Solution and colligative properties

In chemistry, a solution is a homogeneous mixture composed of only

one phase. In such a mixture, a solute is dissolved in another
substance, known as a solvent.

The ability of one compound to

dissolve another compound is
called solubility.
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Concentration expressions for solutions
• Molar solution and Molarity?
• Normal solution and Normality?
• Molal solution and Molality?
• Mole fracction?
• Mole percent?
• Percent
• Percent by weight % w/w
• Percent by volume %v/v
• Percent weight in volume % w/v

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➢ Ideal solution is defined as a solution in which there is no change in
the properties of the components other than dilution when they
are mixed to form the solution

➢ Ideality in solutions means complete uniformity of attractive forces

Raoult’s Law
The partial pressure of solvent, PA, over a solution equals the vapor
pressure of the pure solvent, 𝑃𝐴𝑜 , times the mole fraction of solvent, XA ,
in the solution. Consider a solution of volatile solvent, A, and
nonelectrolyte solute, B, which may be volatile or nonvolatile.

➢PA = 𝑃𝐴𝑜 XA
➢PB = 𝑃𝐵𝑜 XB
➢P = PA + PB
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Vapor pressure composition curve (for previous example)

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Real Solutions
• Ideality in solutions presupposes complete uniformity
of attractive forces.
• In some solution, the “cohesive” attraction of A for A
exceeds the “adhesive” attraction existing between A
and B.
• Similarly, the attractive forces between A and B may
be greater than those between A and A or B and B.
• Such mixtures are real or nonideal; that is, they do
not adhere to Raoult’s law
• Two types of deviation from Raoult’s law are
recognized, negative deviation and positive deviation.

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 Negative deviation

When the “adhesive”

attractions between
molecules of different
species exceed the
“cohesive” attractions
between like molecules,
the vapor pressure of the
solution is less than that
expected from Raoult’s
ideal solution law, and
negative deviation occurs.

Adhesion > Cohesion

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 Positive deviation

When the “adhesive”

attractions between
molecules of different
species are weaker than
“cohesive” attractions
between like molecules,
the vapor pressure of the
solution is more than that
expected from Raoult’s
ideal solution law, and
positive deviation occurs.

Adhesion < Cohesion

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 Colligative properties
Colligative properties of solutions are properties that depend on the
concentration of solute molecules or ions in solution but not on the
chemical identity of the solute

