PRECIPITATION TITRATION AND DETERMINATION OF SOLUBILITY OF

SPARINGLY SOLUBLE SALT

1.INTRODUCTION :
Solubilities in aqueous media of sparingly soluble ionic compounds or homo-genous solid
mixture play an important role in chemical processes, whether carried out on a laboratory or an
industrial scale. The respective solubility phenomena, i.e. dissolution and precipitation
reactions, frequently control procedures for preparing, separating and purifying chemicals.
Moreover, the interactions of the hydrological cycle with the cycle of rocks, the naturally
occurring dissolution of minerals in water, as well as their precipitation on the ocean floor and
in the sediments of rivers and lakes, can often be simply described in terms of solubility
equilibria, although gigantic quantities of material may be involved. Solid—solute equilibrium
chemistry has usually been restricted to pure solids, whereas most minerals are solid solutions.
Consequently, we also deals with homogeneous solid mixtures or solid solutions, whose
solubilities not only depend on those of the respective end members but also on the excess
Gibbs energies of mixing. Apart from these fields of application, solubility equilibria of sparingly
soluble ionic solids provide the experimental basis of several physicochemical methods that are
historically or currently important.[1]

2. SOLUBILITY :
Solubility is understood as a maximum amount of solute that dissolves in a solvent at so
called equilibrium. In chemistry an equilibrium is a state where no more solute can be dissolved
in the solvent in the set conditions (temperature, pressure). Such a solution is called a saturated
solution. The concentration of a substance in its saturated solution is called as its solubility at a
given temperature. It is denoted by letter “S” It is expressed as grams per litre or as moles per
litre at a given temperature.

2.1.SOLUBILITY OF SALTS :
Some ionic solids are highly soluble in water while others are almost insoluble in it. The
solubility of ionic solid depends on lattice enthalpy of the salt and hydration enthalpy of ions in
solution. The lattice enthalpy of salt is defined as the energy required to overcome the
attractive forces between the ions. It is always positive. The hydration enthalpy or solvation
enthalpy is the energy released during the interaction between the ions and solvent molecules.
It is always negative. If salt is to be dissolved then its solvation enthalpy should be greater than
its lattice enthalpy.

2.2.Classification of Solids on the Basis of Solubility:

• The solids having a solubility greater than 0.1 M are classified as soluble solids

e.g. NaCI, Sugar, etc.

• The solids having a solubility between 0.01 M and 0.1 M are classified as slightly soluble solids
e.g. calcium phosphate.

• The solids having a solubility less than 0.01 M are classified as sparingly soluble solids

e.g. barium sulphate, silver chloride, etc.

Sparingly Soluble Salt:

A certain substance like AgCI, PbSO4, BaSO4 etc. have negligible solubility in water at ordinary
temperature. Such substances which are practically insoluble in water are called as sparingly
soluble electrolytes. The amount of such salts getting dissolved is so small that their saturated
solution may be regarded as extremely dilute and hence dissolved part can be considered as
completely ionized.

Solubility Product:
In a saturated solution of a sparingly soluble electrolyte, the product of molar concentration of
ions is constant at a given temperature. This constant”Ksp”is called a solubility product.

Explanation:

Suppose 'BA' is a sparingly soluble electrolyte. In aqueous solution, it dissociates to a very little
extent there exist two equilibria.

BA(s) →BA(aq) ↔ B+(aq) A-(aq)

The mass law equation of the equilibrium is

K = [B+][A-] /[BA]

But [BA] = constant

So K constant = [B+][A+]

Ksp = [B+][A-]

Where Ksp is solubility product. If 'S' moles/dm3 is solubility of electrolyte 'BA' then [B+]= S
and [A-] = S,then
 Ksp = [S] [S]

Ksp = S2

Following table shows Ksp value for different salt types :

Salt Type Relation with Ksp Examples of salt

AB Ksp = [S][S] = S2 AIPO4, AgCI, BaSO4, ZnS

AB2 Ksp = [S][2s]2 = 4S3 PbCl2, HgCl2

A2B Ksp = [2S]2[S] = 4S3 Ag2CrO4, Ag2C2O4, Ag2SO4

AB3 Ksp = [S] [3S]3 = 27S4 Fe(OH)3, Al(OH)3, Cr(OH)3

A3B2 Ksp = [3S]3[2S]2 = 108S2 Ca3(PO4)2, Zn3(PO4)2

A3B4 Ksp = [4S]3[4S]4 = 6912S7 Zn3(PO4)4

RELATIONSHIP BETWEEN SOLUBILITY PRODUCT AND IONIC PRODUCT :

Both ionic product and solubility product represent the product of the concentrations of the
ions in the solution. The term ionic product has a broad meaning since, it is applicable to all
types of solutions, either unsaturated or saturated and varies accordingly.

On the other hand, the term solubility product is applied only to a saturated solution in which
there exists a dynamic equilibrium between the undissolved salt and the ions present in
solution. Thus the solubility product is in fact the highest limit of ionic product for a saturated
solution at a constant temperature.

When ionic product exceeds the solubility product, excess ions combine with each other to
form the precipitate of the salt. Hence to find whether a precipitation can take place or not,
ionic product of salt is calculated and it is then compared with the solubility product of the salt
at the same temperature.

By knowing the molar concentration of ions in a solution and solubility product, it can be
predicted whether precipitation would occur or not. Precipitation is an ionic reaction. According
to the solubility product concept, precipitation occurs only when the ionic product exceeds
solubility product.

In general,when
• Ionic product = Ksp, the solution is saturated (No precipitation)

• Ionic product < Ksp, the solution is unsaturated(No precipitation)

• Ionic product > Ksp, the solution is supersaturated (precipitation)[2]

FACTORS AFFECTING SOLUBILITY :

Temperature:

Basically, solubility increases with temperature. It is the case for most of the solvents. The
situation is though different for gases. With increase of the temperature they became less
soluble in each other and in water, but more soluble in organic solvents.

Polarity:

In most cases solutes dissolve in solvents that have a similar polarity. Chemists use a popular
aphorism to describe this feature of solutes and solvents: "Like dissolves like". Non-polar
solutes do not dissolve in polar solvents and the other way round.

Pressure:
 Solid and liquid solutes:

For majority of solid and liquid solutes, pressure does not affect solubility.

 Gas solutes:

As for gasses the Henry's law states that solubility of gas is directly proportional to the pressure
of this gas. This is mathematically presented as: p = kc, where k is a temperature dependent
constant for a gas. A good proof of Henry's law can be observed when opening a bottle of
carbonated drink. When we decrease the pressure in a bottle, the gas that was dissolved in the
drink bubbles out of it.

Molecular size:

The larger the molecules of the solute are, the more difficult it is for solvent molecules to
surround bigger molecules. If all of the above mentioned factors ale excluded, a general rule
can be found that larger particles are generally less soluble. If the pressure, and temperature
are the same than out of two solutes of the same polarity, the one with smaller particles is
usually more soluble.
Stirring increases the speed of dissolving :

Stirring only increases the speed of the process - it increases move of the solvent what exposes
solute to fresh portions of it, thus enabling solubility. As molecules in liquid substances are in
constant move, the process would take place anyway, but it would take more time. [3]