Notes of chaper-1

Class-XII

Subject- (Chemistry)

Name of chapter- Solution

Solute and Solvent

In a binary solution, solvent is the component which is present in large

quantity while the other component is known as solute.

Classification of Solutions

(A) Following types of solutions are seen on the basis of physical state of
solute and solvent.

[if water is used as a solvent, the solution is called aqueous solution and if not,
the solution is called non-aqueous solution.]

(B) Depending upon the amount of solute dissolved in a solvent we have the
following types of solutions:
(i) Unsaturated solution A solution in which more solute can be dissolved
without raising temperature is called an unsaturated solution.

(ii) Saturated solution A solution in which no solute can be dissolved further

at a given temperature is called a saturated solution.

(iii) Supersaturated solution A solution which contains more solute than that
would be necessary to saturate it at a given temperature is called a
supersaturated solution.

Solubility

The maximum amount of a solute that can be dissolved in a given amount of

solvent (generally 100 g) at a given temperature is termed as its solubility at
that temperature.

The solubility of a solute in a liquid depends upon the following factors:

(i) Nature of the solute

(ii) Nature of the solvent
(iii) Temperature of the solution
(iv) Pressure (in case of gases)

Henry’s Law

The most commonly used form of Henry’s law states “the partial pressure (P)
of the gas in vapour phase is proportional to the mole fraction (x) of the gas in
the solution” and is expressed as

p=K .x
H

Greater the value of K , higher the solubility of the gas. The value of
H

K decreases with increase in the temperature. Thus, aquatic species are

H

more comfortable in cold water [more dissolved O ] rather than Warm water.
2

Applications

1. In manufacture of soft drinks and soda water, CO is passed at high

2

pressure to increase its solubility.

2. To minimise the painful effects (bends) accompanying the decompression
of deep sea divers. O diluted with less soluble. He gas is used as breathing
2

gas.
3. At high altitudes, the partial pressure of O is less then that at the ground
2

level. This leads to low concentrations of O in the blood of climbers which

2

causes ‘anoxia’.

Concentration of Solutions

The concentration of a solution is defined as the relative amount of solute

present in a solution. On the basis of concentration of solution there are two
types of solutions.
(i) Dilute solution
(ii) Concentrated solution

Methods of Expressing Concentration of Solutions

Various expression for the concentrations of solutions can be summarised as

(i) Percentage by weight (w / w %) It is defined as the amount of solute

present in 100 g of solution.

w / w % = weight of solute / weight of solution * 100

(ii) Percentage by volume (w / V%) It is defined as the weight 01 solute

present in 100 mL of solution.

w / V % = weight of solute / weight of solution * 100

or the volume of solute present in 100 mL of solution.

u / V % = volume of solute / volume of solution * 100

(iii) Mole fraction (x) It is defined as the ratio of the number of moles of a
component to the total number of moles of all the components. For a binary
solution, if the number of moles of A and B are n and n respectively, the
A B

mole fraction of A will be

(iv) Parts per million (ppm) It is defined as the parts of a component per
million parts (10 ) of the solution. It is widely used when a solute is present in
6

trace quantities.

ppm = number of parts of the component / total number of parts of all the
components * 10 6

(v) Molarity (M) It is the number of moles of solute present in 1L(dm ) of the
3

solution.

M = number of moles of solute / volume of solution (L)

M = mass of solute (in gram) * 1000 / mol. wt. of solute x volume of solution
(in mL)

Molarity varies with temperature due to change in volume of solution.

[When molarity of a solution is 1 M, it is called a molar solution. 0.1 M solution
is called a decimolar solution while 0.5 M solution is known as semi molar
solution]

Molarity = Percent by mass * density * 10 / molecular weight

Dilution law, M V = M V (for dilution from volume V to V )

1 1 2 2 1 2

For reaction between two reactants, M V / n = M V / n

1 1 1 2 2 2

where, n and n arc stoichiometric coefficient in balanced equation.

1 2

(vi) Molality (m) It is the number of moles of solute per kilogram of the solvent.

Molality = mass of solute in gram * 1000 / mol. wt. of solute * mass of solvent
(in g)

Molality is independent of temperature.

[Whcn solvent used is water, a molar (1 M) solution is more concentrated than

a molal (1 M) solution.]

(vii) Normality (N) The number of gram equivalents of solute present in 1 L of

solution.

