V.N.

Karazin Kharkov National University

Medical Chemistry
Module 1. Lecture 5

Colligative properties of
solutions

Natalya VODOLAZKAYA
[email protected]
28 December 2020 Department of Physical Chemistry
 Lecture topics
√ Colligative properties of solutions
√ Vapor pressure lowering
√ Boiling-point elevation
√ Freezing-point depression
√ Osmosis
√ Colligative properties of electrolyte solutions

2
 Colligative properties of solutions
Colligative properties of solutions are several important
properties that depend on the number of solute particles (atoms,
ions or molecules) in solution and not on the nature of the solute
particles.
It is important to keep in mind that we are talking about relatively
dilute solutions, that is, solutions whose concentrations are less 0.1
mol/L.
The term “colligative properties” denotes “properties that depend
on the collection”.
The colligative properties are:
¾ vapor pressure lowering,
¾ boiling-point elevation,
¾ freezing-point depression,
¾ osmotic pressure.
3
 Colligative properties of solutions:
Vapor pressure lowering

If a solute is nonvolatile, vapor pressure of the solution is

always less than that of the pure solvent and depends on
the concentration of the solute.
The relationship between solution vapor pressure and
solvent vapor pressure is known as Raoult’s law.
This law states that the vapor pressure of a solvent over a
solution (p1) equals the product of vapor pressure of the pure
solvent (p1°) and the mole fraction of the solvent in the solution
(x1):
p1 = x1p1°.
4
 Colligative properties of solutions:
Vapor pressure lowering

In a solution containing only one solute, than x1 = 1 – x2,

where x2 is the mole fraction of the solute.
Equation of the Raoult’s law can therefore be rewritten as

(p1° – p1)/p1° = x2.

One can see that the relative decrease in vapor pressure of

the solvent is directly proportional to the mole fraction of the
solute in solution.

5
 Colligative properties of solutions:
Boiling-point elevation
The boiling of a pure liquid or a solution occurs at that
temperature at which its vapor pressure becomes equal the external
atmospheric pressure.
Because at any temperature the vapor pressure of the solution is
lower than that of the pure solvent, the vapor pressure of solution
reaches atmospheric pressure at a higher temperature than the
normal boiling point of the pure solvent.
This leads to elevation of boiling point of solution in comparison
with pure solvent. The boiling-point elevation is defined as:

ΔTb = Tb − Tb,о > 0

where Tb is the boiling point of the solution, Tb,o – the boiling point
of the pure solvent.
6
 Colligative properties of solutions:
Boiling-point elevation
ΔTb = Kbm,
where m – molality of the solute, Kb is the molal boiling-point
elevation constant.
It has been proved theoretically that Kb is determined only by
properties of the solvent:
RTb2,o ⋅ M1
Kb = o
1000 ⋅ ΔH vap

R – universal gas constant, M1 – molar mass of the solvent, ΔH°vap –

enthalpy change of vaporization of the pure solvent.
The value of boiling-point elevation constant for water is 0.52
K·kg/mol. One can see that if the molality of an aqueous solution
is 1.00 mol/kg, the boiling point will be 100.52 °C.
7
 Colligative properties of solutions:
Freezing-point depression
The pure solvent freezes if its vapor pressures in liquid and solid
states are equal. The vapor pressure of a solid solvent depends on
temperature only and decreases with decrease in temperature.
These leads the temperature of the freezing of solution is lower than
the freezing point of the solvent. The depression of freezing point is
defined as:
ΔT = T − T > 0
f o, f f

To,f – freezing point of the pure solvent, and Tf – freezing point of the
solution. The ΔTf value is proportional to the molal concentration of the
solute:
ΔTf = Kfm,
where m – molality of the solute, and Kf is the molal freezing-point
depression constant. Like Kb, the Kf has the units K·kg·mol–1.

8
 Colligative properties of solutions:
Freezing-point depression
The Kf value depends only on properties of the solvent:

RT f2,o ⋅ M1
Kf =
1000 ⋅ ΔH ofus

ΔHfus is enthalpy change of fusion of the pure solvent.

