In chemistry, colligative properties are properties of solutions that

depend upon the ratio of the number of solute particles to the number of
solvent molecules in a solution, and not on the type of chemical species
present. This number ratio can be related to the various units for
concentration of solutions. Here we shall only consider those properties
which result because of the dissolution of nonvolatile solute in a volatile
liquid solvent. They are independent of the nature of the solute particles,
and are due essentially to the dilution of the solvent by the solute. The
word colligative is derived from the Latin colligatus meaning bound
together.
History
The word colligative (German: kolligativ) was introduced in 1891 by
Wilhelm Ostwald. Ostwald classified solute properties in three
categories:
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 solute.
Colligative properties include:
1. Relative lowering of vapor pressure
2. Elevation of boiling point
3. Depression of freezing point
4. Osmotic pressure.
Measurement of colligative properties for a dilute solution of a nonionized 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.
Alternatively, measurements for ionized solutes can lead to an
estimation of the percentage of ionization taking place.
Colligative properties are mostly studied for dilute solutions, whose
behavior may often be approximated as that of an ideal solution.

Relative lowering of vapor pressure

The vapor pressure of a liquid is the pressure of a vapor in equilibrium
with the liquid phase. The vapor pressure of a solvent is lowered by
addition of a non-volatile solute to form a solution.
For an ideal solution, the equilibrium vapor 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

vapor

pressure

lowering

relative

to

pure

solvent

is

, which is proportional to the mole

fraction of solute.

If the solute dissociates in solution, then the vapor pressure lowering 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

. 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 vapor 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 vapor 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 is the temperature ( ) at which its vapor
pressure is equal to the external pressure. The normal boiling point is the
boiling point at a pressure equal to 1 atmosphere.
The boiling point of a pure solvent is increased by the addition of a nonvolatile solute, and the elevation can be measured by ebullioscopy. It is
found that

Here i 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 A 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 Hvap is the solvent molar enthalpy of vaporization.[4]

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. Again "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
evaluation of the cryoscopic constant as

, where

Hfus is the solvent molar enthalpy of fusion.[4]

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. vant Hoff:

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

directly proportional to its concentration.
2. The osmotic pressure of a solution is directly proportional to its
absolute temperature.
These are analogous to Boyle's law and Charles's Law for gases.
Similarly, the combined ideal gas law,
ideal solutions

, where

, has as analog for

is osmotic pressure; V is the

volume; n is the number of moles of solute; R is the molar gas constant

8.314 J K1 mol1; 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 + .[5]

Experimental Aspects of Membrane Osmometry

Asimple type of osmometer is illustrated in Fig The solution is placed in
a cell with membranes on either side (one or two membranes, but two
gives more area and faster equilibration). The entire assembly is then
immersed in pure solvent. The heights of the liquids in the capillaries are
read and the height dierence gives the osmotic pressure. This apparatus
is called a block type osmometer. It is the type of osmometer used to get
the data that will be given to you in a lab. This osmometer uses a small
cell and a large membrane.

The membrane is supported by stainless steel plates with holes. By

supporting the membrane, the membrane can be made larger; with larger
membrane area equilibrium will be reached sooner. Block osmometers
are called static osmometers because they wait for the natural
development of equilibrium. The problem with static osmometers is that
it can take hours (12-24 hrs) to reach
an accurate equilibrium. The time depends on many factors such as the
membrane area and the speed of transport through the membrane. To
quicken osmotic pressure experiments, dynamic osmometers are
sometimes used. Recall that osmotic pressure develops for the purpose
of raising the activity of the solvent in the solution to 1. By applying a
pressure it is possible to do the same thing. You will know when you
have applied the correct pressure by monitoring ow across the
membrane. When you apply enough pressure to stop the ow you have
articially reached equilibrium. The pressure required can be used to get
the equilibrium osmotic pressure. This quick method, unfortunately, is
less accurate. Finally, we make a few comments about what makes a
good semipermeable membrane. The membrane must be permeable to
solvent and impermeable to polymer. This requirement limits the lowend applicability of osmometry to MN of 20,000 g/mol or more. Note
that we really require all polymers to be above 20,000 g/mol otherwise
the low molecular weight tail will pass through membrane and the
measured MN will be too high (do you see why it would be too high?).

Therefore, polydisperse polymers probably require MN greater than

about 50,000 g/mol; for monodisperse polymers it might be possible to
go down to 20,000 g/mol. There are also some material concerns for the
membrane. An obvious concern is that the mem- brane not be soluble in
the solvent. Perhaps the most common membrane material is gel
cellulose.
Other membranes include cellulose hydrate, cellulose acetate, cellulose
nitrate, polyurethanes, and poly(chlorotriuoroethylene).
Problems 51. In analyzing osmotic pressure data why is a plot ofp(/c)
versus c sometimes used rather than a plot of (/c) versus c?
52. The following are data from osmotic pressure measurements on a
solution of polyester in chloroform at 20C. The results are in terms of
centimeters of solvent. The density of HCCl3 is 1.48 g/cm3. Plot /c
versus c and nd MN under the assumption that you can neglect terms
beyond the second virial coecient.
c (g/dl) h (cm of HCCl3) 0.57 2.829 0.28 1.008 0.17 0.521 0.10 0.275
53. a. Suppose that in a dierent universe that the boiling point
elevation was given instead by HvapTb RT2 b = wBMB M0 = 1
M0X i wiMi (5.47) where wi is the weight fraction of polymer with
molecular weight Mi and M0 is the monomer molecular weight. By this
law, what molecular weight average could by found from boiling point

elevation measurements and give a formula for calculating that molecular weight average. b. The measurement of boiling point elevation is
not very useful for nding the molecular weight of high molecular
weight polymers. If boiling point elevation was given instead by the
formula in part a, would it be a more or less useful approach to nding
the molecular weight of high molecular weight materials?