COLLIGATIVE PROPERTIES

Colligative properties - Vapour Pressure Lowering - Osmosis and Osmotic Pressure - The
boiling Point elevation - The freezing point depression.

Properties depend on the number of solute particles irrespective of their nature

relative to the total number of particles present in the solution are called colligative
properties. (colligative: from Latin: co means together, ligare means to bind).
Colligative properties are relative lowering of vapour pressure, elevation of boiling
point, depression in freezing point and osmotic pressure. Though the magnitude of these
properties are small, they have plenty of practical applications. For example the osmotic
pressure is important for some vital biological systems.

Relative lowering of vapour pressure

Vapour pressure of liquid
Generally, liquids have a tendency to evaporate. If the kinetic energy of molecules
in the liquid state overcomes the intermolecular force of attraction between them, then
the molecules will escape from the liquid state. This process is called 'evaporation' and
it happens on the surface of the liquid.
If evaporation is carried out in a closed container then the vapour remains in
contact with the surface of the liquid. These vapour molecules are in continuous random
motion during which they collide with each other and also with the walls of the container.
As the collision is inelastic, they lose their energy and as result the vapour returns back
to liquid state. This process is called as 'condensation'.
Evaporation and condensation are continuous processes. If the process is carried
out in a closed system, a stage is reached when the rate of evaporation becomes equal
to the rate of condensation. Thus, an equilibrium is established between liquid and its
vapour. The pressure of the vapour in equilibrium with its liquid is called vapour pressure
of the liquid at the given temperature. The vapour pressure of a liquid depends on its
nature, temperature and the surface area. The following simple apparatus demonstrates
the measurement of vapour pressure of a liquid.

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 The vapour pressure of a solution containing a nonvolatile, non-electrolyte solute
is always lower than the vapour pressure of the pure solvent. Consider a closed system
in which a pure solvent is in equilibrium with its vapour. At equilibrium the molar Gibbs
free energies of solvent in the liquid and gaseous phase are equal (ΔG = 0). When a
solute is added to this solvent, the dissolution takes place and its free energy (G)
decreases due to increase in entropy. In order to maintain the equilibrium, the free energy
of the vapour phase must also decrease. At a given temperature, the only way to lower
the free energy of the vapour is to reduce its pressure. Thus the vapour pressure of the
solution must decrease to maintain the equilibrium.

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The French chemist Raoult, proposed a quantitative relationship between the partial
pressures and the mole fractions of two components A & B, which is known as Raoult’s
Law. Raoult’s law states that “in the case of a solution of volatile liquids, the partial
vapour pressure of each component (A & B) of the solution is directly proportional
to its mole fraction”.

According to Dalton’s law of partial pressure the total pressure in a closed vessel
will be equal to the sum of the partial pressures of the individual components.

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 Non volatile solute in volatile solvent
For example, when sodium chloride is added to the water, the vapour pressure of
the salt solution is lowered. The vapour pressure of the solution is determined by the
number of molecules of the solvent present in the surface at any time and is proportional
to the mole fraction of the solvent.

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The above expression gives the relative lowering of vapour pressure. Based on this
expression, an alternate statement of Raoult’s Law is obtained which can be stated as
“the relative lowering of vapour pressure of an ideal solution containing the nonvolatile
solute is equal to the mole fraction of the solute at a given temperature”
Ideal and non-ideal solutions
An ideal solution is a solution in which each component i.e. the solute as well as
the solvent obeys the Raoult’s law over the entire range of concentration. Practically no
solution is ideal over the entire range of concentration. However, when the concentration
of solute is very low, the dilute solution behaves ideally. If the two components present in
the solution (A and B) are identical in size, structure, and having almost similar
intermolecular attractive forces between them (i.e. between A-A, B-B and B-A) and then
the solution tends to behave like an ideal solution.

