INTRODUCTION

We are all chemists. We use chemicals everyday and perform chemical reactions without thinking much
about them. Chemistry is important because everything you do is chemistry! Even your body is made of
chemicals. Chemical reactions occur when you breath, eat or just sit there reading. All matter is made of
chemicals so it follows that as prospective chemical engineers, to understand the basics of how things
work, we must first understand the properties of matter.

Today we shall be considering solutes which are substances that can be dissolved by a solvent to
create a solution. In 1891, Wilhelm Ostwald classified solute properties in three categories;

1. Colligative Properties

2. Additive Properties

3. Constitutional Properties

What are COLLIGATIVE PROPERTIES?

The word colligative has a Latin origin "coligare" which means to bind or unite. It is used to describe
the properties of solutions that depend on the ratio of the number of solute particles to the number of
solvent molecules in a solution, and not on the nature of the chemical species present. This relative
population can be related to the various units for concentration of solutions. That solution properties
are independent of the nature of solute particles is only idealistic but may be approximate for dilute real
solutions.

The extent to which these physical properties differ between those of solution and pure solvent is
provided by the colligative property law; The freezing point, boiling point and vapor pressure of a
solution differ from that of a pure solvent by amounts which are directly proportional to the molar
concentration of the solute.

These properties include;

1. Lowering of the vapor pressure of the solvent.

2. Elevation of the boiling point of the solvent.

3. Depression of the freezing point of the solvent.

4. Exhibition of osmotic pressure.

RELATIVE LOWERING OF VAPOR PRESSURE

 The vapor pressure of a liquid is the pressure of the vapor which is in equilibrium with that liquid.
When a non-volatile solute is dissolved in a solvent, the vapour pressure of the solvent is lowered. Sugar
and some other solids are not volatile. Thus the vapor pressure of an aqueous sugar solution at 20°c is
less than that of pure water at 20°c. The vapor pressure of a liquid is determined by the frequency of
escape of molecules from the surface. In a sugar solution, both sugar and water molecules are found at
the surface. Therefore, the number of water molecules at the surface is less than in pure water; thus the
frequency of escape of water molecules and hence the vapor pressure is lower than in pure water.

For an Ideal Solution, the equilibrium vapor pressure is given by Raoult's law as

P= PaXa + PbXb + ...... Where

Pi is the vapor pressure of the pure component [I= a,b...) and Xi is the mole fraction of the component in
the solution.

For a solution with a solvent (A) and one non-volatile solute (B)

Pb= 0 and P=PaXa

The vapor pressure lowering relative to pure solvent is

∆P = Pa -- P = Pa -- PaXa = Pa(1--Xa) = PaXb

Which is proportional to the mole fraction of solute.

Raoult's law may also be stated as the vapor pressure of the solution in an ideal solution Psoln is
equal to the mole fraction of the solvent, Xsolv multiplied by the vapor pressure of pure solvent Psolv.

Psoln = X'solvPsolv

Xsolv = X1 = N1/ (N1+ N2)

Is the ratio of the number of moles of solvent to the total number of moles of solution.

N1= number of moles of solvent molecules

N2= number of moles of solute molecules

Dilute solutions also tend to exhibit ideal behavior. The decrease in vapor pressure ∆P of an ideal
solution compared to that of the pure solvent, is equal to the mole fraction of the solute, Xsolute
multiplied by the vapor pressure of the pure solvent P°solv

∆P = XsolutePsolv

Xsolute = X2 = N2/(N1+N2)

Example 1
Calculate the vapor pressure of an ideal solution of 92.1g glycerin C3H8O3 in 184g ethanol C2H5OH at
40°c. The vapor pressure of pure ethanol at 40°c is 135.3torr. Glycerin is essentially non volatile at this
temperature.

Solution

Psoln = XsolvPsolv

The solvent is 184g ethanol at40°c

The pressure of the solvent Psolv is 135.3torr

To get Xsolv, we must first determine the number of moles of the solvent C2H5OH and the solute
C3H8O3

Recall; number of moles = mass/molar mass

Mass of ethanol = 184g

Molar mass of ethanol = (12*2) + (1*5) + (16*1) + (1*1) = 46g/mol

. ° . number of moles = 184g/46g/mol = 4mol

Mass of glycerin = 92.1g

Molar mass of glycerin = (12*3) + (1*8) + (16*3) = 92g/mol

. ° . number of moles of glycerin = 92.1g/92.1g/mol = 1mol

Now mole fraction of solvent[ ethanol ] = No of mole of ethanol/ No of mole of ethanol + no of mole of
glycerin

Xsolv = 4/(4+1) = 0.800

.°. Psoln = 0.800 * 135.3torr

Psoln = 108torr

Apparently, the vapor pressure of the solvent ethanol has been lowered from 135.3torr to 108torr by
the addition of the solute Glycerin.