Normality = number of grams – equivalent of solute / volume of solution in L

Number of gram-equivalents of solute = mass of solute in gram / equivalent

weight

[Relationship between normality and molarity N x Eq. weight = M x mol.

weight ]

If two solutions of the same solute having volumes and molarities V , M and 1 1

V , M are mixed, the molarity of the resulting solution is

2 2

To dilute V mL of a solution having molarity M to molarity M up to the final

1 1 2

volume V mL, the volume of water added is

2
(viii) Formality (F) It is the number of formula weights of solute present per
litre of the solution.

Formality = moles of substance added to solution / volume of solution (in L))

(ix) Mass fraction Mass fraction of any component in the solution is the mass
of that component divided by the total mass of the solution.

Molality, mole fraction and mass fraction are preferred over molarity, normality,
etc., because former involve weights which do not change with temperature.

(x) Demal (D) It represents one mole of solute present in 1L of solution at O°C.

Raoult’s Law

The Raoult’s law states “For a solution of two volatile liquids, the vapour
pressure of each liquid in the solution is less than the respective vapour
pressure of the pure liquids and the equilibrium partial vapour pressure of the
liquid is directly proportional to its mole fraction.

For a solution containing two liquids A and B, the partial vapour pressure of
liquid A is

The proportionality constant is obtained by considering the pure liquid when

χ = 1 then k = P° , the vapour pressure of pure liquid, hence
A A

Konowaloff Rule

At any fixed temperature, the vapour phase is always richer in the more
volatile component as compared to the solution phase. In other words, mole
fraction of the more volatile component is always greater in the vapour phase
than in the solution phase.

The composition of vapour phase in equilibrium with the solution is

determined by the partial pressure of components. If Y and Y are the
1 2

component 1 and 2 respectively in the vapour phase then. using Dalton’s law
of partial pressure,

p =y *P
1 1 total

p =y *P
2 2 total

Ideal Solutions

Those solutions in which solute-solute (B-B) and solvent-solvent (A-A)

interactions are almost similar to solvent solute (A-B) interactions are called
ideal solutions. These solutions satisfy the following conditions :

(i) Solution must obey Raoult’s law, i.e.,

(ii) ΔHmix = 0 (No energy evolved or absorbed)

(iii) ΔVmix = 0 (No expansion or contraction on mixing)

Some solutions behave like nearly ideal solutions, e.g., benzene + toluene. n-
hexane + n-heptane, ethyl iodide + ethyl bromide, chlorobenzene +
bromobenzene.

Non-ideal Solutions

Those solutions which shows deviation from Raoult’s law is called non-ideal
solution.

For such solutions,

ΔH ≠ 0
mix

ΔV ≠ 0
mix
(a) Non-ideal solutions showing positive deviation In such a case, the A –
B interactions are weaker than A – A or B – B interactions and the observed
vapour pressure of each component and the total vapour pressure are greater
than that predicted by Raoult’s law.

For such solutions

(b) Non-ideal solution showing negative deviation In such a case, the A –

B interactions are stronger than A – A or B – B interactions and the observed
vapour pressure of each component and the total vapour pressure are lesser
than that predicted by Raoult’s law.
Azeotropic Mixture

A mixture of two liquids which boils at a particular temperature like a pure

liquid and distils over in the same composition is known as constant boiling
mixtures. These are formed by non-ideal solutions.

(i) Minimum boiling azeotropes are formed by those liquid pairs which show
positive deviation from ideal behaviour. Such azeotropes have boiling points
lower than either of the components, e.g., C H OH (95.57%) + H O (4.43%)(by
2 5 2

mass).

(ii) Maximum boiling azeotropes are formed by those liquid pain; which
show negative deviation from ideal behaviour. Such azeotropes have boiling
points higher than either of the components. e.g., H O(20.22O%)+ HCl
2

(79.78%] by mass.

Colligative Properties

[Colligatil1e : from Latin. = Co mean ‘together’; ligare means ‘to bind’.]

Colligative properties are those properties which depends only upon the
number of solute particles in a solution irrespective of their nature.

Relative Lowering of Vapour Pressure

It is the ratio of lowering in vapour pressure to vapour pressure of pure solvent.

The relative lowering in vapour pressure of solution containing a nonvolatile
solute is equal to the mole fraction of solute in the solution.
Above expression is used to find the molecular weight of an unknown solute
dissolved in a given solvent. Where, W and W = mass of Solute and solvent
B A

respectively. M and M = molecular weight of solute and solvent respectively.

