By: Vinay Tyagi (8273274642)

Chapter 2: Solution

NCERT TOPIC 2.1 & 2.2

Solution is the homogeneous mixture of two or more than two non-reacting substance.

Binary solution: Solution which contains only two components know as binary solution.

Solution = Solute + Solvent

Solute: lesser in amount solvent: Higher in amount (you had learnt in previous
classes)

Solute: lesser in no of mole solvent: Higher in no. of mole. (Learn this concept only)

For example

180 g Urea (NH2CONH2) + 90 g water (H2O)

3 mol Urea + 5 mol water

Solute: Urea solvent: water

On the basis of physical state of Solute and Solvent Solution can be classify into nine
category.

Concentration terms

1. Mass percentage
The mass (in gram) of solute per 100g of solution know as mass percentage of
solution.

If a solution is described by 10% glucose in water by mass, it means that 10 g of glucose is

dissolved in 90 g of water resulting in a 100 g solution.

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2. Volume percentage
The volume (in ml) of solute per 100 ml of solution knows as volume percentage of
solution.

For example, 10% ethanol solution in water means that 10 mL of ethanol is dissolved in water
such that the total volume of the solution is 100 ml.

3. Mass by volume percentage (w/v)

It is the mass of solute dissolved in 100 mL of the solution.
mass of solute
mass by volume percentage = x 100
volume of solution
4. Parts per million (ppm)
It is defined as the amount of substance in grams in 106 g of solution. e.g., 10ppm of
SO2 means 10 cm3 of SO2 present in 106 cm3 of air.

5. Mole fractions (x)

It is ratio of number of moles of a particular component to the total number of moles
of all the components.

No. of moles of solvent

𝐌𝐨𝐥𝐞 − 𝐟𝐫𝐚𝐜𝐭𝐢𝐨𝐧 𝐨𝐟 𝐬𝐨𝐥𝐯𝐞𝐧𝐭 (𝐀) =
No. of moles of solute + No. of moles of solvent

6. Molarity ( M)
It is expressed as the number of moles of solute per litre of solution.

7. Molality (m)
It is defined as number of moles of solute per 1000 g or 1 k g of solvent.

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Some Important Relation between Concentration terms

1. Relation between Molarity and Normality

𝐍𝐨𝐫𝐦𝐚𝐥𝐢𝐭𝐲 = 𝐧 × 𝐦𝐨𝐥𝐚𝐫𝐢𝐭𝐲
Where n = basicity/ acidity/ change in no. of O.N. / charge/ valence factor
2. Molarity in terms of mass percentage (x %) and density of solution (d g/ml)
𝐱 × 𝐝 × 𝟏𝟎
𝐌=
𝐦
Where, m = molar mass of solute
3. Molality in terms of mass percentage (x %)
𝐱 × 𝟏𝟎𝟎𝟎
𝐦=
(𝟏𝟎𝟎 − 𝐱) 𝐦
Where, m =molar mass of solute
4. Molality in terms of mole fraction of solute (XA)
𝐗 𝐀 × 𝟏𝟎𝟎𝟎
𝐦=
(𝟏 − 𝐗 𝐀 ) 𝐦𝟐
Where, 𝐦𝟐 = molar mass of solvent
5. Relation between molarity(M) and molality(m)
𝐌 ×𝟏𝟎𝟎𝟎
𝐦= where m1 = molar mass of solute
𝟏𝟎𝟎𝟎×𝐝−𝐌×𝐦𝟏

QUESTION BASED ON MOLALITY, MOLARITY, MASS PERCENTAGE,

VOLUME PERCENTAGE, PARTS PER MILLION MOLE FRACTION

Assignment no. 1

1. How does a change in temperature influence values of molarity and molality.

2. Under what conditions molarity and molality of a solution nearly the same.
3. A solution is heated from 25oC to [Link] its molarity be same less or more.
Comment.
4. Calculate the molarity of a solution containing 5 g of NaOH in 450ml solution.
5. Calculate molality of 2.5g of Ethanoic acid (CH3COOH) in 75g of benzene.
6. Calculate Molality, Molarity & Mole fraction of KI if the density of 20%
(mass/mass) aqueous KI is 1.202g/ml.
7. Concentrated nitric acid used in the laboratory work is 68% nitric acid by mass in
aqueous solution. What should be the molarity of such a sample of the acid if the
density of the solution is 1.504 g/ml?
8. A solution of glucose in water is labelled as 10% w/w. What should be the molality
and mole fraction of each component in the solution? If the density of solution is
1.2g/ml, then what shall be the molarity of the solution?
9. If the solubility product of CuS is 6×10-16, calculate the maximum molarity of CuS
in aqueous solution.
10. Calculate the mole fraction of benzene in solution containing 30% by mass in carbon
tetrachloride (CCl4).

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NCERT TOPIC 2.3, 2.3.1 & 2.3.2

Solubility

The maximum amount of solute dissolved in a specific amount of solvent at a particular

temperature.
Solubility depends upon the following factors
1. Nature of solute
2. Nature of solvent
3. Temperature
4. Pressure ( Specifically for gas in liquid solution)
Solubility principal – Like Dissolve Like
Solubility of solid in liquid
Polar solutes dissolve in polar solvents and non-polar solutes in nonpolar solvents.
When a solid solute is added to the solvent, some solute dissolves and its
concentration increases in solution. This process is known as dissolution.
Some solute particles in solution collide with the solid solute particles and get
separated out of solution. This process is known as crystallisation.
A stage is reached when the two processes occur at the same rate. Under such conditions,
number of solute particles going into solution will be equal to the solute particles separating
out and a state of dynamic equilibrium is reached.
Dissolution
Solute + Solvent Solution
Crystallisation

At this stage the concentration of solute in solution will remain constant under the given
conditions.
Saturated solution: A solution in which no more solute can be dissolved at the same
temperature and pressure is called a saturated solution
Effect of temperature
For Exothermic reaction T↑ Solubility ↓
For Endothermic reaction T↑ Solubility ↑
Effect of Pressure
There is no effect of pressure on solubility of solid in liquid because solid highly
incompressible.
Solubility of gas in liquid
It depends upon the nature of gas.
e.g. NH3 and HCl are highly soluble in water while O2, N2, H2 are slightly soluble.
Effect of temperature
Dissolution of gas in liquid always an exothermic process therefore solubility of gas in liquid
always decreases on increase in temperature.
Effect of Pressure (Henry’s Law)

