CHEMISTRY ASSIGNMENT

COLLIGATIVE PROPERTIES
In chemistry, colligative properties are properties
of solutions that depend upon the ratio of the number of
solute particles to the number of solvent molecules in a
solution.They are independent of the nature of the solute
particles, and are due essentially to the dilution of the
solvent by the solute.
Colligative properties include:
(1) Relative lowering of vapour pressure;
(2) Elevation of boiling point;
(3) Depression of freezing point and
(4) Osmotic pressure.
The word colligative is derived from the latincolligatus
meaning .bound together, since these properties are bound
together by the fact that they all depend on the number of
solute particles and not on the type of chemical species
present.
Measurement of colligative properties for a dilute solution of
a non-ionized solute such as urea or glucose in water or
another solvent can lead to accurate determinations of
relative molar masses. Alternatively, measurements for
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ionized solutes can lead to an estimation of the percentage

of ionization taking place.
Colligative properties are mostly studied for dilute solutions,
whose behavior may often be approximated as that of
an ideal solution.

1.RELATIVE LOWERING OF VAPOUR PRESSURE

The vapor pressure of a liquid is the pressure of a vapor in
equilibrium with the liquid phase. The vapor pressure of a
solvent is lowered by addition of a non-volatile solute to
form a solution.
For an ideal solution, the equilibrium vapor pressure is given
by Raoult's law as
, where
is the vapor pressure of the pure component i (= A, B, ...)
and is the mole fraction of the component i in the solution
For a solution with a solvent (A) and one non-volatile solute
(B), and
The vapor pressure lowering relative to pure solvent
is , which is proportional to the
mole fraction of solute.

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If the solute dissociates in solution, then the vapor pressure

lowering is increased by the van't Hoff factor , which
represents the true number of solute particles for each
formula unit. For example, the strong
electrolyte MgCl2 dissociates into one Mg2+ ion and two Cl-
ions, so that if ionization is complete, i = 3 and .
The measured colligative properties show that i is somewhat
less than 3 due to ion association.
Since relative lowering of vapour pressure depends only upon
the number of moles of the solute dissolved in a definite
number of the moles of solvent and is independent of the
nature of the solute, hence it is a colligative property.

MEASUREMENT OF RELATIVE LOWERING OF VAPOUR PRESSURE:-

Ostwald and Walker apparatus is the arrangement to
calculate relative lowering in vapour pressure. In this
method, a stream of dry air is bubbled successively through
(i) the solution (ii) the solvent and (iii) a reagent which can
absorb the vapours of the solvent. Generally solvent is water
and reagent is anhydrous CaCl2.

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The first three bulbs contain a weighed amount of the

solution and the next three bulbs contain a weighed amount
of the pure solvent. A weighed amount of anhydrous CaCl2 is
taken in the U tube. All the bulbs must be kept at the same
temperature and air must be bubbled gradually to ensure
that it gets saturated with the vapours in each bulb.

The dry air, as it passes through the solution, takes up an

amount of vapour which is proportional to the vapour
pressure of the solution at the prevailing temperature. This
moist air passes through water (solvent), it takes up a further
amount of vapour which is proportional to the difference in
vapour pressure of pure solvent and the solution.

i.e.,
loss in mass of
vapour pressure of solution
solution
P
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loss in mass of vapour pressure of pure solvent - vapour

solvent pressure of solution
Po – P

and

Loss in mass of solution + loss in mass of solvent

P + P0 - P P0

This air is then passed through CaCl2 of U-tube.

The CaCl2 tubes are weighed at the end of the experiment.

The gain in mass should be equal to the total mass of the
solution and solvent which is proportional to Po.

i.e.

2.ELEVATION IN BOILING POINT:-

The boiling point of a liquid is the temperature at which the
vapour pressure of the liquid becomes equal to the
atmospheric pressure.

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Addition of 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.

Since the addition of a non-volatile solute lowers the vapour

pressure of the solvent, the vapour pressure of a solution is
always lower than that of pure solvent and hence it requires a
higher temperature to make its vapour pressure equal to
atmospheric pressure i.e., boiling point of solution is higher
than the pure solvent.

Elevation of boiling point = boiling point of solution - boiling

point of pure solvent

ΔTb = T - T b

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Elevation of boiling point lowering in vapour pressure

ΔTb ΔP ΔP mole fraction of solute

or ΔTb ΔP XB
ΔTb = ( nB <<nA)

ΔTb = and XB

ΔTb =

For 1 kg solvent (WA = 1 kg)

= molality = m

and MA (molecular mass of solvent) is a constant so that

KMA = another constant = Kb

then ΔTb = Kbm

Note:
Kb is molal boiling point elevation constant or ebullioscopic
constant. It depends on only nature of solvent and not on
nature of solute. Unit of Kb is K/m
When m = 1
then ΔTb = Kb
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Molality =

Hence ΔTb = Kb =

Molal boiling point elevation constant and enthalpy of

vapourisation

Kb =

where, T0 = Boiling point of pure solvent

lvap = Latent heat of vapourisation per gram of solvent
ΔH vap = Latent-heat of vapourisation per mole of solvent
MA = Molecular mass of solvent
R = Gas constant [8.314 J K-1 mole-1 (if ΔH vap is in joules) or
2 cal K-1 mole-1 (if ΔHvap is in calories)]

3.DEPRESSION IN FREEZING POINT:-

Freezing point is the temperature at which the
vapourpressure of solid and liquid state of a substance
become equal. ORThe temperature at which the solid and
liquid phase of a substance have the same vapour pressure is
called freezing point.Freezing point of solution is always

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lower than that of the pure solvent. The decrease is called as

depression in freezing point.