B A

Ostwald and Walker method is used to determine the relative lowering of

vapour pressure.

Elevation in Boiling Point (ΔT ) b

Boiling point of a liquid is the temperature at which its vapour pressure

becomes equal to the atmospheric pressure. As the vapour pressure of a
solution containing a nonvolatile solute is lower than that of the pure solvent, it
boiling point will be higher than that of the pure solvent as shown in figure.
The increase in boiling point is known as elevation in boiling point, ΔT b

ΔT = T – T°
b b b
ΔT = K m (where; m = molality)
b b

K is molal elevation constant or ebullioscopic constant. Molecular mass of

b

solute can be calculated as

where, W and W = mass of solute and solvent respectively.

B A

K has units of K / m or K kg mol , for water, K = 0.52 K kg mol

b
-1
b
-1

The boiling point elevation of a solution is determined by

(i) Landsberger’s method

(ii) Cottrell’s method

Depression in Freezing Point (ΔT ) f

Freezing point of a liquid is the temperature at which vapour pressure of the

solvent in its liquid and solid phase become equal. As we know that vapour
pressure of solution containing non-volatile solute is lower than that of pure
solvent, solid form gets separated out at a lower temperature as shown in the
figure.

This decrease in freezing point of a liquid is known as depression in freezing

point.

Depression in freezing point (ΔT ) = T° – T

f f f
To find molecular mass of solute,

where, K is molal depression constant or cryoscopic constant.

f

K has units of K / m or K kg mol .

f
-1

Ethylene glycol is usually added to water in the radiator to lower its freezing
point. It is called antifreeze solution.

[Common salt (NaCI) and anhydrous CaC12 are used to clear snow on the
roads because they depress the freezing point of water. The freezing point
depression is determined by Beckmann method or Rast method.]

Calculations of molal elevation constant (K ) and molal depression constant

b

(K ) f

Osmotic Pressure (π)

Osmosis is the phenomenon of spontaneous flow of the solvent molecules

through a semipermeable membrane from pure solvent to solution or from a
dilute solution to concentrated solution. It was first observed by Abbe Nollet.

Some natural semipermeable membranes are animal bladder, cell membrane

etc.

CU [Fe(CN) ]is an artificial semipermeable membrane which does not work in

2 6

non-aqueous solutions as it dissolves in them.

Osmosis may be

(i) Exosmosis It is outward flow of water or solvent from a cell through

semipermeable membrane.
(ii) Endosmosis It is inward flow of water or solvent from a cell through a
semipermeable membrane.
The hydrostatic pressure developed on the solution which just prevents the
osmosis of pure solvent into the solution through a semipermeable membrane
is called osmotic pressure.

where, d = density, R = solution constant,

T = temperature, M = molar mass of solute

B

Osmotic pressure can be determined by anyone of the method listed below

(i) Pfeffer’s method

(ii) Berkeley and Hartley’s method (very good method)
(iii) Morse and Frazer’s method

On the basis of osmotic pressure, -the solution can be

(i) Hypertonic solution A solution is called hypertonic if its osmotic pressure

is higher than that of the solution from which it is separated by a
semipermeable membrane.

When a plant cell is placed in a hypertonic solution, the fluid from the plant
cell comes out and cell shrinks, this phenomenon is called plasmolysis.

(ii) Hypotonic solution A solution is called hypotonic if its osmotic pressure is

lower than that of the solution from which it is separated by a semipermeable
membrane.

(iii) Isotonic solution Two solutions are called isotonic if they exert the same
osmotic pressure. These solutions have same molar concentration. 0.91%
solution of pure NaCl is isotonic with human RBC’s.

Two solutions are isotonic if they have the same molar concentration, e.g., if
x % solution of X is isotonic with y % solution of Y, this means molar
concentration of X = Molar concentration of Y
Osmotic pressure method is the best method for determining the molecular
masses of polymers since observed value of any other colligative property is
too small to be measured with reasonable accuracy.

Reverse osmosis When the external pressure applied on the solution is

more than osmotic pressure, the solvent flows from the solution to the pure
solvent, I which is called reverse osmosis. Desalination of sea water is done
by reverse Osmosis.

Abnormal Molecular Masses

In some cases, observed colligative properties deviate from their normal

calculated values due to association or dissociation of molecules. As we know,

Colligative property ∝ 1 / M B

lienee, higher and lower values of molar mass is observed in case of

association and dissociation respectively, e.g., in benzene, acetic acid gets
associated, so, its observed molecular mass is 120. Similarly KCI undergoes
dissociation in aqueous solution, so its observed molecular mass is 37.25.