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This effect is given by Henry. According to Henry’s law

“Solubility of gas in liquid is directly proportional to the pressure of the gas over the solution
at definite temperature.”
𝐦  𝐏 𝐨𝐫 𝐦 = 𝐊𝐏
Or
“Mole fraction of a gas in solution is directly proportional to partial pressure of the gas over
solution.”
Or
“The partial pressure of gas in vapour phase (P) is directly proportional to mole fraction of
the gas in solution.”
P, High Pressure

P x
P = KH x
Where, KH is Henry’s Constant. At constant pressure, Henry’s constant of gas
inversely proportional to the mole fraction of gas in solution.
P = partial pressure of gas, x = mole fraction of gas in solution and
Note: Higher is the value of Henry’s constant lower is the solubility of the gas in
liquid.
Applications of Henry’s law
In the production of carbonated beverages: To increase the solubility of CO2 in soft
drinks and soda water, the bottle is sealed under high pressure.

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In the deep sea diving: Scuba divers must cope with high concentrations of dissolved
gases while breathing air at high pressure underwater. Increased pressure increases the
solubility of atmospheric gases in blood. When the divers come towards surface, the
pressure gradually decreases. This releases the dissolved gases and leads to the
formation of bubbles of nitrogen in the blood. This blocks capillaries and creates a
medical condition known as bends, which are painful and dangerous to life. To avoid
bends, as well as, the toxic effects of high concentrations of nitrogen in the blood, the
tanks used by scuba divers are filled with air diluted with helium (11.7% helium, 56.2%
nitrogen and 32.1% oxygen).

At high altitudes the partial pressure of oxygen is less than that at the ground level. This
leads to low concentrations of oxygen in the blood and tissues of people living at high
altitudes or climbers. Low blood oxygen causes climbers to become weak and unable to
think clearly, symptoms of a condition known as anoxia.

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QUESTION BASED ON SOLUBILITY OF A GAS IN A LIQUID, HENRY LAW &

APPLICATIONS

Assignment no. 2

1. Mention some of important applications Henry law.

2. Why do gases always tend to be less soluble in liquids as the temperature is raised?

3. What is the effect of rise in temperature on solubility of a gas?

4. Why do aquatic species remain more comfortable in lakes in winters than in

summers?

5. Explain the following phenomena with the help of Henry’s law. (i) Painful condition

known as bends. (ii) Feeling of weakness and discomfort in breathing at high altitude.

6. Why soda water bottle kept at room temperature fizzes on opening?

7. If N2 gas is bubbled through water at 298 K, how many millimoles of N2 gas would

dissolve in 1 litre of water .Assume that N2 exerts a partial pressure of 0.987 bar.

Henry’s law constant for N2 at 293K is 76.48 bar.

8. H2S a toxic gas with rotten egg like smell is used for the qualitative analysis. If the

solubility of H2S in water at STP is 0.195m, calculate Henry’s law constant

9. Henry’s law constant for CO2 in water is 1.67x 108Pa at 298 K .calculate the quantity

of CO2 in 500ml of soda water when packed under 2.5 atm CO2 pressure at 298 K.

10. Henry’s law constant for the molality of methane in benzene at 298 K is 4.27 × 105

mm Hg. Calculate the solubility of methane in benzene at 298 K under 760 mm Hg.

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NCERT 2.4, 2.4.1, 2.4.2, 2.4.3

VAPOUR PRESSURE OF LIQUID SOLUTION

i. Liquid in Liquid solution ii. Solid in Liquid solution

Vapour pressure of pure liquid

• In liquids, molecules of liquid show almost similar behaviour as gaseous molecule in
gas state.
• When a liquid is taken in an open container at
a certain temperature, the molecules present on
the surface are being pulled inwards or
downwards by the molecules present below
them. This inward pull or attraction prevents
the surface molecules from escaping out of the
surface of the liquid as vapours.
• However, some high energy molecules present
on the surface escape from it in order to
increase their free movement i.e. Entropy (Randomness). In doing so, they take up
certain amount of energy from the rest of molecules resulting in their decreased in
their average kinetic energy or fall in temperature. That is why cooling is observed in
evaporation.
• Escaping of molecules of liquid from the surface is known as evaporation. Therefore
it is a surface phenomenon.
• In open container, the evaporation of the liquid continues because the decrease in
average kinetic energy or loss of energy is compensated by the surrounding.
Ultimately, the entire liquid evaporates from the container.
• In close container, the evaporated molecules cannot escape to the atmosphere.
• The molecules with higher kinetic energy leave the surface of the liquid as vapors. As
a result, the volume of container initially decreases. These vapours get collected in the
space over the liquid surface. They exert more collisions
with the walls of the container resulting in increased
pressure on the surface of the liquid. These molecules
present in the vapour phase are also colliding with the
liquid surface.
• Those with lesser kinetic energy condense at the surface
of the liquid because of the collisions that are taking
place. Thus, the condensation of molecules back to the
liquid state is also taking place.
• Inside the vessel, the liquid changes to vapours resulting
in evaporation and the vapours are changing back to liquid state known as
condensation.

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• At a particular temperature, the liquid

and its vapours are in state of dynamic
equilibrium also called phase
equilibrium.
H2O(l) H2O(g)

Definition of vapour pressure:

“The pressure exerted by the vapours of
the liquid in equilibrium with liquid at a
given temperature.”

Factor affecting Vapour pressure of liquid

1. Nature of liquid: depends upon intermolecular force of attraction
2. Temperature of liquid: Kinetic energy increase on increase in temperature

Vapour pressure of liquid-liquid solution

Let us take a binary solution of two volatile liquids and denote the
two components as A and B in close vessel. Let PA and PB be their partial vapour and xA and
xB be their mole fraction in solution respectively.
According to Dalton’s law
Total pressure (P) = PA + PB

Raoult’s Law for liquid-liquid solution

In 1886, French chemist, F.M. Raoult gave relationship between vapour pressure of a
volatile component and its mole fraction in the solution. This is known as Raoult’s Law.
According to this law,
“The partial vapour pressure of a volatile component present in a solution is directly
proportional to the mole fraction of that component at a given temperature.”