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For an ideal solution
i) there is no change in the volume on mixing the two components (solute & solvents).
(ΔVmixing= 0)
ii) there is no exchange of heat when the solute is dissolved in solvent (ΔHmixing = 0).
iii) escaping tendency of the solute and the solvent present in it should be same as in
pure liquids.
Examples for ideal solutions: benzene & toluene; n-hexane & n-heptane; ethyl
bromide &ethyl iodide; chlorobenzene & bromobenzene.
Non-ideal solutions
The solutions which do not obey Raoult’s law over the entire range of
concentration, are called non-ideal solutions. For a non-ideal solution, there is a change
in the volume and enthalpy upon mixing. i.e. ΔHmixing ≠ 0 and ΔVmixing ≠ 0. The deviation
of the non-ideal solutions from the Raoult’s law can either be positive or negative.
Non-ideal solutions - positive deviation from Rauolt's Law:
Positive Deviation from Raoult’s Law occurs when the vapour pressure of component is
greater than what is expected in Raoult’s Law. For Example, consider two components
A and B to form non-ideal solutions. Let the vapour pressure, pure vapour pressure and
mole fraction of component A be PA , PA0 and xA respectively and that of component B
be PB , PB0 and xB respectively. These liquids will show positive deviation when Raoult’s
Law when:
• PA > PA0 xA and PB > P0B xB, as the total vapour pressure (PA0 xA + P0B xB)
is greater than what it should be according to Raoult’s Law.
• The solute-solvent forces of attraction is weaker than solute-solute and
solvent-solvent interaction that is, A – B < A – A or B – B
• The enthalpy of mixing is positive that is, ΔHmix > 0 because the heat
absorbed to form new molecular interaction is less than the heat released
on breaking of original molecular interaction.
• The volume of mixing is positive that is, ΔVmix > 0 as the volume expands
on dissolution of components A and B.

Examples:

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 • Acetone and Carbon disulphide
• Acetone and Benzene
• Carbon Tetrachloride and Toluene or Chloroform
• Methyl Alcohol and Water
• Acetone and Ethanol
• Ethanol and Water

Negative Deviation from Raoult’s Law

Negative Deviation occurs when the total vapour pressure is less than what it
should be according to Raoult’s Law. Considering the same A and B components to form
a non-ideal solution, it will show negative deviation from Raoult’s Law only when:

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 • PA < PA0 xA and PB < P0B xB as the total vapour pressure (PA0 xA + P0B xB) is
less than what it should be with respect to Raoult’s Law
• The solute-solvent interaction is stronger than solute-solute and solvent-
solvent interaction that is, A – B > A – A or B – B
• The enthalpy of mixing is negative that is, ΔHmix < 0 because more heat is
released when new molecular interactions are formed
• The volume of mixing is negative that is, Δmix V < 0 as the volume
decreases on dissolution of components A and B
Examples: Following are examples of solutions showing negative deviation from Raoult’s
Law
• Chloroform and Benzene
• Chloroform and Diether
• Acetone and Aniline
• Nitric Acid ( HNO3) and water
• Acetic Acid and pyridine
• Hydrochloric Acid ( HCl) and water

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Determination of Molar Masses from Lowering of Vapour Pressure

It is possible to calculate molar masses of non-volatile non-electrolytic solutes by

measuring vapour pressures of their dilute solutions. Suppose, a given mass, w gram, of
a solute of molar mass m, dissolved in W gram of solvent of molar mass M, lowers the
vapour pressure from P0 to P.

Then, from Raulots law

Since in dilute solutions, n is very small as compared to N, above equation may be put
in the approximate form as

Elevation of boiling point

Boiling point is an important physical property of a liquid. The boiling point of a
liquid is the temperature at which its vapour pressure becomes equal to the atmospheric
pressure (1 atm). When a nonvolatile solute is added to a pure solvent at its boiling point,
the vapour pressure of the solution is lowered below 1 atm. To bring the vapour pressure
again to 1 atm, the temperature of the solution has to be increased. As a result,the
solution boils at a higher temperature (Tb) than the boiling point of the pure solvent (Tb°).
This increase in the boiling point (∆Tb) is known as elevation of boiling point. A plot of
vapour pressure versus temperature for water and an aqueous solution is given below