In cold climate
regions, antifreeze
must be used in car
radiators in winter

De-icing of airplanes is based

on freezing-point depression

9
 Figure. Phase diagram illustrating the boiling-point elevation and freezing-
point depression of aqueous solutions.
The dashed curves pertain to the solution, and the solid curves to the pure
solvent. As you can see, the boiling point of the solution is higher than that of
water, and the freezing point of the solution is lower than that of water
10
 Colligative properties of solutions:
Freezing-point depression and
Boiling-point elevation
Table lists values of Kb for several common solvents. You can see that
if the molality of an aqueous solution is 1.00 m, the boiling point will be
100.52°C.

11
 Colligative properties of solutions: Osmosis
Osmosis is the spontaneous movement of a pure solvent into a
solution separated from it by a semipermeable membrane.
The membrane is permeable by the solvent molecules but not by the
solute and allows the solvent, but not the solute, to pass through.

Figure. Osmotic pressure. (a) The levels of the pure solvent (left) and of the solution
(right) are equal at the start. (b) During osmosis, the level on the solution side rises
as a result of the net flow of solvent from left to right. The osmotic pressure is equal
to the hydrostatic pressure exerted by the column of fluid in the right tube at
equilibrium 12
12
 Colligative properties of solutions:
Osmosis
The osmotic pressure is the pressure that must be applied to the
solution to prevent the solvent transfer.
For dilute solutions the osmotic pressure is given by the van't
Hoff equation:
π = cRT,
T – absolute temperature, c – molar concentration of the solute,
R − universal gas constant.

If two solutions are of equal concentration and, hence, of the

same osmotic pressure, they are said to be isotonic.
If two solutions are of unequal osmotic pressures, the more
concentrated solution is said to be hypertonic and the more dilute
solution is described as hypotonic.

13
 Colligative properties of solutions: Osmosis

Figure. A cell in (a) an isotonic solution, (b) a hypotonic solution, and (c) a
hypertonic solution. The cell remains unchanged in (a), swells in (b), and
shrinks in (c). (d) From left to right: a red blood cell in an isotonic solution,
in a hypotonic solution, and in a hypertonic solution.
14
 Colligative properties of electrolyte
solutions
The colligative properties of electrolytes is characterized by
slightly different approach than the one used for the colligative
properties of nonelectrolytes.
The colligative properties of binary electrolyte solution should
be twice as great as those of an electrolyte solution containing a
nonelectrolyte in the same concentration. Similarly, we would
expect a ternary electrolyte solution to depress the freezing point
by three times as much as a nonelectrolyte solution with the
concentration. To account for this effect we must modify the
equations for colligative properties as follows:
¾ ΔTb = iKb·m,
¾ (p1° – p1)/p1° = ix2,
¾ ΔTf = iKf·m,
¾ π = icRT. 15
 Colligative properties of electrolyte
solutions
The variable i is the van’t Hoff’s isotonic factor, which is defined as
the ratio of actual number of particles in solution after dissociation and
number of molecules (structural units) of initially dissolved substance.

Thus, i should be 1 for nonelectrolytes. For strong binary

electrolytes such as NaCl and KNO3, should be 2, and for strong
ternary electrolytes such as Na2SO4 and MgCl2, i should be 3.

16
 References
1. Chang R. Chemistry. 10-th edition. NY: McGraw-Hill, 2010.
1170 p.
2. Chang R. General Chemistry: The Essential Concepts. 6-th
edition. NY: McGraw-Hill, 2011. 853 p.
3. Allen J.P. Biophysical Chemistry. Blackwell Publishing, 2008.
492 p.
4. Atkins P., de Paola J. Physical Chemistry for the Life
Sciences. W.H.Freeman Publishers, 2006. 624 p.
5. S. V. Eltsov, N. A. Vodolazkaya. Practical Medical Chemistry:
manual / Kh.: V. N. Karazin Kharkiv National University, 2018.
196 p.

17