• In a solution, the vapour pressure of a particular component at a given temperature is

equal to the mole fraction of that component in the solution multiplied by its vapour
pressure when present in pure form.
• The total vapour pressure of the binary solution contain volatile component can be
calculated of we know the partial vapour pressured of both the pure component and mole
fraction of any of these.
Mole fraction of the component in the vapour phase
Let mole fraction in vapour phase is YA and YB of component A and B respectively.
According to Dalton’s law

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𝑃𝐴 𝑃𝐵
𝑌𝐴 = , 𝑌𝐵 = and P = PA + PB
𝑃 𝑃
According to Raoult’s law
𝑃𝐴 = 𝑥𝐴 𝑃𝐴𝑂 and 𝑃𝐵 = 𝑥𝐵 𝑃𝐵𝑂
On putting the value of PA, PB and P
𝑥𝐴 𝑃𝐴𝑂 𝑥𝐵 𝑃𝐵𝑂
𝑌𝐴 = and 𝑌𝐴 =
𝑃𝐴 +𝑃𝐵 𝑃𝐴 +𝑃𝐵
Graphical representation discuss on next part in ideal solution.

Vapour pressure of solid-liquid solution

When a small amount of a non-volatile solute is
added to the liquid (solvent) to form solution, it
is observed that vapours pressure of the solution
is less than the vapour pressure of pure solvent.

Raoult’s Law for solid-liquid solution

“The vapour pressure of solution containing

non-volatile solute is directly proportional to
the mole fraction of solvent.”

𝑷𝑨  𝒙𝑨

Or 𝑷𝑨 = 𝑷𝒐𝑨 𝒙𝑨

Graphical representation
y-axis represent vapour pressure
x-axis represent mole fraction of solvent

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Question based on Raoult’s law & Henry’s Law

Assignment No. 4

1. Vapour pressure of chloroform (CHCl3) and dichloroform (CH2Cl2) at 298 K are 200
mm Hg and 415 mm Hg respectively. (i) Calculate the vapour pressure of the solution
prepared by mixing 25.5 g of CHCl3 and 40.0 g of CH2Cl2 at 298 K and (ii) mole
fractions of each component in vapour phase.
2. How is the vapour pressure of a solvent affected when a non-volatile solute is
dissolved in it?
3. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively at
350 K .Find out the composition of the liquid mixture if total vapour pressure is 600
mm Hg. Also find the composition of the vapour phase.
4. Benzene and toluene (C7H8) from ideal solution over entire range of composition .The
vapour pressure of pure benzene and toluene at 300K are 50.71mmHg and 32.06
mmHg respectively. Calculate mol fraction of benzene in vapour phase if 80 g of
benzene is mixed with 100 g toluene.
5. 100 g of liquid A(molar mass 140g/mol) was dissolved in 1000g of liquid B(molar
mass 180g/mol) the vapour pressure of pure B was found to be 500 torr. Calculate the
vapour pressure of pure A and its vapour pressure in solution if total vapour pressure
of a solution is recorded as 475 torr.
6. Heptane and Octane form ideal solution .At 373 K, the vapour pressures of the two
liquid components are 105.2kPa and 46.8kPa respectively. What will be the vapour
pressure, in bar of a mixture of 25.0g heptane and 35.0g of octane?
7. Explain the solubility rule “like dissolves like” in terms of intermolecular forces
that exist in solutions.
8. Match the items given in Column I with the type of solutions given in Column II.
Column I Column II
(i) Soda water (a) A solution of gas in solid
(ii) Sugar solution (b) A solution of gas in gas
(iii) German silver (c) A solution of solid in liquid
(iv) Air (d) A solution of solid in solid
(v) Hydrogen gas in palladium (e) A solution of gas in liquid
(f) A solution of liquid in solid
9. Using Raoult’s law explain how the total vapour pressure over the solution is related
to mole fraction of components in the following solutions. (i) CHCl3 (l) and CH2Cl2(l)
(ii) NaCl(s) and H2O (l)
10. Value of Henry’s constant KH ____________.
(i) Increases with increase in temperature.
(ii) Decreases with increase in temperature.
(iii) Remains constant.
(iv) First increases then decreases.

By: Vinay Tyagi

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Ideal Solution and Non-Ideal Solution

NCERT 2.5

Ideal Solution
A solution is said to be Ideal which obeys Raoult’s law at every temperature and all
concentration.
Let a solution contain two volatile components ‘A’ and ‘B’. According to Raoult’s law
PA = PAo xA & PB = PBo xB
Thus, total vapour pressure,
P = PAo xA + PBo xB
Characteristics of ideal solution
1. An ideal solution forms when both component are identical in molecular size and have
almost same intermolecular forces.
Interaction force between
Solute – solute and solvent – solvent = solute – solvent
A–A + B–B = A–B
2. Volume change of on mixing the two components should be zero.
i.e. Vmix = 0
Volume of solution = volume of solute + volume of solvent
3. Enthalpy of formation of solution should zero.
i.e. Hmix = 0
Neither heat evolved nor absorbed
4. There should be no chemical reaction between solvent and solute.
5. S > 0 and G < 0
6. Solute molecule should not dissociate in the ideal solution.
+ –
NaCl(aq) → Na + Cl
7. Solute molecules should not associate in an ideal solution.
O ............. HO
COOH Dissolve in benzene
2 OH............. O
Association
Example:
(i) Benzene and toluene
(ii) Carbon tetrachloride and silicon tetrachloride
(iii) n-Hexane and n-Heptane
(iv) Ethylene dibromide and Ethylene dichloride
(v) Chlorobenzene and bromobenzene
(vi) Ethyl chloride and Ethyl bromide