Depression in freezing point = Freezing point of pure solvent

- Freezing point of solution

ΔTf=T° - T

and ΔTf m

ΔTf = Kf .m

ΔTf = Kf.

where m = molality of solution

Kf = molal freezing point depression constant or cryoscopic

constant.

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Note: Kf depends on nature of solvent only. It's unit is Wm

(degree/molality) for 1 molal solution, depression in freezing
point of solution is Kf.
ΔTf = Kf

Molal freezing point depression constant and enthalpy

of fusion

Kf =

where, T0 = freezing point of solvent

ΔHf = molar enthalpy of fusion

OSMOTIC PRESSURE:-
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 semipermeable membrane,
which allows the passage of solvent molecules but not of
solute particles. If the two phases are at the same initial
pressure, there is a net transfer of solvent across the
membrane into the solution known asosmosis. The process
stops and equilibrium is attained when the pressure
difference equals the osmotic pressure.

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Two laws governing the osmotic pressure of a dilute solution

were discovered by the German botanist W. F. P. Pfeffer and
the Dutch chemist J. H. van’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.

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These are analogous to Boyle's law and Charles's Law for

gases. Similarly, the combined ideal gas law, , has as
analog for ideal solutions , where is osmotic
pressure; V is the volume; n is the number of moles of
solute; R is the molar gas constant 8.314 J K-1 mol-1; T is
absolute temperature; and i is the Van 't Hoff factor.
The osmotic pressure is then proportional to the molar
concentration , since

The osmotic pressure is proportional to the concentration of

solute particles ‘c x i’ and is 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.

Reverse osmosis (RO):-

Reverse osmosis is a membrane-technology filtration method
that removes many types of large molecules and ions from
solutions by applying pressure to the solution when it is on
one side of a selective membrane. The result is that

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the solute is retained on the pressurized side of the

membrane and the pure solvent is allowed to pass to the
other side. To be "selective," this membrane should not allow
large molecules or ions through the pores (holes), but should
allow smaller components of the solution (such as the
solvent) to pass freely.
In the normal osmosis process, the solvent naturally moves
from an area of low solute concentration (High Water
Potential), through a membrane, to an area of high solute
concentration (Low Water Potential). The movement of a pure
solvent to equalize solute concentrations on each side of a
membrane generates osmotic pressure. Applying an external
pressure to reverse the natural flow of pure solvent, thus, is
reverse osmosis. The process is similar to other membrane
technology applications. However, there are key differences
between reverse osmosis and filtration. The predominant
removal mechanism in membrane filtration is straining, or
size exclusion, so the process can theoretically achieve
perfect exclusion of particles regardless of operational
parameters such as influent pressure and concentration.
Reverse osmosis, however, involves a diffusive mechanism so
that separation efficiency is dependent on solute
concentration, pressure, and water flux rate.[1] Reverse
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osmosis is most commonly known for its use in

drinking water purification fromseawater, removing
the salt and other substances from the water molecules.

Where:-1: Sea water inflow,2: Fresh water flow (40%),

3: Concentrate flow (60%),4: Sea water flow (60%),
5: Concentrate (drain),A: Pump flow (40%),
B: Circulation pump,C: Osmosis unit with membrane,
D: Pressure exchanger

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APPLICATION OF REVERSE OSMOSIS:-

Around the world, household drinking water purification
.systems, including a reverse osmosis step, are commonly
used for improving water for drinking and cooking.
Such systems typically include a number of steps:

 a sediment filter to trap particles, including rust and

calcium carbonate
 optionally, a second sediment filter with smaller pores
 an activated carbon filter to trap organic chemicals
and chlorine, which will attack and degrade TFC reverse
osmosis membranes
 a reverse osmosis (RO) filter, which is a thin film composite
membrane (TFM or TFC)
 optionally, a second carbon filter to capture those
chemicals not removed by the RO membrane
 optionally an ultra-violet lamp for sterilizing any microbes
that may escape filtering by the reverse osmosis
membrane

Water and wastewater purification:-

Rain water collected from storm drains is purified with
reverse osmosis water processors and used for landscape
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irrigation and industrial cooling in Los Angeles and other

cities, as a solution to the problem of water shortages.
In industry, reverse osmosis removes minerals from boiler
water at power plants. The water is boiled and condensed
repeatedly. It must be as pure as possible so that it does not
leave deposits on the machinery or cause corrosion. The
deposits inside or outside the boiler tubes may result in
under-performance of the boiler, bringing down its efficiency
and resulting in poor steam production, hence poor power
production at turbine.
It is also used to clean effluent and brackish groundwater.
The effluent in larger volumes (more than 500 cu. meter per
day) should be treated in an effluent treatment plant first,
and then the clear effluent is subjected to reverse osmosis
system. Treatment cost is reduced significantly and
membrane life of the RO system is increased.
The process of reverse osmosis can be used for the
production of deionized water.
RO process for water purification does not require thermal
energy. Flow through RO system can be regulated by high
pressure pump. The recovery of purified water depends upon
various factors including membrane sizes, membrane pore
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size, temperature, operating pressure and membrane surface

area.