These observed values are corrected by multiplying with van’t Hoff factor (i).

van’t Hoff Factor (i)

It is the ratio of observed value of colligative property to the calculated value

of colligative property.

i = observed value of colligative property / calculated value of colligative

property

or i = normal molecular mass / observed molecular mass

or i = number of particles after association or dissociation / number of particles

initially

So to correct the observed value of molar mass, van’t Hoff factor (i) must be
included in different expressions for colligative properties.

Degree of Dissociation (α) and van’t Hoff Factor (i)

(i) If one molecule of a substance gets dissociated into n particles or
molecules and α is the degree of dissociation then

Degree of Association (α) and van’t Hoff Factor (i)

If n molecules of a substance A associate to form A and α is the degree of

n

association then

van’t Hoff factor (i) > 1 for solutes undergoing dissociation and it is < 1 for
solutes undergoing association.

NCERT TEXTBOOK QUESTIONS SOLVED

2.1. Calculate the mass percentage of benzene (C6H6) and carbon
tetrachloride (CCl4) if 22 g of benzene is dissolved in 122 g of
carbon tetrachloride.
Ans: Mass of solution = Mass of C6H6 + Mass of CCl4
= 22 g+122 g= 144 g
Mass % of benzene = 22/144 x 100 =15.28 %
Mass % of CCl4 = 122/144 x 100 = 84.72 %

2.2. Calculate the mole fraction of benzene in solution containing

30% by mass in carbon tetrachloride.
Ans: 30% by mass of C6H6 in CCl4 => 30 g C6H6 in 100 g solution
.’. no. of moles of C6H6,(nC6h6) = 30/78 = 0.385

2.3. Calculate the molarity of each of the following solutions

(a) 30 g of Co(NO3)26H2O in 4·3 L of solution
(b) 30 mL of 0-5 M H2SO4 diluted to 500 mL.
Ans:

2.4. Calculate the mass of urea (NH2CONH2) required in making

2.5 kg of 0.25 molal aqueous solution.
Ans: 0.25 Molal aqueous solution to urea means that
moles of urea = 0.25 mole
mass of solvent (NH2CONH2) = 60 g mol-1
.’. 0.25 mole of urea = 0.25 x 60=15g
Mass of solution = 1000+15 = 1015g = 1.015 kg
1.015 kg of urea solution contains 15g of urea
.’. 2.5 kg of solution contains urea =15/1.015 x 2.5 = 37 g

2.5. Calculate
(a) molality
(b) molarity and
(c) mole fraction of KI if the density of 20% (mass/mass) aqueous KI
solution is 1·202 g mL-1.
Ans:
Step I. Calculation of molality of solution
Weight of KI in 100 g of the solution = 20 g
Weight of water in the solution = 100 – 20 = 80 g = 0-08 kg
Molar mass of KI = 39 + 127 = 166 g mol-1.
Step II. Calculation of molarity of solution

Step III. Calculation of mole fraction of Kl

2.6. H2 S, a toxic gas with rotten egg like smell, is used for the
qualitative analysis. If the solubility of H2S in water at STP is 0.195
m, calculate Henry’s law constant.
Ans: Solubility of H2S gas = 0.195 m
= 0.195 mole in 1 kg of solvent
1 kg of solvent = 1000g
2.7. Henry’s law constant for CO2 in water is 1.67 x 108 Pa at
298 K. Calculate the quantity of CO2 in 500 mL of soda water
when packed under 2.5 atm CO2 pressure at 298 K.
Ans.:

2.8 The vapour pressures of pure liquids A and B are 450 mm and
700 mm of Hg respectively at 350 K. Calculate the composition of
the liquid mixture if total vapour pressure is 600 mm of Hg. Also
find the composition in the vapour phase.
Ans:

Vapour pressure of pure liquid A (P∘ A) = 450 mm

Vapour pressure of pure liquid B (P∘ B) = 700 mm

Total vapour pressure of the solution (P) = 600 mm

2.9. Vapour pressure of pure water at 298 K is 23.8 m m Hg. 50

g of urea (NH2CONH2) is dissolved in 850 g of water. Calculate the
vapour pressure of water for this solution and its relative lowering.
Ans:
2.10. Boiling point of water at 750 mm Hg is 99.63°C. How much
sucrose is to be added to 500 g of water such that it boils at
100°C.
Ans:

