Expt.

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Cryoscopic Method of Molecular
Weight Determination

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 13.5 Colligative Properties

Freezing-Point Depression

where m is the concentration of solute expressed in

molality and Kf is the molal freezing-point depression
constant.

Like Kb, Kf has units of °C/m.

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Cooling Curves

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Phase equilibrium

Solid  Liquid

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 Phase equilibrium

Solid  Liquid

At the freezing point, the kinetic energy of the particles becomes low enough for inter-particle forces to lock the
particles into fixed positions in the solid crystal structure. However, if solute particles are present, the entropy (state
of disorder) of the liquid phase is increased. To reach the freezing point of the solution, the temperature has to be
lower than it is in the case of the pure solvent. The system must reach the point where the energy and entropy 5 are low
enough for the inter-particle forces to take control and fix the sovent particles in position in the crystal structure.
 Phase equilibrium

Solid  Liquid

Solute particles effectively decrease the surface area of the solid accessible to the solvent molecules. This
decreases the rate at which liquid-phase solvent molecules can stick to the solid. The rate of freezing is
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slowed while the rate of melting is unchanged. As the temperature is lowered, the rate of freezing (sticking) is
increased, and the rate of melting is decreased, until the rates of the two processes equalize (freezing point).
 True Values

Solid A (p-dichlorobenzene) = 146.998 g/mole

Solid B (benzoic acid) = 122.12 g/mole

Kf (napththalene) = 6.94 ºC / m

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 13.6 No. 1
Sample Problem
Ethylene glycol [CH2(OH)CH2(OH)] is a common
automobile antifreeze. It is water soluble and fairly
nonvolatile (b.p. 197°C).

Calculate (a) the freezing point and (b) the boiling point
of a solution containing 685 g of ethylene glycol in 2075
g of water.

Setup
The molar mass of ethylene glycol (C2H6O2) is 62.07
g/mol.

Kf and Kb for water are 1.86°C/m and 0.52°C/m,

respectively. 8
13.6

Solution

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 13.6 Calculations Using Colligative Properties

Calculations of Molar Mass Using Colligative Properties

The colligative properties of nonelectrolyte solutions
provide a means of determining the molar mass of a
solute.

Although any of the four colligative properties can be

used in theory for this purpose, only freezing-point
depression and osmotic pressure are used in practice
because they show the most pronounced, and therefore
the most easily measured, changes.

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 13.6 Calculations Using Colligative Properties

Calculations of Molar Using Colligative Properties

From the experimentally determined freezing-point
depression or osmotic pressure, we can calculate the
solution’s molality or molarity, respectively.

Knowing the mass of dissolved solute, we can readily

determine its molar mass.

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Sample Problem No. 2

A solution made from 0.840 g of a substance dissolved in 25.0

g of camphor froze at 170.80°C. The freezing point of pure
camphor is 178.40 °C and the molal freezing point depression
constant, Kf, for camphor is 37.7 °C/m. Calculate the
molecular weight of the solute.

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 Music Video

“For those about to dissolve,

we solute you”

by Mark Rosengarten

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