ELEVATION OF THE BOILING POINT OF THE SOLVENT

A liquid is at boiling point when its vapor pressure is equal to the external pressure on its surface.
The addition of a solute to form a solution stabilizes the solvent in the liquid phase, and lowers the
solvent chemical potential so that solvent molecules have less tendency to move to the gas or solid
phases. As a result, liquid solutions slightly above the solvent boiling point at a given pressure become
stable, which means that the boiling point increases. The elevation of the boiling point is the same when
solutions of the same concentrations are considered and this elevation can be measured by ebullioscopy
[ a procedure that involves using an ebullioscope for measuring the boiling point of a liquid ]. One mole
of any electrolyte dissolved in 1kg of water raises the boiling point by 0.512°C which is called the
"ebullioscopic constant" of the solvent.

The change in boiling point of a dilute solution, ∆Tb from that of the pure solvent is given by the
expression;

∆Tb = KbM where

Kb is in °C/m and M is the molar concentration with unit mol/kg but denoted by m

KB is the molar boiling point elevation constant [ ebullioscopic constant ]

M is the molar concentration of the solute in the solvent.

It should be emphasized that the extent to which the vapor pressure of a solvent is lowered and the
boiling point is elevated depends on the number of solute particles present in.a given amount of
solvent, not on the mass or size of particles.

Example 2

Find the change in the boiling point of water when 15g of glycerin C3H8O3 is dissolved in 50g of
water. KB = 0.512°c/m

Solution

∆Tb = KbM

M = no of moles of solute/kg mass of solvent

The solute is glycerin C3H803

The mass of solute is 15g

The molar mass of solute is 92g/mol ( from example 1)

.°. No of moles of glycerin = 15g/92g/mol = 0.163mol

Mass of solvent water is 50g

Mass of solvent in Kg = 50/1000 = 0.05kg

.•. M = 0.163/0.05 = 3.26m

 Then ∆Tb = Kb*M = 0.512°c/m * 3.26m

∆Tb = 1.67°c

This means that the boiling point of 50g of water is elevated by 1.67°c when 15g Glycerin is added.

DEPRESSION OF THE FREEZING POINT OF THE SOLVENT

The temperature at which the solid and liquid of a solution are in equilibrium and at which both
have the same vapor pressure is called the FREEZING POINT. The freezing point of a pure solvent is
lowered by the addition of a solute which is insoluble in the solid solvent and the measurement of this
difference is called cryoscopy.

Sea water with its large salt content freezes at lower temperature than fresh water. Pure water
and ice have the same vapor pressure at 0°c. When solutions freeze, the solid that separates out is
almost always pure ice. Thus the vapor pressure of the ice is not affected by the presence of the solute.
However the water in the solution has a lower vapour pressure than ice at 0°c. If the temperature falls,
the vapor in the ice decreases more rapidly than does that of the water in the solution. At some
temperature below 0°c, the ice and the water have the same vapor pressure meaning they are once
again in equilibrium. This is the freezing point of the solution.

Summarily, at the lower freezing point, the vapor pressure of the liquid is equal to the vapor
pressure of the corresponding solid and the chemical potentials of the two phases are equal as well. The
equality of chemical potentials permits the evaluation of the cryoscopic constant which is the molar
freezing point depression constant.

∆Tf = KfM

M is still the molar concentration of the solute in the solvent.

Example 3

What is the freezing point depression of the solution of 97g of phosphorus P in 700g of ethanol
C2H5OH assuming that phosphorus is nonvolatile? Kf for ethanol = -1.99°c/m

Solution

We have to determine the molar concentration M = number of moles of solute/ Kg mass of solvent

The solute is phosphorus P

Mass of P = 97g

Molar mass of P = 30g/mol

 .•. No if moles of P = 97/ 30 = 3.23mol

The solvent is ethanol C2H5OH

Mass in kg = 700/1000 = 0.7kg

M = 3.23/0.7 = 4.61m

.•. ∆Tf = Kf*M = -1.99°c/m * 4.61m

∆Tf = -9.18°c

The freezing point of 700g ethanol is decreased by 9.18°c on the addition of 97g phosphorus.