2.11 Calculate the mass of ascorbic acid (vitamin C, C6H8O6) to be

dissolved in 75 g of acetic acid to lower its melting point by 1·5°C.
(Kf for CH3COOH) = 3·9 K kg mol-1)
Ans:

2.12. Calculate the osmotic pressure in pascals exerted by a solution

prepared by dissolving 1.0 g of polymer of molar mass 185,000 in
450 mL of water at 37°C.
Ans:

NCERT EXERCISES

2.1. Define the terra solution. How many types of solutions are formed?
Write briefly about each type with an example.
Sol: A solution is a homogeneous mixture of two or more chemically
non-reacting substances. Types of solutions: There are nine types of
solutions.
Types of Solution Examples
Gaseous solutions
(a) Gas in gas Air, mixture of 02 and N2, etc.
(b) Liquid in gas Water vapour
(c) Solid in gas Camphor vapours in N2 gas, smoke etc.
Liquid solutions
(a) Gas in liquid C02 dissolved in water (aerated water), and 02 dissolved
in water, etc.
(b) Liquid in liquid Ethanol dissolved in water, etc.
(c) Solid in liquid Sugar dissolved in water, saline water, etc.
Solid solutions
(a) Gas in solid Solution of hydrogen in palladium
(b) Liquid in solid Amalgams, e.g., Na-Hg
(c) Solid in solid Gold ornaments (Cu/Ag with Au)

2.2. Suppose a solid solution is formed between two substances, one

whose particles are very large and the other whose particles are very
small. What type of solid solution is this likely to be ?
Sol: The solution likely to be formed is interstitial solid solution.

2.3 Define the following terms:

(i) Mole fraction
(ii) Molality
(iii) Molarity
(iv) Mass percentage
Sol: (i) Mole fraction: It is defined as the ratio of the number of moles of
the solute to the total number of moles in the solution. If A is the
number of moles of solute dissolved in B moles of solvent, then Mole
fraction of solute

(ii) Molality: It is defined as die number of moles of a solute present in

1000g (1kg) of a solvent.

NOTE: Molality is considered better way of expressing concentration of

solutions, as compared to molarity because molality does not change
with change in temperature since the mass of solvent does not vary with
temperature,
(iii) Molarity: It is defined as the number of moles of solute present in
one litre of solution.
NOTE: Molarity is the most common way of expressing concentration of
a solution in laboratory. However, it has one disadvantage. It changes
with temperature because volume of a solution alters due to expansion
and contraction of the liquid with temperature.
(iv) Mass percentage: It is the amount of solute in grams present in 100g
of solution.

2.4. 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 acid if the density of the solution is 1·504 g mL-1 ?
Sol: Mass of HNO3 in solution = 68 g
Molar mass of HNO3 = 63 g mol-1
Mass of solution = 100 g
Density of solution = 1·504 g mL-1

2.5. A solution of glucose in water is labelled as 10% w/w, what would

be the molality and mole fraction of each component in the solution? If
the density of solution is 1 .2 g m L-1, then what shall be the molarity
of the solution?
Sol: 10 percent w/w solution of glucose in water means 10g glucose and
90g of water.
Molar mass of glucose = 180g mol-1 and molar mass of water = 18g mol-
1
2.6. How many mL of 0.1 M HCl are required to react completely with 1
g mixture of Na2C03 and NaHCO3 containing equimolar amounts of
both?
Sol: Calculation of no. of moles of components in the mixture.
2.7. Calculate the percentage composition in terms of mass of a
solution obtained by mixing 300 g of a 25% and 400 g of a 40% solution
by mass.
Sol:

2.8. An antifreeze solution is prepared from 222.6 g of ethylene glycol,

(C2 H6O2 ) and200 g of water. Calculate the molality of the solution. If
the density of the solution is 1.072 g mL-1, then what shall be the
molarity of the solution?
Sol:

2.9. A sample of drinking water was found to be severely contaminated

with chloroform (CHCl3), supposed to be a carcinogen. The level of
contamination was 15 ppm (by mass).
(i) express this in percent by mass.
(ii) determine the molality of chloroform in the water sample.
Sol: 15 ppm means 15 parts in million (106) by mass in the solution.

