COLLIGATIVE PROPERTIES

In chemistry, colligative properties are those properties of solutions

that depend on the ratio of the number of solute particles to the number

of solvent particles in a solution, and not on the nature of the chemical

species present. The number ratio can be related to the various units for

concentration of a solution, for example, molarity, molality, normality

(chemistry), etc. The assumption that solution properties are independent

of nature of solute particles is exact only for ideal solutions, and is

approximate for dilute real solutions. In other words, colligative

properties are a set of solution properties that can be reasonably

approximated by the assumption that the solution is ideal.

Only properties which result from the dissolution of nonvolatile solute in

a volatile liquid solvent are considered. They are essentially solvent

properties which are changed by the presence of the solute. The solute

particles displace some solvent molecules in the liquid phase and

thereby reduce the concentration of solvent, so that the colligative

properties are independent of the nature of the solute. The word

This indicates that all colligative properties have a common feature,

namely that they are related only to the number of solute molecules

relative to the number of solvent molecules and not to the nature of the

solute.

Colligative properties include:

 Relative lowering of vapour pressure (Raoult's law)

 Elevation of boiling point

 Depression of freezing point

 Osmotic pressure

For a given solute-solvent mass ratio, all colligative properties are

inversely proportional to solute molar mass.

Measurement of colligative properties for a dilute solution of a non-

ionized solute such as urea or glucose in water or another solvent can

lead to determinations of relative molar masses, both for small

molecules and for polymers which cannot be studied by other means.

estimation of the percentage of dissociation taking place.

Colligative properties are studied mostly for dilute solutions, whose

behavior may be approximated as that of an ideal solution. In fact, all of

the properties listed above are colligative only in the dilute limit: at

higher concentrations, the freezing point depression, boiling point

elevation, vapour pressure elevation or depression, and osmotic pressure

are all dependent on the chemical nature of the solvent and the solute.

RELATIVE LOWERING OF VAPOUR PRESSURE

The vapour pressure of a liquid is the pressure of the vapour which is in

equilibrium with that liquid. The vapour pressure of a solvent is lowered

when a non-volatile solute is dissolved in it to form a solution.

For an ideal solution, the equilibrium vapour pressure is given by

Raoult's law as , where is the vapor pressure of the pure component (i=

A, B, ...) and is the mole fraction of the component in the solution For a

solution with a solvent (A) and one non-volatile solute (B), and The
vapour pressure lowering relative to pure solvent is , which is

proportional to the mole fraction of solute.

If the solute dissociates in solution, then the number of moles of solute is

increased by the van 't Hoff factor , which represents the true number of

solute particles for each formula unit. For example, the strong electrolyte

MgCl2 dissociates into one Mg2+ ion and two Cl− ions, so that if

ionization is complete, i = 3 and , where is calculated with moles of

solute i times initial moles and moles of solvent same as initial moles of

solvent before dissociation. The measured colligative properties show

that i is somewhat less than 3 due to ion association.

BOILING POINT AND FREEZING POINT

Addition of solute to form a solution stabilizes the solvent in the liquid

phase, and lowers the solvent chemical potential so that solvent

molecules have less tendency to move to the gas or solid phases. As a

result, liquid solutions slightly above the solvent boiling point at a given

pressure become stable, which means that the boiling point increases.
Similarly, liquid solutions slightly below the solvent freezing point

become stable meaning that the freezing point decreases. Both the

boiling point elevation and the freezing point depression are proportional

to the lowering of vapour pressure in a dilute solution.

These properties are colligative in systems where the solute is essentially

confined to the liquid phase. Boiling point elevation (like vapour

pressure lowering) is colligative for non-volatile solutes where the solute

presence in the gas phase is negligible. Freezing point depression is

colligative for most solutes since very few solutes dissolve appreciably

in solid solvents.

