Theory of Dilute Solution

Colligative Properties
Dilute solution containing non-volatile
solutes exhibit the following properties
1.Lowering
2.Evevation

of the vapour pressure

of the boiling point

3.Depression
4.Osmotic

of the freezing point

pressure

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Lowering of vapour pressure: RAOULTSS

LAW

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Lowering of vapour pressure:

RAOULTSS LAW

PA = XAPA
where

XA is the mole fraction of compound A

PA is the normal vapor pressure of A at that temperature

NOTE: This is one of those times when you want to make sure you have the
vapor pressure of the solvent.
Mole Fraction (X)

moles of A
XA =
total moles in solution
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Solutions

Positive deviations from Raoult's

Law

Assume that we have two

particel, A and B are mixed

Attraction of particel A and A

are greater than A and B

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negative deviations from Raoult's

Law

Attraction of particel A and B

are greater than A and A

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Measurement of lowering of vapour

pressure

1. barometric method

2. manometric method

3. Oswald and Walkers dynamic

method

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Barometer method

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Manometer method

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Oswald and Walkers dynamic

method

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Solutions

Boiling point
elevation

 When

a liquid is heated, its vapour

pressure rises and when it equals the
atmospheric pressure the liquid boils.

The

addition of non-volatile solute

lowers the vapour pressure consequently
elevates the boiling point as the solution
has to be heated a higher temperature to
make its vapoure pressure become equal
to atmospheric pressure.
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 If

Tb boiling point of the solvent

Tboiling point of the solution
Televation of boiling point
so
T=T-Tb
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AB = AD
AC AE

T1
= P-P1
T1-Tb
P-P2

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Determination of molecular
mass from elevation of
boiling point
Since P is constant for the same solvent at a
fixed temperature, from (1) we can write
T= P-P1
P
But from Raoults law for dilute solution
P-P1~ wM
P
Wm
Since M(mol mass of solvent) is constant
P-P1~ w
P
Wm

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 T~

wx1
m W
T= Kb x w x 1
m W
Kb constant
Kb=T x Kg-solvent
mol solute
Kb = RTb2
1000 x L
therefore Kb= 0.52 K/Kg
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Solutions

Measurement of boiling point

elevation
1.

Lanssberger-Walker-Method

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2. Cottrels Method

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Molecular view of Raoults law:

Freezing point depression

Depends on the solute only being in the liquid phase

Fewer water molecules at surface: rate of freezing drops

Ice turns into liquid
Lower temperature to regain balance
Depression of freezing point
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Osmotic pressure
Solvent

passes into more conc

solution increasing its volume
The passage of the solvent can
be prevented by application of
a pressure
The pressure to prevent
transport is the osmotic
pressure
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Calculating osmotic pressure

The

ideal gas law states

But

n/V = M and so

PV nRT

Where

MRT

M is the molar concentration of

particles and is the osmotic
pressure

Note:

molarity is used not molality

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Osmotic pressure and

molecular mass
Molar

mass can be computed

from any of the colligative
properties

Osmotic

pressure provides the

most accurate determination
because of the magnitude of

0.0200 M solution of glucose exerts an osmotic pressure of

374.2 mm Hg but a freezing point depression of only 0.02C
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Beckmanns method

A very sensitive thermometer, called a Beckmann

thermometer is used, which has a large bulb and only six
degrees on the whole scale

Solvent are weighed into the tube A

The tube A is fitted through a cork into a large test-tube B,

which serves as an air-jacket

The tube B is supported in a freezing mixture contained in

the large jar C

The mercury falls steadily to a certain point, when the

solvent is slightly supercooled. Freezing then commences,
the temperature at once runs up to the freezing point, and
afterwards remains stationary

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Rasts Camphor method

A known weight of camphor is taken and powdered finely

To this a known weight of solid solute is added

The mixture is melted to form a homogeneous solution, cooled, and

powdered dry

The mixture is taken in a capillary tube whose one end is sealed

Its melting point is determined carefully by the conventional melting point

determination method

The melting point of the pure sample of camphor is determined separately

using another capillary tube. The difference in the melting points gives Tf
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Application of Beckmann &

Rast Champor Method

m = Molecular weight of solute

T = Freezing/Melting point depression
Kf = Constants
w = Weight of solute
W = Weight of solvent
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Colligative Properties of
Electrolytes
The colligative properties of solution depend
solely on the total number of solute particles
present in solution. The various electrolytes
ionize and yield more than one particle per
formula unit in solutin. Therefore the colligative
effect of an electrolyte solution is always greater
than that of non-electrolyte of the same molal
concentration.

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Vant Hoff Factor

Vant Hoff Factor (i) is defined as the

ratio of the colligative effect produced
by an electrolyte solution to the
corresponding effect for the same
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concentration
of
non-electrolyte
solution.

Relation between Vant Hoff

Factor and Degree of Dissociation

Suppose 1 mole of an electrolyte is

capable of forming n ions on complete
dissociation. And
is degree of
dissociation, then :
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Number of undissociated
moleculs = 1-
Number of ions produced = n
Total number of particles = 1-
+ n
Hence,
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Activity Coefficient

G.N Lewis discovered that the

experimentally determined value of
concentration whether of molecules
or ions in solution is less than the
actual concentration. The apparent
value of concentration is termed
activity, defined as the ratio between
the activity and actual concentration
of the molecul or ion in solution

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