SOLUBILITY AND FACTORS AFFECTING SOLUBILITY

SOLUBILITY OF SOLIDS IN LIQUIDS

• The solubility of a solid in a liquid at any temperature is defined as the

maximum amount of the solid (solute) in grams which can dissolve in 100 g
of the liquid (solvent) to form a solution at that particular temperature.

Depending upon the amount of solute dissolved in a solvent we have the

following types of solutions:

(i) Unsaturated solution: A solution in which more solute can be dissolved

without raising temperature is called an unsaturated solution.
(ii) Saturated solution: A solution in which no more solute can be dissolved
further at a given temperature is called a saturated solution.

(iii) Supersaturated solution: A solution which contains more solute than that
would be necessary to saturate it at a given temperature is called a
supersaturated solution.

FACTORS AFFECTING SOLUBILITY OF SOLIDS IN LIQUIDS

The important factors on which the solubility of a solid in a liquid depends
are:

(1) Nature of the solute and the solvent

(2) Temperature
(1) NATURE OF THE SOLUTE AND THE SOLVENT

• In general, a solid dissolves in a liquid which is chemically similar to it.

• This is expressed by saying "Like dissolves like".

• This statement implies that ionic / polar compounds like NaCl dissolve in
polar solvents like water and are very little soluble or almost insoluble
non-polar solvents like benzene, ether, etc.

• Similarly, non-polar/covalent or organic compounds like naphthalene,

anthracene etc. are soluble in non-polar (i.e. covalent or organic solvents)
like benzene ether, carbon tetrachloride, etc. and are very little soluble
in water.
• For example,

(a) Common salt (an ionic compound) is more soluble in water than sugar
(a covalent compound). Their solubility in water are 5.3 moles per
litre and 3.8 moles per litre respectively.

(b) Iodine (a covalent substance) is more soluble in alcohol or carbon

tetrachloride (covalent liquids) than in water.

It should be noted that water is the best polar solvent (having highest
dielectric constant), liquid ammonia, liquid hydrogen sulphide and liquid
sulphur dioxide are also good solvents for ionic compounds.
• Further, Ionic compounds are only soluble in polar solvents, when
Hydration enthalpy of the substance is greater than its Lattice Enthalpy

ΔhydH > ΔlatticeH

• It may be mentioned here that whereas energy required for the splitting
of the ionic compound into ions (called Lattice enthalpy), energy is given
out when ions gets hydrated (called Hydration Enthalpy).

• For non-polar compounds being dissolved in non-polar solvents, the

solubility is due to similar solute-solute, solute-solvent and solvent-
solvent interactions.
(2) Temperature:
• When a solid solute is added continuously to a liquid solvent, the solute
keeps on dissolving and the concentration of the solution keeps on
increasing. This process is known as dissolution.

• Ultimately, a stage is reached when no more solute dissolves at the given

temperature. This is because from the solution, the solute particles keep
on colliding on the surface of solid solute particles and get separated out
of the solution. The process is known as crystallization.

• No more solute dissolves because the rate of dissolution becomes equal to

rate of crystallisation, i.e. a dynamic equilibrium is reached

Solute + Solvent ⇌ Solution

This is called Dissolution equilibria and it follows Le-Chatelier’s Principle.

Thus, on the basis of the effect of temperature on solubility in water, the
various ionic substances are divided into three categories

(a) Those whose solubility increases continuously with increase of

temperature.
• For example, NaNO3 KNO3, NaCl, KCl, etc. fall into this category.

• The reason for this behaviour is that in case of all such substances, the
process of dissolution is endothermic.

• Applying Le-Chatelier's Solution principle, as the temperature is

increased, equilibrium will shift in a direction in which the heat is
absorbed, i.e. in the forward direction consequently, more of the solute
passes into the solution and so solubility will increase.
(b) Those whose solubility decreases continuously with increase of
temperature.

• There are a few substances like Cerium Sulphate, Lithium Carbonate,

Sodium Carbonate Monohydrate (Na2CO3.H2O), etc, whose solubility
decreases with increase of temperature.

• Obviously, it is due to the fact that the process of dissolution of these

substances is exothermic, i.e. it is accompanied by evolution of heat.

(c) Those substances whose solubility does not increase or decrease

continuously.
• There are some substances which on heating change at a particular
temperature from one polymorphic form to another (like α-form to β-
form as in the case of ammonium nitrate) or from hydrated to anhydrous
form (eg. Na2SO4.10H2O → Na2SO4). Such substances do not show a
continuous increase or decrease of solubility.

• For example, in case of sodium sulphate, the solubility do first

increases upto 32.4°C and then begins to decrease.

• The temperature at which one form of the substance changes into

another is called transition temperature.

• When the solubilities are plotted against temperatures, the curves

obtained are called solubility curves.

NOTE: Pressure has a very little effect on the solubility of solids in

liquids because solids and liquids are highly incompressible.
SOLUBILITY OF GASES IN LIQUIDS
Almost all gases are soluble in water. The existence of aquatic life in lakes
rivers and sea etc. is due to dissolution of oxygen gas in water.