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Graph for an Ideal Solution

Non- Ideal Solution

Those solutions which do not obey Raoult's over the entire range of concentration are called
non-ideal solutions.
When the forces of attraction between A—A, B—B is different from A—B then 'A' and 'B'
form non-ideal solutions.
For these solutions :
(i) Raoult's law is not obeyed. (ii) Hmix  0 ; (iii) Vmix  0.
Types of Non-Ideal Solutions:
A. Non-Ideal Solutions Showing Positive Deviation From Raoult’s Law
B. Non-Ideal Solutions Showing Negative Deviation From Raoult’s Law

A. Positive Deviation From Raoult’s Law

a. In this case, partial pressure of each component A and B is higher than that calculated
from Raoult's law, and hence total pressure over the solution is also higher than if the
solution were ideal.
𝐏𝐀 > 𝐏𝐀𝐨 𝐱 𝐀 & 𝐏𝐁 > 𝐏𝐁𝐨 𝐱 𝐁
Therefore actual vapour pressure of solution 𝐏𝒔 > 𝐏𝐀𝐨 𝐱 𝐀 + 𝐏𝐁𝐨 𝐱 𝐁
b. Boiling point of such a solution is relatively lower than the boiling points of both A
and B.

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Note: Dashed lines represent vapour pressures and total pressure corresponding to ideal
solution
Explanation:
Interaction force between solute – solvent is weaker than solute – solute and solvent –
solvent.
Solute – solute and solvent – solvent > solute – solvent
The fact that the vapour pressure is higher than ideal in these mixtures means that molecules
are breaking away more easily than they do in the pure liquids. That is because the
intermolecular forces between molecules of A and B are less than they are in the pure liquids.
You can see this when you mix the liquids. Less heat is evolved when the new attractions are
set up than was absorbed to break the original ones. Heat will therefore be absorbed when the
liquids mix. The enthalpy change of mixing is endothermic. Volume of solution will
therefore increase also.
Examples: water and ethanol, chloroform and water, ethanol and CCl4, methanol and
chloroform, benzene and methanol, acetic acid and toluene, acetone and ethanol, methanol
and H2O, C2H5OH + cyclohexane.

B. Negative Deviation From Raoult’s Law

a. In this case, partial pressure of each component A and B is lower than that calculated
from Raoult's law, and hence total pressure over the solution is also lower than if the
solution were ideal.
𝐏𝐀 < 𝐏𝐀𝐨 𝐱 𝐀 & 𝐏𝐁 < 𝐏𝐁𝐨 𝐱 𝐁
Therefore actual vapour pressure of solution 𝐏𝒔 < 𝐏𝐀𝐨 𝐱 𝐀 + 𝐏𝐁𝐨 𝐱 𝐁
b. Boiling point of such a solution is relatively higher than the boiling points of both A
and B.

Explanation:
Interaction force between solute – solvent is stronger than solute – solute and solvent –
solvent.
Solute – solute and solvent – solvent < solute – solvent
These are cases where the molecules break away from the mixture less easily than they do
from the pure liquids. New stronger forces must exist in the mixture than in the original
liquids. You can recognise this happening because heat is evolved when you mix the liquids-

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more heat is given out when the new stronger bonds are made than was used in breaking the
original weaker ones.

Examples: chloroform and acetone, chloroform and methyl acetate, H2O and HCl, H2O and
HNO3, acetic acid and pyridine, Phenol & Aniline.

Difference between Positive and negative non-ideal solution

Azeotropes or Azeotropic mixtures

• Very large deviations from ideality lead to a special class of mixtures known as
azeotropes, azeotropic mixtures, or constant-boiling mixtures.
• Azeotropic mixture boils at a constant temperature and having same composition in
liquid phase as well as in vapour phase.
• These mixtures cannot be separated into component by fraction distillation. Because
on distillation we will get same composition as they was in liquid phase. They act as
pure liquid.

• Composition in Boiling Composition in Condensation Composition in

liquid phase
• X: Y
liquid phase liquid phase
X: Y X: Y
•

Azeotropes are of two types:

a) Minimum boiling Azeotropes b) Maximum boiling Azeotropes

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a) Minimum boiling Azeotropes

The solutions which show a large positive deviation from Raoult’s law form minimum
boiling azeotrope at a specific composition. Such azeotropes have boiling points lower than
either of the components.
Example:

Components Boiling points (K)

Mass % of A
A B A B Azeotrope
Water Ethanol 4.43 373 351.3 351.1
Water Propanol 28.31 373 370.0 370.2
Chloroform Ethanol 33.0 334 351.3 332.3
Water Pyridine 43.0 373 398.0 365.6
Ethanol Benzene 32.40 351.3 353.2 340.8
Acetic acid Toluene 28.0 393 383.6 378.4

The figures below show the Temperature vs. composition (at constant pressure) phase
diagram on the left side and Pressure vs. composition (at constant temperature) phase
diagram for a minimum-boiling azeotropic mixture chloroform and methanol.

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b) Maximum boiling Azeotropes

The solutions which show a large negative deviation from Raoult’s law form maximum
boiling azeotrope at a specific composition. Such azeotropes have boiling points higher
than either of the components.
Components Mass % Boiling points (K)
A B of A A B Azeotrope
Water HCl 79.7 373 188 383
Water HNO3 42.0 373 359 393.5
Water HClO4 28.4 373 383 476
Acetic acid Pyridine 35.0 393.1 298 412
Chloroform Acetone 80.0 334 329.1 383

The figures below show the Temperature vs. composition (at constant pressure) phase
diagram on the left side and Pressure vs. composition (at constant temperature) phase
diagram for a maximum-boiling azeotropic mixture water and formic acid.

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COLLIGATIVE PROPERTIES
Colligative properties of ideal or very dilute solutions are the properties which depend only
upon the number of solute particles in definite amount of solvent and irrespective of their
chemical and physical nature.