Lowering of vapor pressure

Vapor pressure:
Pure solvent > solutions
Solvent Solution
 Raoult’s Law for lowering of vapour pressure:
The vapour pressure of a pure solvent is decreased when a non-
volatile solute is dissolved in it. the relative lowering of the vapour
pressure of a dilute solution is equal to the mole fraction of the
solute present in dilute solution.
If p0 is the vapour pressure of the solvent and p that of the solution,
the lowering of vapour pressure is (p0 – p) and relative lowering of
vapour pressure is (p0 – p)/p0. According to Raoult’s law
p0 – p n2
=
p0 n1+ n2 = X2
Where, n1 and n2 are the number of moles of solvent and solutes and
X2 is the mole fraction of solute in the solution.
Lowering of vapour pressure of a dilute solution is a colligative property
The vapour pressure of the pure solvent is caused by the number of
molecules evaporating from its surface. When a nonvolatile solute is
dissolved in solution, the presence of solute molecules in the surface
blocks a fraction of the surface where no evaporation can take place.
This causes the lowering of the vapour pressure.
According to Raoult’s Law of partial pressure of solution
Psolvent = Pºsolvent Xsolvent
Psolute = Pºsolute Xsolute
Now since, the solute used in non volatile only pressure from solvent
can be considered. Hence,
Psolution = Pºsolvent Xsolvent or P = Pº X1 ….. (1)
We knew, X1 + X2 = 1 or X1 = 1- X2 X1= mole fraction of solvent
X2= mole fraction of solute
P = Pº X1= Pº (1- X2)
Pº-P = Pº X2 The relative vapor pressure lowering depends only on the
Pº−P mole fraction of the solute, X2. Therefore, the relative
= X2
Pº vapor pressure lowering is a colligative property.
 Molecular mass determination from the Raoult’s Law
According to Raoult’s law, we have
Since for very dilute solution, the
Pº−P number of moles (molecules) of
= X2 ....... (1)
Pº solute (w2/M2), is very small, it
Where, P and Pº are the vapor
can be neglected in the
pressure of solution and pure
denominator. The equation (2) can
solvent, respectively. X2 is the
now be written as
mole fraction of solute.
If the number of moles of solvent 𝑤2
Pº−P 𝑀2 𝑤2 𝑀1
and solution are n1 and n2, and that = = ….(3)
Pº 𝑤1
𝑀1
𝑤1 𝑀2
of molecular mass are M1 and M2,
respectively. If we consider w1 and
Knowing the experimental value
w2 gram of solvent and solute are Pº−P
present in the solution, then from of , and the molecular mass
Pº
equation (1), we get of the solvent (M1), the molecular
𝑤2 weight of solute (M2) can be
Pº−P n 𝑀2
= X2 = 2 = ….(2) calculated from (3).
Pº n1+n2 𝑤1 𝑤2
+
𝑀1 𝑀2
 Ostwald and Walker’s dynamic method:
This method is used to determine the relative lowering of vapor
pressure directly. The figure below shows the experimental setup
consisting of two sets of bulbs (i) Set A containing the solution, (ii)
Set B containing the solvent. Each set is weighed individually. A
known volume of dry air is first blown through the solution and then
solvent. During the passing, air is made to be saturated by the vapor
of solution and solvent. The loss in mass of solution and solvent
occurs due to saturation air gives the lowering of vapor pressure of
solution.
Consider, the air bubbles through set A is saturated up to the vapor
pressure P of the solution and then up to vapor pressure P0 of solvent in
set B. Thus, the amount of solvent taken up in set A is proportional to P
and the amount taken up in set B is proportional to (Pº -P). If w1 and w2
be the loss of weight in set A and B, respectively.
w1 ∝Pº………………(1)

w2 ∝ Pº - P …………..(2)

Adding (1) and (2)

w1 + w2 ∝ Pº -P + P = Pº ...(3)

Dividing (2) by (3)

Pº−P 𝑤
∝ 2 …… 4
Pº 𝑤1 + 𝑤2

Knowing the loss of mass in set (w2) and the total mass in the two
sets (𝑤1 + 𝑤2 ), relative lower of vapor pressure could be estimated.
Boiling point elevation

Boiling point elevation is a colligative property related to vapor

pressure lowering.

The boiling point is defined as the temperature at which the

vapor pressure of a liquid equals the atmospheric pressure.

Due to vapor pressure lowering, a solution will require a higher

temperature to reach its boiling point than the pure solvent.

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 Relation between Elevation of Boiling Point and
Lowering of Vapour-pressure
When a liquid is heated, its vapour pressure rises and when it equals the
atmospheric pressure, the liquid boils. The addition of a non volatile
solute lowers the vapour pressure and consequently elevates the boiling
point as the solution has to be heated to a higher temperature to make its
vapour pressure become equal to atmospheric pressure. If Tb is the
boiling point of the solvent and T is the boiling point of the solution, the
difference in the boiling points (ΔT) is called the elevation of boiling
point. 𝑝0
T–Tb = ΔTb
The vapour pressure curves of the pure
solvent, and solutions (1) and (2) with
𝑝0
different concentrations of solute are
shown in Fig right. For dilute solutions,
the curves BD and CE are parallel and
straight lines approximately. Therefore for
similar triangles ACE and ABD, we have
 𝑝0
𝐴𝐵 𝐴𝐷 𝑇1 − 𝑇𝑏 − 𝑝1 𝑝0
= => = 0
𝐴𝐶 𝐴𝐸 𝑇2 − 𝑇𝑏 𝑝 − 𝑝2
Where, p – p1 and p – p2 are 𝑝0

