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# Introduction:

## Colligative properties are properties of solutions that depend on the

total number of solute particles in a solvent. The number of solute
particles effects both the freezing point depression and boiling point
elevation of solutions. The more particles that are in a solution, the
greater the depression or elevation, respectively.
One mole of a non-electrolyte, such as sucrose, lowers the freezing
point of 1L of water by 1.86C. However, one mole of an electrolyte,
which dissociates into ions or particles, lowers the freezing point of 1L
of water even more, corresponding to the number of ions produced.
For example, one mole of sodium chloride, which dissociates into Na+
and Cl- ions, contributes two moles of particles to the solution for every
mole of NaCl added. The freezing point depression of NaCl is
approximately (2)(1.86C). Because the ions can reassociate in the
solution in a random manner, the real freezing point depression is
somewhat less than the theoretical value of about 3.72C per mole of
NaCl added. Heidemann Fall NSC Lab Manual pg. 147

Physical properties can be divided into two categories. Extensive properties (such as mass and
volume) depend on the size of the sample. Intensive properties (such as density and
concentration) are characteristic properties of the substance; they do not depend on the size of
the sample being studied. This section introduces a third category that is a subset of the
intensive properties of a system. This third category, known as colligative properties, can only
be applied to solutions. By definition, one of the properties of a solution is a colligative
property if it depends only on the ratio of the number of particles of solute and solvent in the
solution, not the identity of the solute.
Very few of the physical properties of a solution are colligative properties. As an example of this
limited set of physical properties, let's consider what happens to the vapor pressure of the
solvent when we add a solute to form a solution. We'll define Po as the vapor pressure of the
pure liquid

the solvent

and P as the vapor pressure of the solvent after a solute has been

Po = vapor pressure of the pure liquid, or solvent

## P = vapor pressure of the solvent in a solution

When the temperature of a liquid is below its boiling point, we can assume that the only
molecules that can escape from the liquid to form a gas are those that lie near the surface of the
liquid.
When a solute is added to the solvent, some of the solute molecules occupy the space near the
surface of the liquid, as shown in the figure below. When a solute is dissolved in a solvent, the
number of solvent molecules near the surface decreases, and the vapor pressure of the solvent
decreases.

This has no effect on the rate at which solvent molecules in the gas phase condense to form a
liquid. But it decreases the rate at which the solvent molecules in the liquid can escape into the
gas phase. As a result, the vapor pressure of the solvent escaping from a solution should be
smaller than the vapor pressure of the pure solvent.

<

Po

vapor pressure
of the solvent
above a solution

vapor pressure
of the pure solvent

Between 1887 and 1888, Francois-Marie Raoult showed that the vapor pressure of a solution is
equal to the mole fraction of the solvent times the vapor pressure of the pure liquid.

P
vapor pressure
of the solvent
above a solution

solvent Po
vapor pressure of the
pure solvent

This equation, which is known as Raoult's law, is easy to understand. When the solvent is pure,
and the mole fraction of the solvent is equal to 1, P is equal to Po. As the mole fraction of the
solvent becomes smaller, the vapor pressure of the solvent escaping from the solution also
becomes smaller.
Let's assume, for the moment, that the solvent is the only component of the solution that is
volatile enough to have a measurable vapor pressure. If this is true, the vapor pressure of the
solution will be equal to the vapor pressure of the solvent escaping from the solution. Raoult's

law suggests that the difference between the vapor pressure of the pure solvent and the solution
increases as the mole fraction of the solvent decreases.
The change in the vapor pressure that occurs when a solute is added to a solvent is therefore a
colligative property. If it depends on the mole fraction of the solute, then it must depend on the
ratio of the number of particles of solute to solvent in the solution but not the identity of the
solute.
Boiling Point Elevation and Freezing Point Depression
The figure below shows the consequences of the fact that solutes lower the vapor pressure of a
solvent. The solid line connecting points B and C in this phase diagram contains the combinations
of temperature and pressure at which the pure solvent and its vapor are in equilibrium. Each
point on this line therefore describes the vapor pressure of the pure solvent at that temperature.
The dotted line in this figure describes the properties of a solution obtained by dissolving a solute
in the solvent. At any given temperature, the vapor pressure of the solvent escaping from the
solution is smaller than the vapor pressure of the pure solvent. The dotted line therefore lies
below the solid line.