2.10. What role does the molecular interaction play in solution of

alcohol in water?
Sol: In case of alcohol as well as water, the molecules are interlinked by
intermolecular hydrogen bonding. However, the hydrogen bonding is
also present in the molecules of alcohol and water in the solution but it
is comparatively less than both alcohol and water. As a result, the
magnitude of attractive forces tends to decrease and the solution shows
positive deviation from Raoult’s Law. This will lead to increase in vapour
pressure of the solution and also decrease in its boiling point.

2.11. Why do gases always tend to be less soluble in liquids as the

temperature is raised?
Sol: When gases are dissolved in water, it is accompanied by a release of
heat energy, i.e., process is exothermic. When the temperature is
increased, according to Lechatlier’s Principle, the equilibrium shifts in
backward direction, and thus gases becomes less soluble in liquids.

2.12. State Henry’s law and mention some of its important applications.
Sol:
Henry’s law: The solubility of a gas in a liquid at a particular temperature
is directly proportional to the pressure of the gas in equilibrium with the
liquid at that temperature.
or
The partial pressure of a gas in vapour phase is proportional to the mole
fraction of the gas (x) in the solution. p = KHX
where KH is Henry’s law constant.
Applications of Henry’s law :
(i) In order to increase the solubility of CO2 gas in soft drinks and soda
water, the bottles are normally sealed under high pressure. Increase in
pressure increases the solubility of a gas in a solvent according to
Henry’s Law. If the bottle is opened by removing the stopper or seal, the
pressure on the surface of the gas will suddenly decrease. This will cause
a decrease in the solubility of the gas in the liquid i.e. water. As a result,
it will rush out of the bottle producing a hissing noise or with a fiz.
(ii) As pointed above, oxygen to be used by deep sea divers is generally
diluted with helium inorder to reduce or minimise the painfril effects
during decompression.
(iii) As the partial pressure of oxygen in air is high, in lungs it combines
with haemoglobin to form oxyhaemoglobin. In tissues, the partial
pressure of oxygen is comparatively low. Therefore, oxyhaemoglobin
releases oxygen in order to carry out cellular activities.

2.13. The partial pressure of ethane over a solution containing 6.56 ×

10-3 g of ethane is 1 bar. If the solution contains 5.00 × 10-2 g of
ethane, then what shall be the partial pressure of the gas?
Sol:

2.14. According to Raoult’s law, what is meant by positive and negative

deviaitions and how is the sign of ∆solH related to positive and
negative deviations from Raoult’s law?
Sol: Solutions having vapour pressures more than that expected from
Raoult’s law are said to exhibit positive deviation. In these solutions
solvent – solute interactions are weaker and ∆solH is positive because
stronger A – A or B – B interactions are replaced by weaker A – B
interactions. Breaking of the stronger interactions requires more energy
& less energy is released on formation of weaker interactions. So overall
∆sol H is positive. Similarly ∆solV is positive i.e. the volume of solution is
some what more than sum of volumes of solvent and solute.
So there is expansion in volume on solution formation.
Similarly in case of solutions exhibiting negative deviations, A – B
interactions are stronger than A-A&B-B. So weaker interactions are
replaced by stronger interactions so , there is release of energy i.e.
∆sol H is negative.

2.15. An aqueous solution of 2 percent non-volatile solute exerts a

pressure of 1·004 bar at the boiling point of the solvent. What is the
molecular mass of the solute ?
Sol:
According to Raoult’s Law,

2.16 Heptane and octane form an ideal solution. At 373 K, the vapour
pressures of the two liquid components are 105.2 kPa and 46.8 kPa
respectively. What will be the vapour pressure of a mixture of 26.0 g of
heptane and 35.0 g of octane?
Sol.
2.17. The vapour pressure of water is 12.3 kPa at 300 K. Calculate
vapour pressure of 1 molal solution of a non-volatile solute in it
Sol: 1 molal solution of solute means 1 mole of solute in 1000g of the
solvent.