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 The vapour pressure of the solution increases with increase in temperature as
shown in the above figure. The variation of vapour pressure with respect to temperature
for pure water is given by the violet coloured curve. At 100 ⁰C the vapour pressure of
water is equal to 1 atm. Hence the boiling point of water is 100 ⁰C (Tb°). When a solute is
added to water, the vapour pressure of the resultant solution is lowered. The variation of
vapour pressure with respect to temperature for the solution is given by green curve. From
the graph, it evident the vapour pressure of the solution is equal to 1 atm pressure at the
temperature Tb which is greater than Tb°. The difference between these two temperatures
(Tb-Tb°) gives the elevation of boiling point.
The elevation of boiling point (ΔTb) = Tb - Tb°
Experiments have shown that for dilute solutions the elevation of boiling point (ΔTb) is
directly proportional to the molal concentration of the solute in a solution. Thus
ΔTb α m
or ΔTb = Kb m
Here m (molality) is the number of moles of solute dissolved in 1 kg of solvent and the
constant of proportionality, Kb is called Boiling Point Elevation Constant or Molal Elevation
Constant (Ebullioscopic Constant). Molal elevation constant is the elevation in boiling
point of a solution containing 1 gram mole of a solute per 1000 grams of the solvent.The
unit of Kb is K kg mol-1.

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If w2 gram of solute of molar mass M2 is dissolved in w1 gram of solvent, produces the
elevation in boiling point ΔTb of the solvent then molality, m of the solution is given by the
expression:

Substituting the value of molality in equation we get

Thus, in order to determine M2, molar mass of the solute, known mass of solute in a
known mass of the solvent is taken and Tb is determined experimentally for a known
solvent whose Kb value is known.
Depression in freezing point
Freezing point is defined as “the temperature at which the solid and the liquid
states of the substance have the same vapour pressure”. At freezing point, the solid and
liquid phases of the substance are in equilibrium. For example, the freezing point of water
is 0 ˚C. At this temperature the ice and the water are in equilibrium. When a nonvolatile
solute is added to water at its freezing point, the freezing point of the solution is lowered
from 0 ˚C. The lowering of the freezing point of the solvent when a solute is added is
called depression in freezing point (ΔTf).

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The depression in freezing temperature (ΔTf) can be expressed as,
ΔTf = Tfo- Tf
Tfo is the freezing point of pure solvent and Tf be its freezing point when non-volatile
solute is dissolved in it.
Similar to elevation of boiling point, for dilute solutions the elevation of boiling point (ΔTf)
is directly proportional to the molal concentration of the solute in a solution. Thus
ΔTf α m
or ΔTf = Kf m
Here m (molality) is the number of moles of solute dissolved in 1 kg of solvent and the
constant of proportionality, Kf is called Freezing Point Depression Constant or Molal
Depression Constant or Cryoscopic Constant. The unit of Kf is K kg mol-1.
Molal Depression Constant is the depression in freezing point of a solution containing 1
gram mole of a solute per 1000 grams of the solvent.

If w2 gram of solute of molar mass M2 is dissolved in w1 gram of solvent, produces the

depression in freezing point ΔTf of the solvent then molality, m of the solution is given by
the expression:

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Substituting the value of molality in equation we get

Thus, in order to determine M2, molar mass of the solute, known mass of solute in a
known mass of the solvent is taken and Tb is determined experimentally for a known
solvent whose Kf value is known.
Determination of Kf and Kb values from heat of fusion and vapourization

Osmosis and osmotic pressure

Osmosis is a spontaneous process by which the solvent molecules pass through
a semi permeable membrane from a solution of lower concentration to a solution of higher
concentration. The name osmosis is derived from the Greek word ‘osmos’ which means
‘to push’. Semipermeable membrane selectively allows solvent molecules in the solution
to pass through it but not others.

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 Assume that only solvent molecules can pass through these semipermeable
membranes. If this membrane is placed between the solvent and solution as shown in
Figure the solvent molecules will flow through the membrane from pure solvent to the
solution. This process of flow of the solvent is called osmosis.