The colligative properties are:

1. Relative lowering in vapour pressure

2. Elevation in boiling point
3. Depression in freezing point
4. Osmotic pressure

1. Relative lowering in vapour pressure

Let, a solution contain
Volatile solvent A – N mole
Non-volatile Solute B – n mole,

 PBo = 0

According to Raoult’s law

𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵

𝑃𝑇 = PAo 𝑥𝐴 + PBo 𝑥𝐵

𝑃𝑇 = PAo 𝑥𝐴 Since PBo = 0

PT = PAo (1 − xB )

Po
A − PT
= 𝑥𝑩
Po
A

Po
A − PT 𝑛
=
Po
A 𝑛+𝑁

∆P 𝑛
=
Po
A 𝑛+𝑁

For very dilute solution, since n <<< N therefore n + N  N

∆P 𝑛 𝑊𝐵 ⁄𝑀𝐵
= =
Po
A 𝑁 𝑊𝐴 ⁄𝑀𝐴

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Numerical Related to RLVP and Raoult’s Law

1. Vapour pressure of water at 293K is 17.5 mm Hg. Calculate vapour pressure of solution
at 293 K when 15g of glucose is dissolved in 150 g of water. [Ans. 17.3 mm Hg]
[CBSE 2015]
2. 30 g of urea (M = 60 g mol –1) is dissolved in 864 g of water. Calculate the vapour
pressure of water for this solution if vapour pressure of pure water at 298 K is 23.8 mm
Hg. [Ans. 23.55 mm Hg]
[CBSE 2017]
3. Vapour pressure of water at 293K is 17.5 mm Hg. Calculate vapour pressure of solution
at 293 K when 68.4g of sucrose is dissolved in 1000 g of water.
[CBSE 2006]
Solution:
Po
A − Ps 𝑛 𝑊𝐵 ⁄𝑀𝐵
According to Raoult’s law = =
Po
A 𝑁 𝑊𝐴 ⁄𝑀𝐴

o
4. The vapour pressure of pure water at 30 C is 31.80 mm Hg. How many grams of urea
should be dissolved in 1000 g water lower the vapour pressure by 0.25 mm Hg?
[CBSE 2006]
Solution:

PAo = 31.80 mm; ∆P = PAo − Ps = 0.25 𝑚𝑚

WA = 1000 g; MB = 60 g mol –1; MA = 18 g mol –1

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2. Elevation in Boling point

NCERT 2.6.2
Boling point: The boiling point of a liquid is the temperature at which it boils or the
pressure on the surface of the liquid becomes equal to the external pressure.
If the external pressure is one atmosphere, the boiling point temperature of liquid is
known as normal boiling temperature.
It is observed that when non-volatile solute added to a solvent, the vapour pressure of
solvent decreases. This means that solution will have to be heated to a higher
temperature for equalize its vapour pressure to atmospheric pressure. And temperature
will be boiling point of solution.
Hence, boiling point of solution containing non-volatile solute is higher than that of pure
solvent.
o
Elevation in b.p. temperature (Tb) = TS – T
o
Ts is boiling point of solution and T is boiling point of pure solvent.

Assuming that solutions are very dilute, these curves may be approximately taken as
straight line near boiling point. Thus, ACE and ABD are similar,
Therefore,

According to Raoult’s Law

𝑤𝐵
∆𝑃 𝑚 (Molality of solution)
𝑚𝐵 ×𝑤𝐴
𝑤𝐵
Or ∆𝑇 𝑚
𝑚𝐵 ×𝑤𝐴
∆𝑻 = 𝑲𝒃 × 𝒎

𝑤𝐵 × 1000
∆𝑇 = 𝑲𝒃
𝑚𝐵 × 𝑤𝐴

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Where, Kb is called the molal elevation constant or ebulliscopic constant.

If m = 1 then ∆𝑇 = 𝐾𝑏

Hence, molal elevation constant defined as the elevation in boiling point when the molality of
the solution is unit.

Unit of Kb is K Kg mol– 1

Molal elevation constant is characteristic of a particular solvent and can be calculated from
the thermodynamical relationship,

𝐑(𝐓𝐛𝒐 )𝟐 𝐌
𝐊𝐛 =
𝟏𝟎𝟎𝟎 × ∆𝐇𝐯𝐚𝐩

𝟐
𝐑𝐓𝐛
Or 𝑲𝒃 = 𝟏𝟎𝟎𝟎×𝐋
𝐯𝐚𝐩

Where,
∆Hvap is molar enthalpy of vaporization of solvent in calories per mol or J/mol
∆Hvap
Lvap is Latent heat of vaporization in Cal/g or J/mol Lvap =
M
M is molar mass of solvent.

Numerical Related Elevation in boiling points

1. 8 g glucose (C6H12O6) is dissolved in 1 kg of water in a saucepan. At what temperature

will water boil under 1.013 bar pressure? Given K for water is 0.52 [Link] –1.
[CBSE 2013]
2. 18 g glucose C6H12O6 is dissolved in 1 kg of water in a saucepan. At what temperature
will solution boil? Kb for water is 0.512 [Link]-1.
3. Find the boiling point of a solution containing 0.520 g of glucose dissolved in 80.2 g of
water. Kb for water is 0.52 [Link]-1.
4. A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in
500 g of water. This solution has a boiling point of 100.42°C. What mass of glycerol
was dissolved to make this solution? (Kb for water = 0.512 K kg mol–1).
5. The boiling point of benzene is [Link] 1.80 g of a non-volatile solute was
dissolved in 90 g of benzene; the boiling point is raised to [Link] the molar
mass of the solute? Kb for benzene is 2.53 K kg mol–1.
6. Boiling point of water at 750 mmHg is [Link] much sucrose is to added to 500 g
water such that it boils at 100oC.
7. A solution of 3.800 g of sulphur in 100 g of CS2 (boiling point = 46.30° C) boils at
46.66° C. What is the formula of sulphur molecule in this solution? (Atomic mass of
sulphur = 32 g mol -1 and Kb for CS2 = 2.40 K kg mol-1).

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8. What would be the molar mass of a compound if 6.21 g of its dissolved in 24 g of

chloroform to form a solution that has a boiling point of 68.04oC .The boiling point of
pure chloroform is 61.7oC and Kb for chloroform is 3.63oC /m.
9. A solution prepared by dissolving 1.25g of oil of wintergreen in 99.0g of benzene has a
boiling point of 80.31oC .Determine the molar mass of this compound(B.P. of pure
benzene = 80.10oC and Kb for benzene is 2.53 [Link]–1).
10. 10 g of sucrose and 10 g of glucose are dissolved in same volume of water to prepare
two solutions X and Y .will they have same or different boiling points?