lowering of vapour pressure for

solution 1 and solution 2
respectively. Hence the elevation of
boiling point is directly
proportional to the lowering of
vapour pressure. According to Raoult’s law for
dilute solution, we get
 ΔTb ∝ 𝑝0 − 𝑝 ……….. (1) Pº−P 𝑤2 𝑀1
= … … (3)
Pº 𝑤1 𝑀2
Since 𝑝0 is constant for the same
Since, M1 (the molar mass of the
solvent at a fixed temperature, from
solvent) is constant.
(1) we can write
Pº−P 𝑤2
𝑝0 −𝑝 ∝ … … (4)
ΔTb ∝ ……….. (2) Pº 𝑤1 𝑀2
𝑝0
 From equation (2) and (4), we have
𝑤2
ΔTb ∝
𝑤1 𝑀2
𝑤2 1 1
∝ . = 𝐾𝑏 𝑛2 . = 𝐾𝑏 . 𝑚2
𝑀2 𝑤1 𝑤1
=> ΔTb = 𝐾𝑏 × Molality of solute …(5)
Here, 𝐾𝑏 is called a boiling point constant or molal elevation constant.
If 𝑛2 = 1, w1 = 1, then, Kb =ΔTb; thus
Molal elevation constant may be defined as the boiling-point elevation
produced when 1 mole of solute is dissolved in one kg (1000 g) of the solvent.
If the mass of the solvent (w1) is given in grams, it has to be converted
into kilograms. Thus the expression (5) assumes the form
1 𝑤2 1
ΔTb = 𝐾𝑏𝑛2. = 𝐾𝑏 .
𝑤1 𝑀2 𝑤1 /1000
1000 ×𝐾𝑏× 𝑤2
M ………….(6)
=> 2 = 𝑤1 ×ΔTb

Where, ΔTb = elevation of boiling point; Kb = molal elevation

constant; w2 = mass of solute in grams; M2 = mol mass of solute; and
w1 = mass of solvent in grams.
Landsberger-Walker Method.
The apparatus used in this method is
consists of : (i) An inner tube with a hole in
its side and graduated in ml; (ii) A boiling
flask which sends solvent vapour in to
the graduated tube through a ‘rosehead’ (a
bulb with several holes)’ (iii) An outer tube
which receives hot solvent vapour issuing
from the side-hole of the inner tube; (iv) A
thermometer reading to 0.01 K, dipping in
solvent or solution in the inner tube.
Procedure: Pure solvent is placed in the
graduated tube and vapour of the same
solvent boiling in a separate flask is passed
into it. The vapour causes the solvent in the
tube to boil by its latent heat of
condensation.
 When the solvent starts boiling and temperature
becomes constant, its boiling point is recorded.
Now the supply of vapour is temporarily cut off
and a weighed pellet of the solute is dropped into
the solvent in the inner tube. The solvent vapour
is again passed through until the boiling point of
the solution is reached and this is recorded. The
solvent vapour is then cut off, thermometer and
rosehead raised out of the solution, and the
volume of the solution read.
From a difference in the boiling points of solvent
and solution, molecular weight
of the solute could be find out by
1000 ×𝐾𝑏× 𝑤2
M2 =
𝑤1 ×ΔTb
where w1 = weight of solute taken, w2 = weight of solvent which is
given by the volume of solvent (or solution) measured in ml
multiplied by the density of the solvent at its boiling point.
Freezing Point

Every liquid has a freezing point - the temperature at which a

liquid undergoes a phase change from liquid to solid.

When solutes are added to a liquid, forming a solution, the

solute molecules disrupt the formation of crystals of the
solvent.

That disruption in the freezing process results in a depression of

the freezing point for the solution relative to the pure solvent.

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Relation between Depression of Freezing-point and
Lowering of Vapour-pressure
has shown by the curve ABC, in Fig. There is a sharp break at B, which
corresponds to the freezing point of pure solvent, Tf. The vapour pressure
curve of a solution (solution 1) of a nonvolatile solute in the same
solvent is also shown in the Figure. It meets the freezing point curve at
F, indicating that T1 is the freezing point of the solution. Thus, the
depression of freezing point (ΔTf ) is ΔTf = Tf–T1

