COLLIGATIVE PROPERTIES

CHEMISTRY ASSIGNMENT

Submitted by:Jubin Abraham

S1 S2 AUE C

NO 31
 Colligative Properties
Some of the properties of a solution are dependent primarily on the identity of the solvent and
the amount (rather than the identity) of the solute. These properties are known collectively as
colligative properties.

Vapor Pressure Lowering and Raoult's Law

In solutions that have a non-volatile solute and a liquid solvent, the presence of the solute alters
the behavior of the solvent. The vapor pressure of a pure solvent is always higher than the vapor
pressure of a solution. We can use kinetic molecular theory to understand this effect. Vapor
pressure is due to the evaporation of a small amount of the liquid. Remember the discussion on
phase changes. If the liquid is part of a solution, the non-volatile solute molecules act to disrupt
the evaporation process by attracting the solute molecules, since they have intermolecular forces
at least as strong as the liquid molecules, they impede evaporation. The presence of the solute
does not affect the condensation process, because, since it is non-volatile, it is not present in the
vapor phase.

'My Dog Has Fleas' Analogy

The solvent molecules outnumber the solute, and they are spread uniformly throughout the
solution, so how do they ‘block’ the surface and prevent evaporation? It is a common
misconception to think of the solute as a film on the surface that forms an impenetrable barrier to
prevent vaporization. WRONG.  Remember that substances dissolve because they have
favorable intermolecular attractions with the solvent. Each solute molecule has a sphere of solute
with which it is interacting. The solvent sphere, in turn, has another layer of solvent molecules
with which they are interacting, and so on, like layers of an onion. Because the non-volatile
solute will not enter the vapor phase, the solvent molecules interacting with the solute are less
likely to vaporize than if the solute were not there.

To understand the effect of a non-volatile solute on the vapor pressure, imagine that the solute
molecules are pet fleas. I keep my pet fleas in my yard which is surrounded by a chain link
fence. The fleas are energetic and tiny, so the ones inside the yard can hop through the fence (this
is vaporization). The fleas outside the fence are free to hop back inside (this is condensation) just
as easily as other fleas hop out. After a while, the number of fleas inside the yard and the number
outside the yard settles down and stays fairly constant, even though individual fleas are moving
in and out (this is the vapor pressure). Suppose I get a pet dog and keep it in the yard with the
fleas. The dog will disrupt the flow of fleas out of the yard, but not because he blocks up all the
holes in the fence. While some of the fleas, unaware of the dog, continue to hop in and out as
before, some of the fleas are busy interacting with the dog. The dog is too big to fit through the
holes in the chain link fence (he is non-volatile), so he wanders randomly throughout the yard.
Fleas outside the fence are just as likely to hop inside as before. Fleas inside the fence can still
hop out, but fewer choose to do so because they prefer to pursue a dog-related lifestyle (these are
part of the solvent shell surrounding the solute particles). Eventually, the number of fleas outside
the fence will drop relative to the pre-dog conditions (the vapor pressure of the solution is lower
than that of the pure solvent). Note that this process doesn’t depend on the type of dog I have. I
could get a pet Chihuahua or Doberman or a cat or even an elephant. Any pet that fleas like
(solute) that is too large to fit through the fence (non-volatile) will decrease the number of fleas
outside the fence (lower the vapor pressure).

Raoult’s Law

To calculate the extent of the vapor pressure lowering we can use Raoult’s Law:

                                                              

where P is the partial pressure of the component A, X is the mole fraction of component A, and
P° is the partial pressure of component A.

An ideal solution is one that obeys Raoult’s law, but the behavior of a real solution follows that
predicted by Raoult’s law only approximately. If the intermolecular attractions between the
solute and solvent are very strong, the vapor pressure of the solution is even lower than what is
predicted by Raoult’s Law. The solute molecules have strong enough attractions to the solvent to
prevent evaporation to a greater degree. If the intermolecular attractions between solute and
solvent are weaker than those of the pure solvent for itself, the vapor pressure will be lower than
that predicted by Raoult’s Law. The vapor pressure will still be lower than that of the pure
solvent because part of the surface is physically blocked by solute. However, the lower
intermolecular forces allow the solvent molecules to evaporate more easily than they would if the
solute had stronger attractions.

Vapor pressure lowering is not often observed in a freshman chemistry lab because it is difficult
to accurately measure small pressure differences unless students have access to expensive
equipment.

Boiling Point Elevation

The boiling point of a pure liquid is lower than the boiling point of a mixture at any given
pressure. The presence of solute molecules hinders the liquid leaving the mixture, so it takes
higher average kinetic energy and higher temperature. The mechanism of this effect is similar to
that of vapor pressure lowering—the solute contributes to the attractive force holding the liquid
phase together without taking part in the vaporization.

The extent of the increase in temperature of the boiling point follows the formula

                                                      

where ΔTb is the boiling point increase in degrees Celsius, m is molality of the solution in
mol/kg, Kb is a proportionality constant with units of °C kg/mol, and i is the van’t Hoff i-factor,
which is does not have units. The boiling point elevation constant is unique for each solvent. The
i-factor is a measure of the number of particles each solute particle dissociates into when it
dissolves. For non-electrolytes, i = 1. For weak solutions of strong electrolytes, i is about equal to
the number of ions in the formula unit.

Note that the identity of the solute is not important, only the amount of solute in the solution
matters. The properties of the solvent determine the value for the boiling point elevation constant
and the boiling temperature of the pure liquid.

The boiling point elevation may be observed qualitatively by measuring the temperature of salt
water that has reached a rolling boil and comparing this to the normal boiling temperature of 100
°C. It is not practical to measure the boiling point elevation quantitatively, however, because the
concentration of the solution increases as the solvent vaporizes, so it is very difficult to
determine the molality.