3. Depression in Freezing point Temperature (Cryoscopy)

NCERT 2.6.3
Freezing point: freezing point of a liquid is defined as the temperature at which the vapour
pressure of its liquid is equal to the vapour pressure of the corresponding solid.

Reason for Depression in Freezing Point

At the freezing point, the vapour pressure of solid and liquid is equal. When non-volatile
solute is dissolves in the solvent, the vapour pressure of solvent in the solution decreases. It
means vapour pressure of solid and liquid solvent will become equal at lower temperature,
i.e. freezing point of solvent in solution is lower than that of pure solvent.

Depression in Freezing Point:

The difference between freezing point of pure solvent Tfº and freezing point of solution T is
called depression in freezing point (Tf).

Depression in freezing point temperature is proportional to the molality (m) of the solution.
∆𝑇𝑓  𝑚
∆𝑇𝑓 = 𝐾𝑓 × 𝑚

𝒘𝑩 × 𝟏𝟎𝟎𝟎
∆𝑻𝒇 = 𝑲𝒇
𝒎 𝑩 × 𝒘𝑨
Here 𝐾𝑓 is molal depression constant or molal cryoscopic constant.
If m = 1 then 𝐾𝑓 = ∆𝑇𝑓

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Molal elevation constant is defines as “It is depression in freezing point temperature for
1 molal solution.”
The Molal depression constant can also be calculate from the thermodynamic relationship.

𝐑(𝐓𝒇𝐨 )𝟐 𝐌
𝐊𝒇 =
𝟏𝟎𝟎𝟎 × ∆𝐇𝒇𝒖𝒔
∆𝐇𝒇𝒖𝒔 is molar enthalpy of fusion of solvent.
𝐌 is molar mass of solvent.
𝐓𝒇𝐨 is freezing point temperature of solvent.

Unit of Kf is K Kg mol– 1

Application
Anti-freeze solutions:

Water is used in the car radiators. In the cold

countries where the atmospheric temperature
becomes less than zero degree, the water in
radiator would freeze.

If this happens then water pump may be

explode or some other damage.

What should we have to do?

We use Anti-freeze solutions for this.

In presence of Anti-freeze solutions water does not freeze.

Examples – Ethylene glycol, Glycerol etc.

H2C OH
H2C OH HC OH
H2C OH H2C OH
Ethylene Glycol Glycerol

Freezing mixture:

It is a mixture of ice and common salt (NaCl). It is used in the making of ice-cream and in the
laboratories to create low temperature. – 33oC temperature can be achieved by this mixture.

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 By: Vinay Tyagi (8273274642)

Question: How does sprinkling of salt help in clearing the snow covered roads in hilly areas?
Explain the phenomenon involved in the process.

OR

Explain why sodium chloride or anhydrous calcium chloride is used to clear snow on road?

Numerical Questions

1. Ethylene glycol ( M = 62 g mol-1) is a common automobile antifreeze. Calculate

the freezing point of a solution containing 12.4 g of this substance in 100 g of
water. . ( Kf = 1.86 K kg mol -1). [CBSE 2010]
2. 45 g of ethylene glycol (C2H6O2) is mixed with 600 g of water. Calculate (a) the
freezing point depression and (b) the freezing point of the solution. ( Kf = 1.86 K kg
mol -1). [CBSE 2015]
Solution:
wB ×1000
(a) ∆Tf = K f
mB ×wA
∆Tf = 2.25 K
(b) Freezing point of solution
= 273.15 – 2.25 = 270.90 K
3. 1.00 g a non-electrolyte solute dissolve in 50.0 g of benzene lowered the freezing
point of freezing point of benzene by 0.40 K. the freezing point depression constant
of benzene is 5.12 K kg mol – 1. Find the molar mass of the solute.
[CBSE 2013]
Solution:
wB × 1000
∆Tf = K f
mB × wA
wB × 1000
mB = K f
∆Tf × wA
mB = 256 g mol−1

Numerical for self-Practice

4. Calculate the mass of ascorbic acid (C6H8O6) to be dissolved in 75g of acetic acid to
lower its melting point by 1.5oC. Kf for acetic acid = 3.9 K kg mol -1
5. A solution containing 2.56 gm of sulphur in 100 g of carbon disulphide gave a
freezing point lowering of 0.383 K .Calculate the molecular formulae of Sulphur [k f
of carbon disulphide = 3.83 K kg/mol Atomic mass of S =32 amu]
6. 15g of an unknown molecular substance was dissolved in 450g of water. The
resulting solution freezes at -[Link] is the molar mass of the substance.

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 By: Vinay Tyagi (8273274642)

7. What mass of ethylene glycol (molar mass =62) must be added to 5.50 kg of water to
lower the freezing point from 0oC to -10oC?( Kf for water = 1.86 K kg mol-1)
8. A 5% solution (by mass) of cane sugar in water has freezing point of 271.15 K.
calculate the freezing point of 5% glucose in water if freezing point of water is
273.15 K.

4. Osmotic pressure
NCERT 2.6.4
Diffusion
Spontaneous flow of particles from high concentration region to lower concentration
region is known as diffusion.

Osmosis
Osmosis is the spontaneous flow of solvent molecules through semipermeable
membrane from a pure solvent to a solution or from a dilute solution to a concentrated
solution.

Semipermeable Membrane (SPM)

A membrane which allows only solvent particles to move across it.
a. Natural Semipermeable membrane: Animal/plant cell membrane formed just
below the outer skins.
b. Artificial membrane - copper ferrocyanide Cu2[Fe(CN)6], Silicates of Ni, Fe, Co 3

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Osmotic pressure ()

It is minimum external pressure that has to be applied on the solution to prevent the
osmosis of the solvent into solution through SPM.

It is indicated by – 
Osmotic pressure can be determined by Hydrostatic method.