When more of the solute is added to

the solution 1, we get a more
concentrated solution (solution 2). The
vapour pressure of solution 2 meets
the freezing-point at C, indicating a
further lowering of freezing point to
T2.
For dilute solutions FD and CE are
approximately parallel straight lines and
BC is also a straight line. Since the 𝑝0
triangles BDF and BEC are similar,
𝐷𝐹 𝐵𝐷 𝑇𝑓 − 𝑇1 𝑝0 − 𝑝1
= => = 0
𝐸𝐶 𝐵𝐸 𝑇𝑓 − 𝑇2 𝑝 − 𝑝2
Where, p1 and p2 are vapour pressure of
solution 1 and solution 2, respectively.
Hence, depression of freezing point is
directly proportional to the lowering of
vapour pressure.
 ΔTf ∝ 𝑝0 − 𝑝 ……….. (1)
Since 𝑝0 is constant for the same solvent at a fixed temperature, from
(1) we can write
𝑝0 −𝑝
ΔTf ∝ ……..(2)
𝑝0
 According to Raoult’s law for Molal depression constant may be
dilute solution, we get defined as the freezing-point
depression produced when 1 mole of
Pº−P 𝑤2 𝑀1 solute is dissolved in one kg (1000 g)
= … … (3)
Pº 𝑤1 𝑀2 of the solvent.
Since, M1 (the molar mass of the If the mass of the solvent (w1) is
solvent) is constant. given in grams, it has to be
Pº−P 𝑤2 converted into kilograms. Thus the
∝ … … (4)
Pº 𝑤1 𝑀2 expression (5) assumes the form
1 𝑤2 1
From equation (2) and (4), we have ΔTf = 𝐾𝑓𝑛2. 𝑤 = 𝐾𝑓 𝑀 . 𝑤 /1000
1 2 1
𝑤2 1000 ×𝐾𝑓× 𝑤2
ΔTf ∝ => M2 = ………….(6)
𝑤1 𝑀2 𝑤1 ×ΔTf
𝑤 1 1
∝ 2 . = 𝐾𝑓𝑛2. = 𝐾𝑓 . 𝑚2 Where, ΔTf = elevation of boiling
𝑀2 𝑤1 𝑤1
=> ΔTf = 𝐾𝑓 × Molality of solute …(5) point; Kf = molal elevation
Here, 𝐾𝑏 is called a freezing-point constant; w2 = mass of solute in
constant or molal depression grams; M2 = mol mass of solute;
constant. If 𝑛 = 1, w = 1, then, K and w1 = mass of solvent in grams.
2 1 f
=ΔTf; thus
Beckmann’s Method for measuring
depression of Freezing point:
Apparatus used to measure depression of
freezing point consists of (i) A freezing
tube with a side-arm to contain the solvent or
solution, while the solute can be introduced
through the side-arm; (ii) An outer larger tube
into which the freezing tube is fixed , the space
in between providing an air jacket which
ensures a slower and more uniform rate of
cooling; (iii) A large jar containing a freezing
mixture e.g., ice and salt, and having a stirrer.
Procedure: 15 to 20 g of the solvent is taken in the freezing point of
the solvent by directly coding the freezing point tube and the apparatus
set up as shown in Fig. so that the bulb of the thermometer is
completely immersed in the solvent. First determine the approximate
freezing point of the solvent by directly cooling the freezing point tube
in the cooling bath.
When this has been done, melt the solvent and place the freezing-
point tube again in the freezing bath and allow the temperature to fall.
When it has come down to within about a degree of the approximate
freezing point determined above, dry the tube and place it cautiously
in the air jacket. Let the temperature fall slowly and when it has come
down again to about 0.5° below the freezing point, stir vigorously.
This will cause the solid to separate and the temperature will rise
owing to the latent heat set free. Note the highest temperature reached
and repeat the process to get concordant value of freezing point.
The freezing point of the solvent having been accurately determined,
the solvent is remelted by removing the tube from the bath, and a
weighed amount (0.1–0.2 g) of the solute is introduced through the
side tube. Now the freezing point of the solution is determined in the
same way as that of the solvent. Knowing the depression of the
freezing point, the molecular weight of the solute can be determined
by using the expression
1000 ×𝐾𝑓× 𝑤2
M2 =
𝑤1 ×ΔTf
 Osmosis
Osmosis is the phenomenon of solvent flow through a semipermeable
membrane to equalize the solute concentrations on both sides of the
membrane.
Osmotic pressure of a solution equal to the external pressure that,
when applied to the solution, just stops osmosis.

