COLLIGATIVE PROPERTY

We are accustomed to describing a solution in terms of the

concentration of the one or more solutes. However, many of the
simportant physical properties of a solution depend more directly on
the concentration of the solvent. These properties include the vapor
pressure, the freezing point, the boiling point, and the osmotic
pressure. Because they are "tied together" (Latin, co ligare) in this
way, they are referred to as the colligative properties of solutions.

The colligative properties that we will consider in this and the next unit
apply to to solutions in which the solute is non-volatile; that is, it does
not make a significant contribution to the overall vapor pressure of the
solution. Solutions of salt or sugar in water fulfill this condition exactly.
Other solutes that have very small vapor pressures, such as iodine or
ethylene glycol antifreeze, can often be considered nonvolatile in
comparison to the solvent at the same temperature. Solutions in which
both components possess significant vapor pressures, such as alcohol
in water, will be treated in another section farther on.

1. Vapour pressure of solutions:

The colligative properties really depend on the escaping tendency of
solvent molecules from the liquid phase. You will recall that the vapour
pressure is a direct measure of escaping tendency, so we can use
these terms more or less interchangeably.
The tendency of molecules to escape from a liquid phase into the gas
phase depends in part on how much of an increase in entropy can be
achieved in doing so. Evaporation of solvent molecules from the liquid
always leads to a large increase in entropy because of the greater
volume occupied by the molecules in the gaseous state. But if the
liquid solvent is initially diluted with solute, its entropy is already
larger to start with, so the amount by which it can increase on
entering the gas phase will be less. There will accordingly be less
tendency for the solvent molecules to enter the gas phase, and so the
vapor pressure of the solution diminishes as the concentration of
solute increases and that of solvent decreases.

The number 55.5 mol L1 (= 1000 g L1 18 g mol1) is a

useful one to remember if you are dealing a lot with

aqueous solutions; this represents the concentration of

water in pure water. (Strictly speaking, this is the molal
concentration of H2O; it is only the molar concentration at
temperatures around 4 C, where the density of water is
closest to 1.000 g cm1.)

Diagram represents pure water whose

concentration in the liquid is 55.5 M. A tiny fraction
of the H2O molecules will escape into the vapor
space, and if the top of the container is closed, the
pressure of water vapor builds up until equilibrium
is achieved. Once this happens, water molecules
continue to pass between the liquid and vapor in
both directions, but at equal rates, so the partial
pressure of H2O in the vapor remains constant at a
value known as the vapor pressure of water at
the particular temperature.
In the system on the right, we have replaced a
fraction of the water molecules with a substance
that has zero or negligible vapor pressure
a nonvolatile solute such as salt or sugar. This has
the effect of diluting the water, reducing its
escaping tendency and thus its vapor pressure.

What's important to
remember is that the
reduction in the
vapor pressure of a

solution of this kind is directly proportional to the fraction of the

[volatile] solute molecules in the liquid that is, to the mole fraction
of the solvent. The reduced vapor pressure is given by Raoult's law :

2.Boiling point elevation

If addition of a nonvolatile solute lowers the
vapor pressure of the solution, then it follows
that the temperature must be raised to
restore the vapor pressure to the value

corresponding to the pure solvent. In

particular, the temperature at which the vapor
pressure is 1 atm will be higher than the
normal boiling point by an amount known as
the boiling point elevation.
The exact relation between the boiling point
of the solution and the mole fraction of the
solvent is rather complicated, but for dilute
solutions the elevation of the boiling point is
directly proportional to the molalconcentration
of the solute:

Bear in mind that the proportionality constant KB is

a property of the solvent because this is the only
component that contributes to the vapor pressure
in the model we are considering in this section.
Boiling point elevation constants
solvent

normal
Kb , K
bp, C mol1 kg

water

100

0.514

ethanol

79

1.19

acetic acid

118

2.93

carbon
tetrachloride

76.5

5.03

3. Freezing point depression

The freezing point of a substance is the
temperature at which the solid and liquid
forms can coexist indefinitely that is, they
are in equilibrium. Under these conditions
molecules pass between the two phases at

equal rates because their escaping tendencies

from the two phases are identical.
Suppose that a liquid solvent and its solid
(water and ice, for example) are in
equilibrium , and we add a non-volatile solute
(such as salt, sugar, or automotive antifreeze
liquid) to the water. This will have the effect
of reducing the mole fraction of H2O
molecules in the liquid phase, and thus
reduce the tendency of these molecules to
escape from it, not only into the vapor phase
(as we saw above), but also into the solid
(ice) phase. This will have no effect on the
rate at which H2O molecules escape from the
ice into the water phase, so the system will
no longer be in equilibrium and the ice will
begin to melt .