The flow will continue till the equilibrium is attained. The flow of the solvent from
its side to solution side across a semipermeable membrane can be stopped if some extra
pressure is applied on the solution. The excess pressure applied on the solution side just
prevent osmosis (flow of solvent) is called osmotic pressure (π) of the solution.
Solvent molecules always flow from lower concentration to higher concentration of
solution. The osmotic pressure has been found to depend on the concentration of the
solution.
Most commonly used semipermeable membranes are copper ferrocyanide,
calcium phosphate, cellulose nitrate, polyamides, polysulfones etc. Semipermeable
membrane of copper ferrocyanide is most widely used in lab. Since it can resist high
pressure of about 150 atm and also easy to prepare.

Preparation of copper ferrocyanide semipermeable membrane

The porous pot in which SPM is to be prepared is first thoroughly cleaned by washing it
with acid, water, alkali and finally with distilled water. The air bubbles in the pores of the
pot are removed by forcing water through the pot under pressure.The pot is then filled
with 2.5% solution of copper sulfate. And also then placed in a container with a solution
of potassium ferrocyanide of the same strength.

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Copper ions go out of the pot. While ferrocyanide ions come into the pot. They meet
somewhere in the walls of the pot to form a membrane of copper ferrocyanide.
2CuSO4 + K4[Fe(CN)6] → Cu2 [Fe(CN)6] + 2K2SO4
2Cu²+ + Fe(CN)6 → Cu2[Fe(CN)6]
copper ferrocyanide

For dilute solutions, it has been found experimentally that osmotic pressure is proportional
to the molarity, C of the solution at a given temperature T.

Determination of molar mass from osmotic pressure

According to van’t Hoff equation

Here, n= number of moles of solute dissolved in ‘V’ litre of the solution .

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If the solution is prepared by dissolving wB g of nonvolatile solute in wA g of solvent, then
the number of moles ‘n’ is,

Significances of osmotic pressure over other colligative properties

Unlike elevation of boiling point (for 1 molal solution the elevation in boiling point
is 0.512 ˚C for water) and the depression in freezing point (for 1 molal solution the
depression in freezing point is 1.86 ˚C for water), the magnitude of osmotic pressure is
large. According to the Van't Hoff equation, an ideal solution containing 1 mole of
dissolved particles per liter of solvent at 0° C will have an osmotic pressure of 22.4 atm.
Even for a very dilute solution, the osmotic pressure is large. The osmotic pressure can
be measured at room temperature enables to determine the molecular mass of
biomolecules which are unstable at higher temperatures.
Isotonic solutions Two solutions having same osmotic pressure at a given
temperature are called isotonic solutions. When such solutions are separated by a
semipermeable membrane, solvent flow between one to the other on either direction is
same, i.e. the net solvent flow between the two isotonic solutions is zero. The osmotic
pressure of the blood cells is approximately equal to 7 atm at 37˚C. The intravenous
injections should have same osmotic pressure as that of the blood (isotonic with blood).
If the Intravenous solutions are too dilute that is hypotonic, the solvent from outside of the
cells will flow into the cell to normalise the osmotic pressure and this process which is
called hemolysis, causes the cells to burst. On the other hand, if the solution is too
concentrated, that is hypertonic, the solvent molecules will flow out of the cells, which

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causes the cells to shrink and die. For this reason, the Intravenous fluids are prepared
such they are isotonic to blood (0.9 % mass/ volume sodium chloride solution).
Hypertonic solution is a solution that has a greater concentration of solutes on the
outside of a cell when compared with the inside of a cell (it has higher osmotic pressure
than outside solution).
Hypotonic solution is a solution that has a lower concentration of solutes on the outside
of a cell when compared with the inside of a cell (it has lower osmotic pressure outside
solution).
Isotonic solution is a solution that has equal concentration of solutes outside the cell
and inside of the cell (outside and inside solutions have same osmotic pressure).

Osmosis Diffusion
Happens only in liquid state. Occurs in liquids or gases.

Movement of only water or solvent from Any type of substance that moves from
higher concentration to lower higher concentration to lower
concentration. concentration.

Applied only for the solvent part of the Applied for all states of matter.
solution.

Does not require semipermeable

Requires semipermeable membrane.
membrane.