FACTORS AFFECTING THE SOLUBILITY OF A GAS IN A LIQUID

(1) Nature of the gas and the solvent:

• Gases like Hydrogen, Oxygen, Nitrogen, etc. dissolve only to a small

extent whereas Gases like CO2, HCl, NH3 etc. are highly soluble.

• The greater solubility of latter gases is due to their reaction with the
solvent.
• Again Oxygen, Nitrogen and Carbon dioxide are much more soluble in
ethyl alcohol than in water at the same temperature and pressure while
H2S and NH3 be more soluble in water than in ethyl alcohol.

• Evidently, the greater solubility of gas in a solvent is again due to the

chemical similarity between the gas and the solvent.

(2)Effect of temperature:
• The solubility of a gas decreases with increase in temperature.

• The dissolution of a gas in a liquid is an exothermic process, as

dissolution can be considered as equivalent to process of condensation
which is exothermic.
Gas + Solvent ⇌ Solution + Heat
• Applying Le Chatelier's principle, it is evident that increase of
temperature would shift the equilibrium in the backward direction, i.e. the
solubility would decrease.

• Though O2 gas is more soluble than N2 gas at any temperature, the

solubility of both the gases decreases with increase of temperature.

• That is why, aquatic species feel more comfortable in cold water with
respect to hot water.
•
(3) EFFECT OF PRESSURE (HENRY'S LAW)
• This is the most important factor influencing
the solubility gas in a liquid at a particular
temperature.

• A little thought clearly reveals that as we

compress the gas over liquid (i.e. we increase
the pressure), the solubility will increase.

• Quantitatively, the effect of pressure on the solubility of a gas in a liquid

was studied by Henry(in 1803) and is called Henry's law. It states as
follows:
“The mass of a gas dissolved in a given volume of the liquid at constant
temperature is directly proportional to the pressure of the gas present in
equilibrium with the liquid.”
 m∝ p or m=K×p
• Dalton a contemporary of Henry, also concluded independently that the
solubility of a gas in a liquid is a function of partial pressure of the gas.

• If we use mole fraction of a gas in the solution as a measure of its

solubility, then it the most commonly used form of Henry’s law states
that

“The partial pressure of the gas in vapour phase (pA) is proportional to the
mole fraction of the gas(𝜒A) in solution”.

Mathematically, pA = KH χA

where, KH = Henry’s Law Constant. Its unit is atm or bar.

• Different gases have different values of KH at same temperatures.
• From these values, the following results may be drawn

(1) Henry's constant, KH is a function of the nature of the gas.

(2) Greater the value of KH lower is the solubility of the gas at the same
partial pressure at a particular temperature.
(3) The value of KH increases with increase of temperature implying that
the solubility decreases with increase of temperature at the same
pressure.

Limitations of Henry's law

Henry's law is applicable only if the following conditions are satisfied:

(1) The pressure should be low and the temperature should be high, i.e.
the gas should behave like an ideal gas.

(2) The gas should not undergo compound formation with the solvent or
association or dissociation the solvent.
For example, the law is not applicable in case of dissolution of ammonia in
water because it undergoes compound formation followed by dissociation:

NH3 (g) + H2O → NH4OH (aq)

NH4OH (aq) ⇌ 𝑵𝑯+

𝟒 (aq) + 𝑶𝑯 (aq)
−

APPLICATIONS OF HENRY'S LAW:

(1) To increase the solubility of CO2 in soft drinks, Soda water as well as
beer, champagne, etc. the bottles are sealed under high pressure. When
the bottle is opened to air, the partial pressure of CO2 above the
solution decreases. As a result, solubility decreases and hence CO2
bubbles out.
(2) When a diver goes underwater his body is subjected to high pressure.
• Due to this the body tissues absorbs more gases.

• The breathed in oxygen is required for cellular respiration to provide

energy to the diver.

• But the nitrogen gets absorbed into the body tissues.

• The pressure increases with the increase in depth. With this increase in
pressure more nitrogen gets absorbed by the body tissues.

• But as he approaches upward to come out of the water body the pressure
starts decreasing with the decrease in depth.
• This in turn decreases the amount of nitrogen
getting absorbed by the body tissues.

• This causes the formation of bubbles of

nitrogen in the body and give rise to a
disease called BENDS or DECOMPRESSION
SICKNESS.

• They are difficult and can even cause threat

to their life.

• To protect the divers from such situation the

water utilized by scuba divers are loaded with
diluted air containing 11.7% helium, 56.2%
nitrogen and 32.1% oxygen.
(3) At high heights the partial pressure of
oxygen is not as much as that at the ground
level.

• This stimulates low concentrations of

oxygen in the blood and tissues of
individuals living at high heights or
climbers.

• Low blood oxygen causes climbers to feel

feeble and not able to think properly,
indications of a condition known as
ANOXIA.