 = h..g

Van’t Hoff theory of dilute solutions

Similarities exist between gases and dilute solution in sense that the gas laws which are
applicable to gases can also be applied to dilute solutions.

C
T
𝐧𝐑𝐓 𝐰𝐑𝐓 𝐑𝐓
 = RCT or  = = =
𝐕 𝐕𝐌 𝐝𝐌

Note: osmotic pressure is a colligative property but not osmosis.

Question1: Why is osmosis method used to determine molecular mass of biomolecules

like proteins, polymer & other macromolecules? [AIPMT]
Answer: because at higher these molecule are not stable

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Types of solution on basis of concentration

1. Isotonic solution: Two solutions have same osmotic pressure at a given temp called
isotonic solution.
When these solutions these solutions are separated by SPM there is no osmosis.
2. Hypertonic and Hypotonic solution: if two solutions 1 and 2 are such that 2 > 1
then 2 solutions is called hypertonic solution and 1 is called hypotonic solution.
s
Applied pressure P= 2 - 1

Intravenous drip of saline water:

Osmotic pressure of blood = 0.9 % (W/V) of NaCl
Case I: saline water of 0.9 % (W/V) – Cells neither swell nor shrink
Case II: saline water of greater than 0.9 % (W/V) (Hypertonic solution) – Cell shrink
called as plasmolysis or exosmosis.
Case III: saline water of lesser than 0.9% (W/v) (Hypotonic solution) – cells swell up
called as endosmosis.
Edema: When a person take a lot of salt or salty food, water retention in tissue cells and
intercellular spaces because of osmosis. As a result cell swells up called as Edema.
Reverse Osmosis (RO)
“If the pressure applied on the solution side is more than osmotic pressure of the solution
then the solvent particles will move from solution to solvent side. This process is known
as reverse osmosis.”
This process is used for water purification.

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Some phenomena’s explained on the basis of osmosis

• A raw mango placed in concentrated salt solution loses water via osmosis and shrivel
into pickle.
• Wilted flowers revive when placed in fresh water. A carrot that has become limp
because of water loss into the atmosphere can be placed into the water making it firm
once again. Water will move into them through osmosis.
• When placed in water containing less than 0.9% (mass/volume) salt, blood cells
collapse due to loss of water by osmosis.
• People taking a lot of salt or salty food experience water retention in tissue cells and
intercellular spaces because of osmosis. The resulting puffiness or swelling is called
edema.
• Water movement from soil into plant roots and subsequently into upper portion of the
plant is partly due to osmosis.
• The preservation of meat by salting and of fruits by adding sugar protects against
bacterial action. Through the process of osmosis, a bacterium on salted meat or candid
fruit loses water, shrivels and dies.

Numerical for practice

Questions2: A 5% solution of cane sugar (Mw = 342 g/mol) is isotonic with 1 %

solution of a substance X. The molecular weight of X is –

a) 34.2 b) 171.2 c) 68.4 d) 136.8 [AIPMT]

Solution: 1 = 2
𝟓⁄𝟑𝟒𝟐 𝟏 ⁄𝐌
𝐑𝐓 = 𝐑𝐓 M= 68.4 Ans. c
𝟏𝟎𝟎 𝟏𝟎𝟎

Questions3: A solution is prepared by 10 g of an organic compound in one litre solution

o
at 27 C, osmotic pressure of solution is 1.64 atm. Calculate molar mass of solvent.

Solution:  = CRT

𝐰⁄𝐌
10.64 = 𝐑𝐓
𝐕
M = 150 g/mol

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Numerical for self-Practice

1. 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein .The osmotic
pressure of such a solution at 300K is found to be2.57×[Link] the molar
mass of the protein.
2. 10.0 gm of an organic substance when dissolved in 2 litres of water gave an osmotic
pressure of 0. 60 atm. at 270C. Calculate the molecular mass of substance.
3. Calculate the osmotic pressure in Pascals exerted by a solution prepared by dissolving
1.0 g of polymer of molar mass 185,000 in 450ml of water at 37oC
4. At 300 k, 36g of glucose present per litre in its solution has an osmotic pressure of 4.98
bar. If the osmotic pressure of solution is 1.52 bars at the same temperature, what
would be the concentration of solution?
5. A 5 % solution of cane sugar is isotonic with 0.877% of substance X. Find the
molecular weight of X.
6. 100 mg of a protein is dissolved in enough water to make 10ml of a solution. If this
solution has an osmotic pressure of 13.3 mm Hg at 250C, what is the molar mass of
protein?(R=0.0821 L atm mol-1K-1 and 760 mmHg = 1atm)
7. A solution prepared by dissolving 8.95 mg of a gene fragment in 35.0ml of water has
an osmotic pressure of 0.335 torr at 250C .Calculate its molar mass.

Abnormal colligative properties – Van’t Hoff Factor (i)

NCERT 2.7

The colligative properties of solutions depend on the number of solute particles present in
the solution. Various relations derived for colligative properties hold good in dilute
solution only when there is no charge in molecular state of solute. In case the total
number of particles of the solute in solution changes, the colligative properties also
change accordingly. These changed colligative properties known as abnormal colligative
properties.
If solute does not change number of particle in solution then colligative properties known
as normal colligative properties.
Since, colligative property is inversely proportional to molecular masses of solute; if we
calculate molecular mass of solute from abnormal colligative property then these
molecular masses of solute known as abnormal molecular mass.
Number of particles in solution may change in two ways:
(i) By dissociation
In this case,
Abnormal colligative properties > Normal colligative properties
Abnormal molecular mass < Normal molecular mass

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(ii) By association
In this case,
Abnormal colligative properties < Normal colligative properties
Abnormal molecular mass > Normal molecular mass

Abnormal molecular mass: When the molecular mass, calculated with the help of
colligative property, is different from theoretical molecular mass, it is called abnormal
molecular mass.

Van’t Hoff Factor (i)

It is the ratio of abnormal colligative property and normal colligative property.