OSMOSIS AND OSMOTIC PRESSURE

The osmotic pressure of a solution is the difference in pressure between the solution and the
pure liquid solvent when the two are in equilibrium across a semi permeable membrane, which allows
the passage of solvent molecules but not of solute particles. Osmosis can be defined as the flow of
solvent from a dilute solution into a more concentrated one, when the two liquids are separated
from.each other by a semi permeable membrane; a thin barrier that allows the solvent molecules to
pass in both directions but is impermeable to solute particles. A semi permeable membrane must
therefore obviously possess minute pores through which the solvent molecules can travel.

Depending on the system, parchment, gelatin, plastic, animal skin or other substances can be used
as a semi permeable membrane. The membrane does not act as a filter in the sense that the solute
molecules are too large to pass through the pores. The most likely explanation is that the solvent
molecules can attach themselves to the surface of the membrane by means of chemical bonds such as
hydrogen bond and then work their way through the fine network of pores.

Two laws governing the osmotic pressure of a dilute solution were discovered by the German
botanist W. F. P. Pleffer and the Dutch chemist J. H. Can't Hoff ;

1. The osmotic pressure of a dilute solution at constant temperature is directly proportional to its
concentration.

2. The osmotic pressure of a solution is directly proportional to its absolute temperature.

These are analogous to Boyle's law and Charles's law for gases. Similarly, the combined ideal gas
law

PV =nRT has an analog for Ideal solutions πV = nRT

Where;

π is the osmotic pressure

 V is the volume

n is the number of moles of solute

R is the molar gas constant 8.314J/K/mol

T is absolute temperature

The osmotic pressure is then proportional to the molar concentration C = n/V since

π = nRT/V = CRT

The osmotic pressure is proportional to the concentration C of the solute particles and therefore a
colligative property.

As with the other colligative properties, this equation is a consequence of the equality of solvent
chemical potentials of the two phases in equilibrium. In this case the phases are the pure solvent at
pressure P and the solution at total pressure P+π

Example 4

One liter of an aqueous solution containing 20.0g of haemoglobin has an osmotic pressure of
5.9torr at 22°c. What is the molecular weight of haemoglobin?

Solution

From π = CRT we can relate the osmotic pressure to the molar concentration, provided the
pressure is expressed in atmospheres. The units in R[ 0.08206Latm/mol/K ] and the temperature is
expressed on the kelvin scale [ T = 273+22 = 295K ]

1atn = 760torr

.•. π = 5.9torr * 1atm/760torr = 7.8 * 10^-3atm

Making C SOF

C = π/RT

C = 7.8 * 10^-3 / 0.08206 * 295

C= 3.2 * 10^-4 mol/L

Since the volume of the solution containing 20g haemoglobin is 1L, 20g of haemoglobin has 3.2 *
10^-4 mol

Molar mass = mass / no of mole

 .•. Molar mass of haemoglobin = 20g /( 3.2 * 10^-4)mol

= 62000g/mol

The molecular weight of haemoglobin is 62000g/mol

CONCLUSION

Chemistry explains how food changes as you cook it, how it rots, how to preserve food, how your
body uses the food you eat and how the ingredients interact to make food. Studying the colligative
properties of solutions gives us as much deeper understanding. Freezing point depression is used in
winter to melt snow on the roads by putting salt on it. Trees apply osmotic pressure to get water to their
leaves and water can be desalinated using pressure and semi permeable membranes. These are but few
applications so the importance of colligative properties cannot be overstated.

FURTHER EXERCISES

1. calculate the drop in vapor pressure of 299g of ethanol C2H5OH at 49°c and 135.3torr when 921g
glycerin is dissolved in it.

2. A very dilute solution, 0.0010M sugar in water, is separated from pure water by a semi permeable
membrane. What osmotic pressure in torr develops at 25°c?

REFERENCES

KL Kapoor Applications of thermodynamics volume 3.

H.W. Smith, Circulation 21, 808 (1960) Theory of Solutions; A knowledge of the law of solutions.

Russell John B. (1981) Megrew Hill, Auckland

First year Inorganic and Physical Chemistry; Department of chemistry, University of Benin, Nigeria.