Freezing Point Depression

The freezing point of a pure liquid is higher than the freezing point of a mixture. The presence of
solute molecules hinders the formation of the solid phase. We can use kinetic molecular theory to
explain this if we think of the freezing point as being the same as the melting point, just from a
different perspective. When an ideal mixture freezes, the molecules of one of the components
group together to form a crystal structure held together by intermolecular forces. A pure
crystalline solid forms as the remaining liquid gets more and more concentrated with the solute
impurities. The molecules need kinetic energy to separate them physically from the mixture, so
the solidification process doesn’t start until the liquid is colder than the temperature required to
freeze the pure liquid. As the liquid freezes, molecules must move through the solute to join the
crystal. At the same time, some of the individual molecules of pure solid are melting and mixing
with the liquid solution. It is easier for the pure solid to melt than for the solvent to move through
the solution so that it can freeze (by easier we mean less restricted by attractions with foreign
particles). At a temperature that would be low enough to freeze a pure liquid, the melting process
is easier than the freezing process, so the mixture remains liquid. The mixture has to be cooled
lower than the normal freezing point for the pure crystalline solid to form from the mixture.

The extent of the decrease in temperature of the freezing point follows the formula

                                                       

where ΔTf is the freezing point decrease in degrees Celsius, m is molality of the solution in
mol/kg, Kf is a proportionality constant with units of °C kg/mol, and i is the van’t Hoff i-factor,
which is does not have units. The freezing point depression constant is unique for each solvent.
The i-factor is a measure of the number of particles each solute particle dissociates into when it
dissolves. For non-electrolytes, i = 1. For weak solutions of strong electrolytes, i is about equal to
the number of ions in the formula unit.

Note that the identity of the solute is not important, only the amount of solute in the solution
matters. The properties of the solvent determine the value for the boiling point elevation constant
and the boiling temperature of the pure liquid.

Freshman chemistry students usually perform a freezing point depression experiment to illustrate
colligative properties. The purpose of the experiment is often to determine the formula weight of
an unknown solute, unfortunately. This confuses some students; the main thrust of colligative
properties is that they depend on the identity of the solvent and the amount of the solute yet, in
this type of experiment, we use the information to find a formula weight for the solute—it seems
contradictory!  The explanation is that the experiment uses the freezing point depression to find
the molality. If you know the mass of the solvent used to make a solution with a specific
molality, you can find the moles of solute. Divide the mass of the solute by the number of moles
to get the formula weight of the solute.

A real world example of freezing point depression is the use of antifreeze in a car radiator,
salting roads to melt ice, and using rock salt when you make ice cream.

Concept Check: If used to melt ice, which would do a better job, sugar (a non-electrolyte), salt,
or calcium chloride?

Answer: The calcium chloride would work better. Because the sugar is a non-electrolyte, it does
not break apart into smaller but more numerous ions when it dissolves. The sodium chloride and
calcium chloride are ionic compounds. These ionize in solution to form two and three ions per
formula unit, respectively. Because calcium chloride forms more ions, and colligative properties
depend on the number of solute particles, the calcium chloride will result in a larger freezing
point depression.

Additional benefits can be seen if we investigate cost (sugar is the most expensive, salt is the
least expensive), damage (salt harms concrete and brick), and heat (calcium chloride actually
releases considerable heat when it dissolves as we will see in the unit about thermochemistry).

Concept Check: Automobile antifreeze is ethylene glycol, C2H6O2. It is a non-electrolyte. If a

radiator contains 40.0% antifreeze and 60.0% water, by mass, what is the freezing point of the
solution in the radiator? The normal freezing point for water is 0.0 °C and Kf is 1.86 °C mol/kg.
Answer: Find the molality of the solution. The mass of the solvent is 0.0600 kg and the formula
weight of the solute is 62.066 g/mol.

                                         

Use the freezing point depression formula

                                

Osmosis
Osmosis is the passage of certain molecules through a membrane. For example, water will flow
through a cell membrane. Membranes are semi-permeable, because they permit molecules that
are small enough to pass while serving as a barrier to other molecules. For example, animal cells
are surrounded by cell membranes which keep the contents of the cell inside but allow water to
flow in and out.

If solutions of differing concentrations are separated by a semi-permeable membrane, small

molecules will flow through the membrane from the side with the most to the side with the least
until the amounts on both sides of the membrane are equal. Frequently, water is able to pass
through a semi-permeable membrane, since it is a small molecule, but solute molecules cannot.
If this is the case, water will flow from the side with the lowest concentration (more water
relative to solute) to the side with the highest concentration (less water relative to solute),
diluting it until both sides are equal.

We can use kinetic molecular theory to explain this process. If we examine a semi-permeable
membrane under magnification, we see that it is porous. Small molecules can fit inside the pores.
Random molecular motions send small molecules from one side of the membrane to the other
through the pores. Large molecules cannot fit through the pores, though. Not only do the large
molecules stay on one side of the barrier, they hinder the movement of small molecules through,
rather like they hinder liquid molecules from evaporating from a solution (remember the dog and
fleas analogy). The small molecules can travel into the side with large solute more readily than
they can travel out of the side with the solute.

 
 

The force generated by the net flow of small molecules through a semi-permeable membrane
will support a column of liquid; much like air pressure supports a column of mercury in a
barometer. We can prevent the flow of small molecules by exerting pressure against the direction
of the flow. The amount of force needed to equal the force due to the flow of small molecules is
called the osmotic pressure, π.

The osmotic pressure for an ideal solution is analogous to the ideal gas law

                                                              

where T is temperature in Kelvin, V is volume, R is the gas constant and n is the number of
moles of solute. This can be rearranged to

                                                         

where M is molarity of the solution, since n is number of moles of solute and V is the volume of
the solution.