Van’t Hoff equation for osmotic pressure

Van’t Hoff reasoned that
(a)The osmotic pressure (π) of a solution at a given temperature is
directly proportional to its molar concentration (M).
i.e. π ∝ CM ........ (1) , where, T is constant.
(b) The osmotic pressure (π) of a solution of a given concentration is
directly proportional to the absolute temperature (T) .
i.e. π ∝ T ..........(2) , when, M is constant.
Now combining the equation (1) and (2), we get
π ∝ CMT
=> Π = RTCM ........(3)
Where, R is called real gas constant. Now if n moles of solute is
dissoved in a volume of V. Then,
𝑛
𝐶𝑀 = .......(4)
𝑉
𝑛
Hence, π= RT
𝑉
 πV= 𝑛 RT………(5) This is called Van’t Hoff equation for osmotic
pressure.

Determination of Molar mass from osmotic pressure

From Vant’t Hoff equation we have,

𝑤
πV= 𝑛 RT = RT
𝑀
𝑊𝑅𝑇
=> M = … … … (6)
𝜋𝑉
Berkeley and Hartley Method: This technique apply external pressure
on the solution to prevent osmosis. The osmometer used by them is
illustrated in Fig. A porcelain tube with copper ferrocyanide membrane
deposited in its walls is enclosed in a metallic jacket. The tube is fitted
with a reservoir of pure solvent at one end and a capillary tube at the
other. Mechanical pressure can be applied on the solution with a piston
connected to a pressure gauge.
Procedure: The inner porcelain tube is
filled with pure solvent and the jacket
with the solution whose osmotic
pressure is to be determined. The level
of the solvent meniscus in the capillary
tube will tend to move down as solvent
flows into the solution across the membrane.
Pressure is then applied through the piston so that the meniscus becomes
stationary. It indicates that osmosis has been stopped and now the
pressure recorded by the pressure gauge gives the osmotic pressure of the
solution.
 Henry’s Law
At constant temperature, the solubility of a gas or concentration of the
gas that dissolves in the solvent is directly proportional to the partial
pressure of the gas above the solution.
C∝P
 C = kHP

Where, C is the concentration of the gas, P is the partial pressure and kH

is Henry’s law constant for the gas for a particular liquid at a given
temperature
Limitations of Henry’s Law
It applies closely to gases with nearly ideal behaviour.
(1) at moderate temperature and pressure.
(2) if the solubility of the gas in the solvent is low.
(3) the gas does not react with the solvent to form a new species. Thus
ammonia (or HCl) which react with water do not obey Henry’s Law.
NH3+H2O = NH4++OH–
(4) the gas does not associate or dissociate on dissolving in the solvent.
• Calculate the relative vapor pressure lowering at 20◦C
for a solution containing 171.2 g of sucrose (w2) in 100 g
(w1) of water. The molecular weight of sucrose (M2) is
342.3 and the molecular weight of water (M1) is 18.02
g/mole.

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Math1: Camphor is a white solid that melts at 179.5 C and its freezing-point-depression
constant (40 C/m. a. A 1.07-mg sample of a compound was dissolved in 78.1 mg of camphor.
The solution melted at 176.0 C. What is the molecular mass of the compound? b. If the
empirical formula of the compound is CH, what is the molecular formula?
Math2: Calculate the osmotic pressure at 20 C of an aqueous solution containing 5.0 g of
sucrose, C12H22O11, in 100.0 mL of solution.
Math3: What is the boiling-point elevation of a solution made from 20.1 g of a nonelectrolyte
solute and 400.0 g of water? The molar mass of the solute is 62.0 g.
Math 4: What is the boiling-point elevation of a solution made from 20.1 g of a nonelectrolyte
solute and 400.0 g of water? The molar mass of the solute is 62.0 g.
Math 5: What is the freezing-point depression of water in a solution of 17.1 g of sucrose,
C12H22O11, in 200. g of water? What is the actual freezing point of the solution?
Math 6: A water solution containing an unknown quantity of a nonelectrolyte solute is found
to have a freezing point of -0.23°C. What is the molal concentration of the solution?