2.18. Calculate the mass of a non-volatile solute (molecular mass 40 g

mol-1) that should be dissolved in 114 g of octane to reduce its
pressure to 80%. (C.B.S.E. Outside Delhi 2008)
Sol: According to Raoult’s Law,

2.19. A solution containing 30g of non-volatile solute exactly in 90 g of

water has a vapour pressure of 2.8 kPa at 298 K. Further, 18g of water
is then added to the solution and the new of vapour pressure becomes
2.9 kPa at 298 K. Calculate
(i) molar mass of the solute.
(ii) vapour pressure of water at 298 K.
Sol: Let the molar mass of solute = Mg mol-1
2.20. A 5% solution (by mass) of cane sugar in water has freezing point
of 271 K. Calculate the freezing point of 5% glucose in water if freezing
point of pure water is 273.15 K.
Sol: Mass of sugar in 5% (by mass) solution means 5gin 100g of solvent
(water)

2.21. Two elements A and B form compounds having formula AB2 and
AB4. When dissolved in 20g of benzene (C6H6), 1 g of AB2 lowers the
freezing point by 2.3 K whereas 1.0 g of AB4 lowers it by 1.3 K. The
molar depression constant for benzene is 5.1 K kg mol-1. Calculate
atomic masses of A and B.
Sol:

2.22. At 300 K, 36 g glucose present per litre in its solution has osmotic
pressure of 4·98 bar. If the osmotic pressure of the solution is 1·52 bar
at the same temperature, what would be its concentration?
Sol:
2.23. Suggest the most important type of intermolecular attractive
interaction in the following pairs:
(i) n-hexane and n-octane
(ii) I2 and CCl4.
(iii) NaCl04 and water
(iv) methanol and acetone
(v) acetonitrile (CH3CN) and acetone (C3H60)
Sol: (i) Both w-hexane and n-octane are non-polar. Thus, the
intermolecular interactions will be London dispersion forces.
(ii) Both I2 and CCl4 are non-polar. Thus, the intermolecular interactions
will be London dispersion forces.
(iii) NaCl04 is an ionic compound and gives Na+ and Cl04– ions in the
Solution. Water is a polar molecule. Thus, the intermolecular
interactions will be ion-dipole interactions.
(iv) Both methanol and acetone are polar molecules. Thus,
intermolecular interactions will be dipole-dipole interactions.
(v) Both CH3CN and C3H6O are polar molecules. Thus, intermolecular
interactions will be dipole-dipole interactions.

2.24. Based on solute solvent interactions, arrange the following in

order of increasing solubility in n-octane and explain. Cyclohexane, KCl,
CH3OH, CH3CN.
Sol: n-octane (C8H18) is a non-polar liquid and solubility is governed by
the principle that like dissolve like. Keeping this in view, the increasing
order of solubility of different solutes is:
KCl < CH3OH < CH3C=N < C6H12 (cyclohexane).

2.25. Amongst the following compounds, identify which are insoluble,

partially soluble and highly soluble in water?
(i) phenol
(ii) toluene
(iii) formic acid
(iv) ethylene glycol
(v) chloroform
(vi) pentanol
Sol: (i) Phenol (having polar – OH group) – Partially soluble.
(ii) Toluene (non-polar) – Insoluble.
(iii) Formic acid (form hydrogen bonds with water molecules) – Highly
soluble.
(iv) Ethylene glycol (form hydrogen bonds with water molecules) Highly
soluble.
(v) Chloroform (non-polar)- Insoluble.
(vi) Pentanol (having polar -OH) – Partially soluble.

2.26. If the density of lake water is 1·25 g mL-1, and it contains 92 g of

Na+ ions per kg of water, calculate the molality of Na+ ions in the lake.
(C.B.S.E. Outside Delhi 2008)
Sol:

2.27. If the solubility product of CuS is 6 x 10-16, calculate the

maximum molarity of CuS in aqueous solution.
Sol:

2.28. Calculate the mass percentage of aspirin (C9H8O4 in acetonitrile

(CH3CN) when 6.5g of CHO is dissolved in 450 g of CH3CN.
Solution:
Mass of aspirin = 6.5 g
Mass of acetonitrile = 450 g
Then, total mass of the solution = (6.5 + 450) g = 456.5 g
Therefore, mass percentage of C9H8O4 = 6.5456.5 × 100%
= 1.424%

2.29. Nalorphene (C19H21NO3), similar to morphine, is used to combat

withdrawal symptoms in narcotic users. Dose of nalorphene generally
given is 1.5 mg. Calculate the mass of 1.5 x 10-3 m aqueous solution
required for the above dose.
Solution:

2.30. Calculate the amount of benzoic acid (C5H5COOH) required for

preparing 250 mL of 0· 15 M solution in methanol.
Solution:

2.31. The depression in freezing point of water observed for the same
amount of acetic acid, trichloroacetic acid and trifluoroacetic acid
increases in the order given above. Explain briefly.
Solution:

Fluorine being more electronegative than chlorine has the highest

electron withdrawing inductive effect. Thus, triflouroacetic acid is the
strongest trichloroacetic acid is second most and acetic acid is the
weakest acid due to absence of any electron withdrawing group. Thus,
F3CCOOH ionizes to the largest extent while CH3COOH ionizes to
minimum extent in water. Greater the extent of ionization greater is the
depression in freezing point. Hence, the order of depression in freezing
point will be CH3COOH < Cl3CCOOH < F3CCOOH.