If we wish to keep the solid from melting, the

escaping tendency of molecules from the solid
must be reduced. This can be accomplished
by reducing the temperature; this lowers the
escaping tendency of molecules from both
phases, but it affects those in the solid more
than those in the liquid, so we eventually
reach the new, lower freezing point where the
two quantities are again in exact balance and
both phases can co-exist .
If you prefer to think in terms of vapor
pressures, you can use the same argument if
you bear in mind that the vapor pressures of
the solid and liquid must be the same at the
freezing point. Dilution of the liquid (the
solvent) by the nonvolatile solute reduces the
vapor pressure of the solvent according to
Raoults law, thus reducing the temperature
at which the vapor pressures of the liquid and
frozen forms of the solution will be equal.
As with boiling point elevation, in dilute
solutions there is a simple linear relation
between the freezing point depression and
the molality of the solute:

Note that Kf values are all negative!

Freezing point depression
constants
normal
fp , C

solvent

Kf , K mol
1
kg

water

0.0

1.86

acetic acid

16.7

3.90

benzene

5.5

5.10

camphor

180

40.0

cyclohexane

6.5

20.2

phenol

40

7.3

The use of salt to de-ice roads is a common application of this principle. The solution formed
when some of the salt dissolves in the moist ice reduces the freezing point of the ice. If the
freezing point falls below the ambient temperature, the ice melts. In very cold weather, the
ambient temperature may be below that of the salt solution, and the salt will have no effect.
The effectiveness of a de-icing salt depends on the number of particles it releases on
dissociation and on its solubility in water:

name
ammonium

formula

lowest practical
T, C

(NH4)2SO4 7

sulfate
calcium
chloride

CaCl2

29

potassium
chloride

KCl

15

sodium
chloride

NaCl

urea

(NH2)2CO

Automotive radiator antifreezes are mostly based on ethylene glycol, (CH2OH)2. Owing to
the strong hydrogen-bonding properties of this double alcohol, this substance is miscible
with water in all proportions, and contributes only a very small vapor pressure of its own.
Besides lowering the freezing point, antifreeze also raises the boiling point, increasing the
operating range of the cooling system. The pure glycol freezes at 12.9C and boils at
197C, allowing water-glycol mixtures to be tailored to a wide range of conditions.

All these effects result from dilution of the

solvent by the added solute, and because of
this commonality they are referred to
as colligative properties (Lat. co ligare,
connected to.) The key role of the solvent

concentration is obscured by the greatlysimplified expressions used to calculate the

magnitude of these effects, in which only the
solute concentration appears. The details of
how to carry out these calculations and the
many important applications of colligative
properties are covered elsewhere. Our
purpose here is to offer a more complete
explanation of whythese phenomena occur.
Basically, these all result from the effect
of dilution of the solvent on its entropy,
and thus in the increase in the density of
energy states of the system in the solution
compared to that in the pure liquid.
Equilibrium between two phases (liquid-gas
for boiling and solid-liquid for freezing) occurs
when the energy states in each phase can be
populated at equal densities. The
temperatures at which this occurs are
depicted by the shading.
Dilution of the solvent
adds new energy states
to the liquid, but does

not affect the vapor phase. This raises the

temperature required to make equal numbers
of microstates accessible in the two phases.

Dilution of the solvent

adds new energy
states to the liquid, but
does not affect
the solid phase. This
reduces the
temperature required to make equal numbers
of states accessible in the two phases.

4. Osmotic pressure
When a liquid is subjected to hydrostatic pressure
for example, by an inert, non-dissolving gas that
occupies the vapor space above the surface, the
vapor pressure of the liquid is raised. The pressure
acts to compress the liquid very slightly, effectively
narrowing the potential energy well in which the

individual molecules reside and thus increasing

their tendency to escape from the liquid phase.
(Because liquids are not very compressible, the
effect is quite small; a 100-atm applied pressure
will raise the vapor pressure of water at 25C by
only about 2 torr.) In terms of the entropy, we can
say that the applied pressure reduces the
dimensions of the "box" within which the principal
translational motions of the molecules are confined
within the liquid, thus reducing the density of
energy states in the liquid phase.
Applying hydrostatic
pressure to a liquid
increases the spacing of its
microstates, so that the
number of energetically
accessible states in the
gas, although unchanged, is relatively greater
thus increasing the tendency of molecules to
escape into the vapor phase. In terms of free
energy, the higher pressure raises the free energy
of the liquid, but does not affect that of the gas
phase.

This phenomenon can explain osmotic pressure.

Osmotic pressure, students must be reminded, is
not what drives osmosis, but is rather the
hydrostatic pressure that must be applied to the
more concentrated solution (more dilute solvent) in
order to stop osmotic flow of solvent into the
solution. The effect of this pressure is to slightly
increase the spacing of solvent energy states on
the high-pressure (dilute-solvent) side of the
membrane to match that of the pure solvent,
restoring osmotic equilibrium.

Osmotic pressure, the fourth member of the

quartet of colligative properties that arise from the
dilution of a solvent by non-volatile solutes, is
covered in the next chapter.