DEPRESSION OF FREEZING POINT:

Before the explanation of this topic , we should know “What is meant by Freezing
point and on what factors it depends?”

FREEZING POINT:
When a liquid is cool, the average energy of the molecules decreases. At some
point, the amount of heat removed is great enough that the attractive forces
between molecules obviously draw the molecules together and liquid freezes to a
solid. So,

“THE FREEZING POINT OF A SUBSTANCE IS THE TEMPERATURE AT

WHICH THE SOLID AND THE LIQUID PHASES OF THE SUBSTANCE
COEXISTS.”

OR

“THE TEMPERTURE AT WHICH A LIQUID TURNS INTO A SOLID WHEN

COOLED.”

For a given substance, we should know that the freezing point of its liquid form is
the same as the melting point of its solid form.

FACTORS AFFECTING THE FREEZING POINT:

There are three important properties of a substance on which depression of the
freezing point depends.

 The first property is the molar mass of the molecules that make up that
substance.
 The second property is the nature of the intermolecular forces that hold the
molecules of a substance together.
 The third property is the shape of molecules that make up the substance.
DEPRESSION OF FREEZING POINT:
As we know, in order to observe this colligative property (The property that
depends on the number of solute and solvent molecules or ions) following
conditions should be fulfilled by the solutions.

 Solution should be dilute.

 Solute should be non -volatile.
 Solute should be non- electrolyte.

So,The depression of the freezing point is defined as:

“WHEN A NON VOLATILE SOLUTE IS ADDED TO A SOLVENT, ITS

VAPOUR PRESSURE IS DECREASED.THIS IS KNOWN AS DEPRESSION
OF FREEZING POINT.”

Now, for a freezing point,we have two things in the vessel that are
“Liquid solution” and “Solid solvent”.The temperature at which the
vapour pressure of liquid solution and solid solvent are same then the
solution will freeze at this temperature.That means,a solution should
freeze at a temperature that is lower than the pure solvent.

GRAPHICAL REPRESENTATION:
In order to explain how the vapour pressure of the solution is lower than
the pure solvent lets explain it through graph.The graph is plotted for
the depression of the freezing point.It shows the vapour pressure at the
Y-Axis and the temperature at the X-Axis.We observe two curves in the
graph.The first curve EBC is for the pure solvent.Now ,this curve
represents that solvent freezes at a temperature 𝑇1 corresponds to the
point B.When the vapour pressure of the freezing solvent is 𝑃0 .Now in
the curve EBC the portion of the curve BE is for
solid solvent and the portion of the curve BC is for the pure
solvent.Now,in the portion BE we can conclude that this portion has a
great slope.It means that change of the vapour pressure with the change
of temperature in this curve is more rapid.Now,the curve DFE represents
the vapour pressure of solution.This curve will meet the curve BE at the
point F.Now this point represents the freezing point of the solution 𝑇2 .

Now, from the graph we conclude that vapour pressure of the pure
solvent is greater than the vapour pressure of the solution(it can been
seen in the graph).

CALCULATION OF DEPRESSION OF FREEZING POINT:

As we know depression of the freezing point is equal to the freezing point of the
pure solvent minus the freezing point of the solution.
Depression of freezing point = Freezing oint of pure solvent – Freezing point of
solution

So, 𝑻𝒇 =𝑻𝟏− 𝑻𝟐

This depression in freezing point 𝑇𝑓 is related to the molality of the solution not
the molarity.The reason is that freezing point depression and boiling point
elevation are COLLIGATIVE PROPERTIES, which means that they depend on
the AMOUNT of substance, more specifically the amount of solute, that is in a
given amount of solution. Since molarity = moles solute / liters solution, it cannot
be used since liters is a unit of volume, not a unit of mass, and hence, not an
AMOUNT. On the other hand, molality can be used since: molality = moles solute
/ kilograms solvent, both of which are mass quantities, and both of which directly
involve the AMOUNT of substance in terms of mass. And since freezing point
depression and boiling point elevation depend on their colligative nature for their
values, the AMOUNT of subtance (in mass) directly affects the values of boiling
point elevation and freezing point depression. Hence, since only molality involves
the AMOUNT of both the solute and solvent, and because boiling point elevation
and freezing point depression are colligative properties, only molality can be used
to determine the new freezing or boiling point of the solution. And thus, molarity
cannot be used since it does not directly involve the AMOUNTS of both the solute
and solvent of the solution.So,

𝑇𝑓 ∝ m

𝑇𝑓 =𝐾𝑓 *m

K is called the molar freezing point constant or the cryoscopic constant and m is
the molarity of the solution.As,molality is equal to:
1000∗𝑊2
m=
𝑀2 ∗𝑊1

By putting the values:

1000∗𝑊2
𝑇𝑓 =
𝑀2 ∗𝑊1

Where,
𝑊2 = Mass of solute.

𝑀2 = Molar mass of solute.

𝑊1 = Mass of solvent in kg.

MEASUREMENT OF FREEZING POINT DEPRESSION:

For the measurement of freezing point depression, the apparatus used and easy to
perform is BECKMANN’S FREEZING POINT APPARATUS

BECKMANN’S FREEZING POINT APPARATUS:

It consists of a test tube A, provided with a side inlet tube D, and a cork through
which a thermometer T and a platinum wire stirrer S2 pass. This test tube is
surrounded by a larger tube B, the space between the two forming an air jacket.
Both are surrounded by a larger vessel C, which call be filled with a suitable
freezing mixture. The latter is kept in circulation by means of the wire stirrer S1.
mixture is introduced into C, and the whole apparatus is allowed to stand till the

thermometer T indicates a temperature one or two

degrees below the probable freezing point of the liquid. The platinum wire stirrer
S2 is then moved briskly up and down, when solidification will generally occur.
The temperature indicated by T rises and shortly attains a value which remains
constant some time. This temperature is the freezing point of the liquid.

APPLICATIONS OF FREEZING POINT DEPRESSION:

Apart from the molecular mass determination the presence of a solute increases the
liquid range of the solution. Both by raising the boiling point and lowering the
freezing point. Some of the applications are as follows:
 It is used to prevent car from freezing by adding anti freeze.The anti freeze
also causes an elevation in boiling point.So,it prevents the car from
overheating in summer.In U.S.A, there was an antifreeze called Prestone that
advertise itself as winter summer protection.
 The most prominent use is to find the molar mass of an unknown compound
dissolved in a solvent.
 The freezing point of pure water is 0 degree Celsius.But the melting point
can be depressed by adding of a solvent such as salt.With use of ordinary
salt like NaCl on icy roads in the winter helps to melt the ice from the roads
by lowering the melting point of ice.