1.11 THE INDEPENDENT MIGRATION OF IONS.

CALCULATION OF CONDUCTIVITIES FROM

IONIC MOBILITIES

For strong electrolytes the limiting value of the molar conductivity, Ao , may be determined
by extending the measurements to low concentrations and then extrapolating the grap of
conductivity against concentration to zero concentration. For weak electrolytes, such as
acetic acid and ammonia, this method cannot be employed,since the dissociation is far from
complete at the lowest concentration at which measurements can be conveniently made
(~10-4).

Kohlraush found that the difference in molar conductivities of pairs of salt, containing
similiar anions and always the same two cations, is constant and independent of the nature
anion.

Kohlraush drew the conclusion that the molar conductivity of an electrolyte is made up as
the sum of conductivities of the componen ions. Mathematically this can be expressed as

Are the limiting molar conductivities or mobilities of the cation and anion respectively. the
ionic mobilities are computed from values of Ao with the aid of transference numbers. These
represent the current carried by the cation and anion respectively, and can be determined
experimentally from the difference of concentration of electrolytes between thebulk of
sloution and part of the solution close to the cathode and anode.

1.12 MODERN THEORY OF STRONG ELECTROLITY

It became clear that substances which are classified as strong electrolytes are made up of
ions even in the solid (crytalline) form. The teory of electrolytic dissociation was in excellent
agreement with the fact that the molar conductivity of strong electrolytes varies
considerably with concentration at higher concentration.

1.13 CHEMICAL EQUILIBRUM ; THE LAW OF MASS ACTION

one of the most important facts about chemical reactions is that all chemical reactions are
reversible.

This condition of chemical equilibrum can most easily be derrived from the law of mass
action. This law was stated originally by guldberg and waage in 1867 in the following form :
the velocity of a chemical reactions at constat temperature is proportional to the product of
the concentration of the reacting substance.

We can write

K is the equilibrum constant of the reactions. Its value is independent of the concentration
of the species involved ; it varies slightly with temperature and pressure.

Expressed in the wrd ; when equilibrum is reached in a reversible reaction at constant

temperature and pressure, the product of the moleculer concentration of the resultans (the
subtances on the right hand side of the equation), divided by the product of the moleculer
concentration of the reactans (the substances on the left-hand side of the equation), each
concentration being raised to the power equal to the number of species of that susbtance
taking pary in the reaction, is constant
1.14 ACTIVITY AND ACTIVITY COEFICIENTS

C. CLASSICAL THEORY OF ACID-BASE REACTIONS

1.15 ACIDS, BASES, AND SALTS

Inorganic substance can be classified into three important groups : acids, bases and salts. An
acids is most simply defind as a substance which, when dissolved in water, undergoes
dissociation with the formation of hydrogen ions as the only positive ions.

All theacids mentioned so far produce one hydrogen ion per molecule when
dissociating ; these are thermed monobasic acids. Other monobasic acids are : perchloric
acid (HCLO4), hydrobromic acid (HBr), hydriodic acid (HI) etc.

Polybasic acids dissociate in more steps, yielding more than ono hydrogen ion per
molecule, sulphuric acid is a dibasic and dissociates in two steps