CONCEPT OF ISOTONIC, HYPOTONIC AND

HYPERTONIC:-
ISOTONIC SOLUTION:-
An isotonic solution is one in which its effective osmotic
concentration is the same as the solute concentration of
another solution with which it is compared. This occurs, for
example, when the concentration of both water and total
solute molecules are the same in an external solution as in
the cell content. Water molecules diffuse through the plasma
membrane in both directions, and as the rate of water
diffusion is the same in each direction that cell will neither
gain nor lose water.

HYPERTONIC SOLUTION:-
Hypertonic refers to a greater concentration. In biology, a
hypertonic solution is one with a higher concentration of
solutes on the outside of the cell. When a cell is immersed
into a hypertonic solution, the tendency is for water to want
to flow out of the cell in order to balance the concentration
of the solutes.
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However, a hypertonic cell has a higher concentration of

solutes than the surrounding solution, causing water to rush
into the cell in an effort to balance out the concentration of
solutes. The affinity of water wanting to rush in can be
quantified as the osmotic pressure.

HYPOTONIC SOLUTION:- Hypotonic refers to a lesser

concentration. A hypotonic solution has a lower
concentration of solutes than its surroundings, so in an
attempt to balance concentrations, water will rush into the
cell, causing swelling. [3]

When plant cells are hypotonic, the flexible cell

membrane pulls away from the rigid cell wall, but remains
joined to the cell wall at points called plasmodesmata. The
cell takes on the appearance of a pincushion, and the
plasmodesmata almost cease to function because they
become constricted: a condition known as plasmolysis. In
plant cells the terms isotonic, hypotonic and hypertonic
cannot strictly be used accurately because the pressure
exerted by the cell wall significantly affects the osmotic
equilibrium point.
Some organisms have evolved intricate methods of
circumventing hypotonicity. For example, saltwater is
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hypertonic to the fish that live in it. They need a large surface
area in their gills in contact with seawater for gas exchange,
thus they lose water osmotically to the sea from gill cells.
They respond to the loss by drinking large amounts of
saltwater, and actively excreting the excess salt. This process
is called osmoregulation.

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DISSOCIATION AND ASSOCIATION OF SOLUTE

IN DILUTE SOLUTION:-
Van't Hoff Factor and Abnormal Molecular Masses
Van't Hoff factor 'i' is defined as ratio of the experimental
value of colligative property to the calculated value (normal
value) of colligative property.

When the solute associates or dissociates in solution,

abnormal results (for all colligative properties and molar
masses) are obtained. i.e., experimental value for colligative
properties and molar mass deviates from calculated or
normal value. The deviation depends on extent of
dissociation or association of solute.

To calculate the extent of association or dissociation, Van't

Hoff in 1886 introduced a factor 'i' called Van't Hoff factor.

Van't Hoff factor 'i' is defined as ratio of the experimental

value of colligative property to the calculated value (normal

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value) of colligative property.

i.e., i =

or i =

or i =

Using Van't Hoff factor, the colligative properties are

modified as follows:
Relative lowering of vapour pressure,

Elevation of boiling point,

ΔTb = iKbm
Depression in freezing point,
ΔTf = iKf .m
Osmotic pressure,
= i CRT

Association of Solute
Many organic solutes when dissolved in non-aqueous (non
polar) solvent associate to form a bigger molecule. Thus the
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no. of molecules decreases and hence colligative properties

decrease.
Examples:
Acetic acid in benzene, chloro acetic acid in naphthalene

Association of two molecules (dimerisation) of acetic acid in

benzene.
Consider the following reaction for association

nA --> (A)n
1 0 moles before association
(1 - α) moles after association

i=

i=

obviously, i< 1 i.e., colligative properties decrease on

association.

Dissociation of Solute
Some solutes (organic acids, bases and salts) in aqueous
solution undergo dissociation. In such case no. of particles
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increases and hence colligative properties increase.

Examples:
Dissociation of NaCl in aqueous solution.
Consider the following dissociation reaction,

NaCl Na+(aq) + Cl- (aq)

(1 - α) α α moles after dissociation

i=

obviously, i> 1 i.e., colligative properties increases.

DISSOCIATION CONSTANT:-
For reversible dissociations in a chemical equilibrium
AB A+B
the dissociation constant Kd is the ratio of dissociated to
undissociated compound

where the brackets denote the equilibrium concentrations of

the species.

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