BOILING POINT ELEVATION (EBULLIOSCOPY)

The boiling point of a liquid at a given external pressure is the

temperature at which the vapor pressure of the liquid equals the external

pressure. The normal boiling point is the boiling point at a pressure

equal to 1 atm.
The boiling point of a pure solvent is increased by the addition of a non-

volatile solute, and the elevation can be measured by ebullioscopy. It is

found that Here is the van 't Hoff factor as above, Kb is the ebullioscopic

constant of the solvent (equal to 0.512 °C kg/mol for water), and m is the

molality of the solution.

The boiling point is the temperature at which there is equilibrium

between liquid and gas phases. At the boiling point, the number of gas

molecules condensing to liquid equals the number of liquid molecules

evaporating to gas. Adding a solute dilutes the concentration of the

liquid molecules and reduces the rate of evaporation. To compensate for

this and re-attain equilibrium, the boiling point occurs at a higher

temperature.

If the solution is assumed to be an ideal solution, Kb can be evaluated

from the thermodynamic condition for liquid-vapor equilibrium. At the

boiling point the chemical potential μA of the solvent in the solution

phase equals the chemical potential in the pure vapor phase above the

solution.
where the asterisks indicate pure phases. This leads to the result ,

where R is the molar gas constant, M is the solvent molar mass and

ΔHvap is the solvent molar enthalpy of vaporization.

FREEZING POINT DEPRESSION (CRYOSCOPY)

The freezing point of a pure solvent is lowered by the addition of a

solute which is insoluble in the solid solvent, and the measurement of

this difference is called cryoscopy. It is found that Here Kf is the

cryoscopic constant (equal to 1.86 °C kg/mol for the freezing point of

water), i is the van 't Hoff factor, and m the molality.

In the liquid solution, the solvent is diluted by the addition of a solute, so

that fewer molecules are available to freeze. Re-establishment of

equilibrium is achieved at a lower temperature at which the rate of

freezing becomes equal to the rate of liquefying. At the lower freezing

point, the vapor pressure of the liquid is equal to the vapor pressure of

the corresponding solid, and the chemical potentials of the two phases

are equal as well. The equality of chemical potentials permits the

molar enthalpy of fusion.

OSMOTIC PRESSURE

The osmotic pressure of a solution is the difference in pressure between

the solution and the pure liquid solvent when the two are in equilibrium

across a semipermeable membrane, which allows the passage of solvent

molecules but not of solute particles. If the two phases are at the same

initial pressure, there is a net transfer of solvent across the membrane

into the solution known as osmosis. The process stops and equilibrium is

attained when the pressure difference equals the osmotic pressure.

Two laws governing the osmotic pressure of a dilute solution were

discovered by the German botanist W. F. P. Pfeffer and the Dutch

chemist J. H. van’t Hoff:

1. The osmotic pressure of a dilute solution at constant temperature

is directly proportional to its concentration.

absolute temperature.

These are analogous to Boyle's law and Charles's Law for gases.

Similarly, the combined ideal gas law, has as analog for ideal solutions

where is osmotic pressure; V is the volume; n is the number of

moles of solute; R is the molar gas constant 8.314 J K−1 mol−1; T is

absolute temperature; and i is the Van 't Hoff factor. The osmotic

pressure is then proportional to the molar concentration , since The

osmotic pressure is proportional to the concentration of solute particles

ci and is therefore a colligative property.

As with the other colligative properties, this equation is a consequence

of the equality of solvent chemical potentials of the two phases in

equilibrium. In this case the phases are the pure solvent at pressure P and

the solution at total pressure (P + π).

The word colligative (Latin: co, ligare) was introduced in 1891 by

Wilhelm Ostwald. Ostwald classified solute properties in three

categorie.

1. colligative properties which depend only on solute concentration

and temperature, and are independent of the nature of the solute

particles

2. additive properties such as mass, which are the sums of properties

of the constituent particles and therefore depend also on the

composition (or molecular formula) of the solute, and

3. constitutional properties which depend further on the molecular

structure of the given solute.