Colligative

properties

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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
molecules in a solution, and not on the
nature of the chemical species present.[1]
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 only exact 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 assuming
that the solution is ideal.

Only properties which result from the

dissolution of nonvolatile solute in a
volatile liquid solvent are considered.[2]
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
therefore reduce the concentration of
solvent, so that the colligative properties
are independent of the nature of the
solute. The word colligative is derived
from the Latin colligatus meaning bound
together.[3] 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.[4]

Colligative properties include:

 Relative lowering of vapour pressure
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. Alternatively,
measurements for ionized solutes can
lead to an estimation of the percentage of
dissociation taking place.

Colligative properties are mostly studied

for dilute solutions, whose behavior may
be approximated as that of an ideal
solution. In fact, all of the properties listed
above are only colligative 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 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 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.[5]

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 evaluation
of the cryoscopic constant as
, where ΔHfus is
the solvent molar enthalpy of fusion.[5]

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.
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, , 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).[6]

History
The word colligative (Latin: co, ligare) was
introduced in 1891 by Wilhelm Ostwald.
Ostwald classified solute properties in
three categories:[7][8]

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.

References
1. McQuarrie, Donald, et al. Colligative
properties of Solutions" General
Chemistry Mill Valley: Library of
Congress, 2011. ISBN 978-1-89138-
960-3.
2. KL Kapoor Applications of
Thermodynamics Volume 3
3. K.J. Laidler and J.L. Meiser, Physical
Chemistry (Benjamin/Cummings
1982), p.196
4. Castellan, Gilbert W. (1983). Physical
Chemistry (3rd ed.). Addison-Wesley.
p. 281. ISBN 978-0201103861.
Retrieved 20 July 2019.
5. T. Engel and P. Reid, Physical
Chemistry (Pearson Benjamin
Cummings 2006) p.204-5
. Engel and Reid p.207
7. W.B. Jensen, J. Chem. Educ. 75, 679
(1998) Logic, History, and the
 Chemistry Textbook I. Does Chemistry
Have a Logical Structure?
. H.W. Smith, Circulation 21, 808 (1960)
Theory of Solutions: A Knowledge of
the Laws of Solutions ...

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