In this process, concentration of solvent is Concentration of whole substance will be

not equalized. equalized.

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Process is slower when compared to Process is faster when compared to
diffusion osmosis

Determination of osmotic pressure: Berkeley and Hartley’s method

Various methods are employed for the measurement of osmotic pressure but
the best known method was suggested by Berkeley and Hartley. The apparatus used is
shown in Figure. A porcelain tube having copper ferrocyanide membrane(semi
permeable) in its walls in enclosed in a metallic jacket. The porcelain tube is fitted with a
reservoir of pure solvent at one end and a capillary tube at the other end. In a metallic
jacket is an arrangement for applying external pressure which is measured with the help
of pressure eggs.
Procedure:
The porcelain tube is filled with pure solvent and the metallic jacket with solution. The
level in the capillary tube will tend to move down as the solvent flows towards solution
due to osmosis. External pressure is now applied on the solution by the piston so that
level in capillary remain stationary. The reading of pressure gauge is recorded. This is the
osmotic pressure of the solution.

Reverse osmosis

The direction of osmosis can be reversed if a pressure larger than the osmotic pressure
is applied to the solution side. That is, now the pure solvent flows out of the solution
through the semi permeable membrane. This phenomenon is called reverse osmosis.

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 Reverse osmosis is used in the desalination of sea water and also in the
purification of drinking water. A simple set up used in both the process is shown in the
figure. When a pressure higher than the osmotic pressure is applied on the solution side
(sea water) the water molecules moves from solution side to the solvent side through
semipermeable membrane (Opposite to the Osmotic flow). The pure water can be
collected. There are different types of semipermeable membranes used in this process.
The membrane used for reverse osmosis has to withstand high pressures. Generally,
cellulose acetate or polyamide membranes are commonly used in commercial systems.

Abnormal molar mass

Association or dissociation of solute molecules:
Normally, the molar mass determination using measured colligative properties
assumes that the solute does not dissociate or associate.
Association
In certain solvents, solute molecules associate to form a dimer or trimer etc… This
reduces the total number of particles (molecules) formed in solution and as a result the
calculated molar mass will be higher than the actual molar mass.
Let us consider a solution of acetic acid in benzene. It is already established that
acetic acid forms inter molecular hydrogen bonds as shown in the figure and exists as a
dimer in benzene.

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The molar mass of acetic acid calculated using colligative properties is found to be
-1
around 120 g mol-1 is two times the actual molar mass (60 g mol ).

Dissociation
The electrolytes such as KCl or NaCl dissociates completely into its constitutent
ions in their aqueous solution. This causes an increase in the total number of particles
(ions) present in the solution. The calculated molar mass using colligative property
measurement for this type of solutions will be lower than the actual molar mass.
For example, the sodium chloride dissociates into Na+ ions and Cl- ions in aqueous
solution, as shown below.

When we dissolve 1 mole of NaCl (58.4 g) in water, it dissociates and gives 1 mole
of Na+ and 1 mole of Cl-. Hence, the solution will have 2 moles of particles. Thus, the
colligative properties would be double the expected value.

van’t Hoff factor

To quantify the extent of association or dissociation of solutes in solution, van’t

Hoff introduced a term 'i' which is now called van’t Hoff factor. It is defined as the ratio of
the actual molar mass to the abnormal (calculated) molar mass of the solute. Here, the
abnormal molar mass is the molar mass calculated using the experimentally determined
colligative property.

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 The estimated Van’t Hoff factor for acetic acid solution in Benzene is 0.5 and that
of sodium chloride solution in water is 2

For association

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 For a solute that does not dissociate or associate the van’t Hoff factor is equal to
1 (i = 1) and the molar mass will be close to the actual molar mass.
For the solutes that associate to form higher oligomers in solution the van’t Hoff
factor will be less than one (i <1) and the observed molar mass will be greater than the
actual molar mass.

For solutes that dissociates into their constituent ions the van’t Hoff factor will be
more than one (i > 1) and the observed molar mass will be less than the normal molar
mass.
The equations relating the four colligative properties with the concentration of the
solutes can be rewritten as follow by incorporating the van’t Hoff factor

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