Abnormal Colligative property
𝑖=
Normal colligative propeties
Experimental determined value of colligative propery
𝑖=
Calculated by normal formula of colligative propeties
Normal molecular mass
𝑖=
Abnormal molecular mass
Number of particles in solution after dissociation or association
𝑖=
Number of particles in solution before dissociation or association

𝒊 = 𝟏; Normal state, neither association nor dissociation

𝒊 > 𝟏; Dissociation of solute in solution
𝒊 < 𝟏; Association of solute in solution
Modified formulae of colligative properties
Po
A − Ps 𝒊∙𝑛
1. RLVP =
Po
A 𝒊∙𝑛+𝑁
2. Elevation in boiling point , ∆Tb = i × K b × m
3. Depression in freezing point, ∆Tf = i × K f × m
4. Osmotic pressure,  = 𝒊 ∙ 𝐶𝑅𝑇

Calculation of degree of dissociation () by using Van’t hoff factor (i)

𝑨 𝒏𝑨′
t=0 C 0

at eq. C − C nC

Number of particles in solution after dissociation or association

𝑖=
Number of particles in solution before dissociation or association

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C − C + nC
𝑖=
C
1 −  + n
𝑖=
1
𝐢−𝟏
=
𝐧−𝟏
Calculation of degree of association () by using Van’t hoff factor (i)

𝒏𝑨 𝑨′
t=0 nC 0

at eq. 𝑛C − nC nC

Number of particles in solution after dissociation or association

𝑖=
Number of particles in solution before dissociation or association
𝑛C − nC + C
𝑖=
nC
𝑛 − n + 
𝑖=
n
𝟏−𝒊
 =
𝟏 − 𝟏/𝒏

Numerical Related to Van’t Hoff Factor (i)

1. Define abnormal molecular mass.
2. What is Van’t Hoff’s factor? What is value of Van’t Hoff’s factor when the solute
undergoes (a) association (b) dissociation?
3. Write the modified equations of colligative properties when Van’t Hoff’s factor is
introduced.
4. How is Van’t Hoff’s factor related to degree of dissociation & degree of
[Link] Expressions?
5. Why is the mass determined by measuring a colligative property in case of some
solutes abnormal? Discuss it with the help of Van’t Hoff factor.
6. Elevation of boiling point of 1M KCl solution is nearly doubled than that of 1 M
sugar solution. Explain.
7. A 1m aqueous solution of trichloroacetic acid is heated to its boiling point .The
solution has the boiling point 100.18oC .Determine the vant Hoff factor for
trichloroacetic acid. Kb for water is 0.512 KKgmol–1.
8. Calculate the boiling points of solution when 2 gm of Na2SO4 (molecular mass 142
gm/mol) was dissolved in 50 gm of water assuming Na2SO4 undergoes complete
ionization. Kb for water = 0.512 K Kg mol –1
9. Calculate the boiling point elevation for a solution prepared by adding 10 g of CaCl2
to 200 g of water. Kb for water = 0.512 [Link] –1 & Molar mass of CaCl2= 111
g/mol.

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10. Calculate the freezing point of an aqueous solution containing 10.5g of magnesium
bromide in 200g of water assuming complete dissociation of magnesium bromide
.(Molar mass of magnesium bromide= 184 g/mol & Kf for water is 1.86 [Link] –1)
11. Calculate the boiling point of solution containing 4.0 g of magnesium sulphate in
100g of water assuming complete dissociation of magnesium sulphate.(Molar mass of
magnesium sulphate = 120 g/mol Kb for water = 0.52 K Kg mol –1.)
12. Calculate the boiling point of solution containing 15.0 g of NaCl in 250g of
water.(Molar mass of NaCl = 58.44 g/mol Kb for water = 0.512 [Link]–1.)
13. Calculate the mass of NaCl (molar mass =58.5) must be dissolved in 37.2 g of water
to lower the freezing point by 20C assuming complete dissociation of NaCl. Kf for
water is 1.86 [Link] -1 &.
14. What mass of NaCl (molar mass =58.5) must be dissolved in 65g of water to lower
the freezing point by 7.50C? Assume Van’t Hoff’s factor =1.87.
15. Calculate the freezing point depression for 0.711m aqueous solution of sodium
sulphate if it is completely ionised in solution. If this solution actually freezes at –
0.3200C, what is the value of Van’t Hoff factor for it at the freezing point?
16. A 0.561 m solution of unknown electrolyte depresses the freezing point of water by
2.930C. What is the value of Van’t Hoff factor for this electrolyte? Kf for water is
1.86 KKgmol -1
17. Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 litre of water such that its
osmotic pressure is 0.75 atm at 27°C.
18. Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4
in 2 litre of water at 25° C, assuming that it is completely dissociated.
19. Osmotic pressure of a 0.0103 molar solution of an electrolyte is found to be 0.70 atm
at 270C. Calculate Vant Hoff factor.( R=0.082 L atom mol -1 K-1)
20. 3.9g of Benzoic acid dissolved in 49 g of benzene shows a depression in freezing
point equal to 1.62 K. calculate Vant Hoff factor and predict the nature of solute
associated or dissociated. (Kf for benzene is 4.9 K Kg mol –1 & molar mass of Benzoic
acid = 122 g/mol.)
21. 2g of Benzoic acid dissolved in 25 g of benzene shows a depression in freezing point
equal to 1.62 K. Kf for benzene is 4.9 K Kg mol -1. What is the percentage association
of acid if it forms dimer?
22. Phenol associates in benzene to a certain extent to form a dimer .A solution
containing 20g phenol in 1.0 kg of benzene has its freezing point lowered by
[Link] the fraction of phenol that has dimerised. Kf for benzene is 5.1 K Kg
mol -1
23. Calculate the boiling point of one molar aqueous solution .Density of KBr is 1.06
g/ml. (Atomic mass of K = 39 & Br = 80, Kb for water = 0.52 K Kg mol -1.)
24. 19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing
point of water observed is 1.00 C. Calculate the Van’t Hoff factor and dissociation
constant of fluoroacetic acid.
25. Calculate the depression in the freezing point of water when 10 g of
CH3CH2CHClCOOH is added to 250 g of water. Ka = 1.4 × 10–3, Kf = 1.86 K kg mol–1

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