The decrease in the vapor pressure of the solvent that occurs when a solute is
added to the solvent causes an increase in the boiling point and decrease in
the melting point of the solution.
According to this figure, the solution can't boil at the same temperature as the pure solvent. If
the vapor pressure of the solvent escaping from the solution is smaller than the vapor pressure
of the pure solvent at any given temperature, the solution must be heated to a higher

temperature before it boils. The lowering of the vapor pressure of the solvent that occurs when it
is used to form a solution therefore increases the boiling point of the liquid.
When phase diagrams were introduced, the triple point was defined as the only combination of
temperature and pressure at which the gas, liquid, and solid can exist at the same time. The
figure above shows that the triple point of the solution occurs at a lower temperature than the
triple point of the pure solvent. By itself, the change in the triple point is not important. But it
results in a change in the temperature at which the solution freezes or melts. To understand why,
we have to look carefully at the line that separates the solid and liquid regions in the phase
diagram. This line is almost vertical because the melting point of a substance is not very
sensitive to pressure.
Adding a solute to a solvent doesn't change the way the melting point depends on pressure. The
line that separates the solid and liquid regions of the solution is therefore parallel to the line that
serves the same function for the pure solvent. This line must pass through the triple point for the
solution, however. The decrease in the triple point that occurs when a solute is dissolved in a
solvent therefore decreases the melting point of the solution.
The figure above shows how the change in vapor pressure that occurs when a solute dissolves in
a solvent leads to changes in the melting point and the boiling point of the solvent as well.
Because the change in vapor pressure is a colligative property, which depends only on the
relative number of solute and solvent particles, the changes in the boiling point and the melting
point of the solvent are also colligative properties.

## freezing point depression

the change in the freezing point that occurs when the solute

dissolves in the solvent -- and kf is the molal freezing point depression constant for the solvent.
A negative sign is used in this equation to indicate that the freezing point of the solvent
decreases when a solute is added.
Values of kf and kb as well as the freezing points and boiling points for a number of pure solvents
are given in the tables below.
Here,

TBP is the boiling point elevation -- the change in the boiling point that occurs when a

## point elevation constant for the solvent.

A similar equation can be written to describe what happens to the freezing point (or melting
point) of a solvent when a solute is added to the solvent.
TFP = -kf m

It is well known that when you add salt to ice, the ice not only melts but will actually
get colder. From chemistry books I know that salt will lower the freezing point of
water. But Im a little confused as to why it results in a drop in temperature instead
of just ending up with water at 0 C.

What is occurring when salt melts the ice to make the temperature lower?

This ice cube will do what any ice cube above its melting point will do: it will melt. As
it melts, it cools down, since energy is being used to break bonds in the solid state.

(Note that the above point can be confusing if you're new to thinking about phase
transitions. An ice cube melting will take up energy, while an ice cube freezing will give off
energy. I like to think of it in terms of Le Chatelier's principle: if you need to lower the
temperature to freeze an ice cube, this means that the water gives off heat as it freezes.)
The cooling you get, therefore, comes from the fact that some of the bonds in the ice are
broken to form water, taking energy with them. The loss of energy from the ice cube is what
causes it to cool.

## We know that melting or freezing is an equilibrium process. The energy that is

required to melt an ice cube will not contribute in elevating its temperature until all
the solid water is molten.

If we take two ice cubes and add salt to one of them, then put each of them at room
temperature, both of the ice cubes will absorb energy from the surroundings, and this
energy as we said will contribute in breaking down the bonds between water molecules.
The cube that has not salt been added to, has a melting point 0 C0 C and so if we measure
its temperature during melting it will remain zero until all ice is molten. That ice cube to

which we have added salt, the salt that is added lowers the melting and freezing points of
water because it lowers the vapour pressure of water. This ice cube will absorb energy from
environment to help break bonds between water molecules. We know that the salt added
will dissolve in the melted portion of the ice. This formed solution of salt will have a lowered
freezing point, so the equilibrium between the solid phase and the aqueous phase will be
shifted towards the liquid phase, since such a solution will freeze at say 2 C2 C. Since
both phases are close together, the ice will absorb energy from the salt solution and will
reduce its temperature to the 2 C2 C to maintain the equilibrium. When all ice is
molten we end up with a salt solution that has got a temperature of say 1.5 C1.5 C.
This is due to the solution being diluted now. After that it will start absorbing heat from the
room and reach zero and above.

Best Answer: when you make ice cream, you usually use salt water to super-cool your ice
cream. normal water freezes at 0 degrees celcius, and that's not good enough to make ice cream.
adding salt to the water lowers its freezing point (freezing point depression, which is a colligative
property). the water will now stay liquid at lower temperatures, which is required to make ice
cream.
as a side note, this is also why people salt the roads in the winter to get rid of ice. adding salt
lowers freezing point, so the ice will melt more easily at a lower temperature.