, dissociation constant may be given as K = [A+][B-]/[AB] = (C = C 2 /(1- ) ....... (i) For very weak electrolytes, <<< 1, (1 ) = 1 .. K = C 2 = K/C (ii) Concentration of any ion = C = CK . From equation (ii) it is a clear that degree of ionization increases on dilution. * C )/C(1- )

.......

Thus, degree of dissociation of a weak electrolyte is proportional to the square root of dilution.

Limitations of Ostwald's dilution law: The law holds good only for weak electrolytes and fails completely in the case of strong electrolytes. The value of ' ' is determined by conductivity measurements by applying the formula / . The value of ' ' determined at various dilutions of an electrolyte when substituted in Eq. (i) gives a constant value of K only in the case of weak electrolytes like CH3COOH, NH4OH, etc. the cause of failure of Ostwald's dilution law in the case of strong electrolytes is due to the following factors" (i) The law is based on the fact that only a portion of the electrolyte is dissociated into ions at ordinary dilution and completely at infinite dilution. Strong electrolytes are almost completely ionized at all dilutions and / does not give accurate value of ' '. (ii) When concentration of the ions is very high, the presence of charges on the ions appreciably effects the equilibrium. Hence, law of mass action its simple form cannot be strictly applied in the case of strong electrolytes.

Kc constant of dissociation
c 0

equivalent conductivity boundary conductivity concentration of electrolyte

of an

Ostwalds dilution law is a relation for the concentration dependence of the molar conductivity electrolyte solution, viz.

where c is the solute concentration, Kc is the equilibrium constant for dissociation of the solute, and L0 is the conductivity at c Ostwald (1853-1932). = 0. The law was first put forward by the German chemist Wilhelm

KOHLRAUSCH'S LAW
(1) Kohlrausch law states that, At time infinite dilution, the molar conductivity of an electrolyte can be expressed as the sum of the contributions from its individual ions i.e. m = v+ + + v-, where, v+ and V- are the number of cations and anions per formula unit of electrolyte respectively and, + and - are the molar conductivities of the cation and anion at infinite dilution respectively. The use of above equation in expressing the molar conductivity of an electrolyte is illustrated as, The molar conductivity of HCl at infinite dilution can be expressed as,

= VH+ H + VCI- CI-; For HCI, VH+ = 1 and VCI- = 1. So, HCI = (1 x H+) + (1 x H); Hence, HCI = H+ + CI(2) Applications of Kohlrausch's law: Some typical applications of the Kohlrausch's law are described below, (i) Determination of m for weak electrolytes: The molar conductivity of a weak electrolyte at infinite dilution ( m) cannot be determined by extrapolation method. However, m values for weak electrolytes can be determined by using the Kohlrausch's equation. CH3 COOH = CH3COONa + CHI NaCI (ii) Determination of the degree of ionization of a weak electrolyte: The Kohlrausch's law can be used for determining the degree of ionization of a weak electrolyte at any concentration. If cm is the molar conductivity of a weak electrolyte at any concentration C and, cm is the molar conductivity of a electrolyte at infinite dilution. Then, the degree of ionization is given by, ac = cm = m = cm/(v+ + + v- -) Thus, knowing the value of cm , and m (From the Kohlrausch's equation), the degree of ionization at any concentration (ac) can be determined. (iii) Determination of the ionization constant of a weak electrolyte : Weak electrolytes in aqueous solutions ionize to a very small extent. The extent of ionization is described in terms of the degree of ionization ( a ). In solution, the ions are in dynamic equilibrium with the unionized molecules. Such an equilibrium can be described by a constant called ionization constant. For example, for a weak electrolyte AB, the ionization equilibrium is, AB A+ + B-; If C is the initial concentration of the electrolyte AB in solution, then the equilibrium concentrations of various species in the solution are, [AB} = C (1 - A), [A+] = Ca and [B-] = Ca Then, the ionisation constant of AB is given by, K = [A+] [B-]/[AB] = Ca.Ca/C (1 - A) = Ca2/( 1 - a ) We know, that at any concentration C, the degree of ionisation ( a ) is given by, a = cm / m Then, (K) = C( cm/ m)2/[1 - ( cm/ m)] = C( cm)2/ m - cm); Thus, knowing m and cm at any concentration, the ionisation constant (K) of the electrolyte can be determined. (iv) Determination of the solubility of a sparingly soluble salt : The solubility of a sparingly soluble salt in a solvent is quite low. Even a saturated solution of such a salt is so dilute that it can be assumed to be at infinite dilution. Then, the molar conductivity of a sparingly soluble salt at infinite dilution ( m) can be obtained from the relationship, m = V+ + + V- ........(i) The conductivity of the saturated solution of the sparingly soluble salt is measured. From this, the conductivity of the salt (Ksalt) can be obtained by using the relationship, Ksalt = Ksol Kwater, where, Kwater is the conductivity of the water used in the preparation of the saturated solution of the salt. salt = 1000 ksalt/Cm ........(ii) From equation (i) and (ii) ; Cm = 1000 ksalt/(V+ + + V- -), Cm is the molar concentration of the sparingly soluble salt in its saturated solution. Thus,Cm is equal to the solubility of the sparingly soluble salt in the mole per litre units. The solubility of the salt in gram per litre units can be obtained by multiplying Cm with the molar mass of the salt.

HCI