June, 1933 353
FREEZING-POINT LOWERING
THOMAS B. GREENSLADE
The City College of the College of the City of New York
lowering of the freezing point of a pure sol-
THE vent by the addition of a solute is a common
currence
oc-
in everyday life. Yet few texts in first-
year college chemistry attempt an explanation of this
phenomenon.
Some authors “explain” the lowering by means of a
diagram showing the vapor pressure-temperature rela-
tionships between ice, water, vapor, and solution. It
must be pointed out, however, that this method of ap-
proach is not understood by first-year students, and
does not effect an explanation of the phenomenon, but
rather a proof that equilibrium may exist only at the
lowered temperature.
Since almost all texts explain the lowering of the
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vapor pressure of a solvent and the elevation of the
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boiling point due to the addition of a non-volatile solute
on the basis of the kinetic molecular theory, it would
seem desirable to undertake an analogous explana-
tion for the freezing-point depression. With this idea
in mind, the following explanation is offered for use in
first-year college classes.
Molecules in the solid state are in constant vibratory
motion. The kinetic energy of these molecules in-
creases as the temperature increases. Some of those
near the surface may gain sufficient energy to overcome
the forces holding them in place in the crystal lattice.
In that case they break away from the solid and enter
the liquid state.
As soon as any liquid is formed, some of the molecules
in the liquid state begin to go back to the solid state.
When the number of molecules leaving the solid and
going into the liquid state is equal to the number going
from the liquid to the solid, equilibrium is established.
Let us consider a unit surface between water and ice
in equilibrium at 0°C. In any given unit of time there
are as many molecules leaving the ice and entering the
liquid state as there are molecules leaving the water and
forming solid. Suppose now that we add a solute such
as sodium chloride to the mixture. The salt dissolves
in the water, and we have a solution in contact with
ice. Since the number of water molecules per unit
volume in the liquid has been diminished by this addi-
tion of solute molecules, the rate of ice formation is de-
creased, Now there are more molecules changing from
the solid to the liquid state than are returning to the
solid, heat is absorbed, and the temperature falls.
This lowering of the temperature continues until it
effects an equalization of the rates of ice and water for-
mation. At the temperature at which this occurs a
new equilibrium is established between ice and solu-
tion, and they can exist in contact with each other.
This is, by definition, the freezing point of the solution.