2.32. Calculate the depression in the freezing point of water when 10g
of CH3CH2CHClCOOH is added to 250g of water. Ka = 1.4 x 1o-3 Kg =
1.86 K kg mol-1.

Solution:
Mass of solute (CH3CH2CHClCOOH) = 10 g
Molar mass of
CH3CH2CHClC00H = 4 × 12 + 7 × 1 + 1 × 35.5 + 2 × 16 = 48 + 7 + 35.5 + 32
= 122.5 g mol-1
\frac{\text { Mass / Molar mass }}{\text { Mass of solvent (Kg) }} = Mass /
Molar mass Mass of solvent
(Kg) [latex/latex]=[latex]10 g(122.5 g mol−1)×(0.25Kg)
= 0.326 m
Let α be the degree of dissociation of CH3CH2CHClCOOH then
Total no. of moles after dissociation = 1 – α + α + α
=1+α
Van’t Hoff factor
Total no. of moles after dissociation

∴ i = 1+α1
=1+α
= 1 + 0.0655
= 1.0655
Hence, the depression in the freezing point of water is given as:
ΔTf = i.Kfm
= 1.0655 × 1.86 kg mol-1 × 0.326 mol kg-1
= 0.65K

2.33. 19.5g of CH2FCOOH is dissolved in 500g of water. The depression

in the freezing point of water observed is 1.0°C. Calculate the van’s
Hoff factor and dissociation constant of fluoroacetic acid.

Solution:
Calculation of Van’t Hoff factor (i)
Given, w1 = 500 g = 0.5 kg, w2 = 19.5 g, Kf = 1.86 K kg mol-1, ΔTf = 1 K
Molar mass of CH2FCOOH (M2)
= 2 × 12 + 3 × 1 + 1 × 19 + 2 × 16
= 24 + 3 + 19 + 32
= 78 g mol-1
ΔTf = i Kf m
2.34. Vapour pressure of water at 293 K is 17·535 mm Hg. Calculate the
vapour pressure of water at 293 K when 25 g of glucose is dissolved in
450 g of water.
Solution:
According to Raoult’s Law,
2.35. Henry’s law constant for the molality of methane in benzene at
298 K is 4.27 x 105 mm Hg. Calculate the solubility of methane in
benzene at 298 K under 760 mm Hg.

Solution:
Here, p = 760 mm Hg, KH = 4.27 × 105 mm Hg (at 298 K)
According to Henry’s law, p = KHχ
χ = pkH
= 760 mmHg4.27×105 mmHg
= 177.99 × 10-5
= 178 × 10-5
Hence, the mole fraction of methane in benzene is 178 × 10-5.

2.36. 100g of liquid A (molar mass 140 g mol-1) was dissolved in 1000g
of liquid B (molar mass 180g mol-1). The vapour pressure of pure liquid
B was found to be 500 torr. Calculate the vapour pressure of pure
liquid A and its vapour pressure in the solution if the total vapour
pressure of the solution is 475 torr.

Solution:
Number of moles of liquid A, nA = w1M1 = 100140 mol = 0.714 mol
Number of moles of liquid B,nB = w2M2 = 1000180 mol = 5.556 mol
Then, mole fraction of A, χA = nAnA+nB
= 0.714 mol(0.714+5.556)mol = 0.114
Mole fraction of B, χB = 1 – 0.114 = 0.886
Vapour pressure of pure liquid B, p0B = 500 torr
Therefore, vapour pressure of liquid B in the solution,
PB = p0BχB
= 500 × 0.886
= 443 torr
Total vapour pressure of the solution, ptotal = 475 torr
∴ Vapour pressure of liquid A in the solution,
PA = Ptotal – PB
= 475 – 443 = 32 torr
Now, PA = p0AχA
⇒ pAχA = 320.114
= 280.7 torr
Hence, the vapour pressure of pure liquid A is 280.7 torr.
2.37. Vapour pressures of pure acetone and chloroform at 328 K are
741.8 mm Hg and 632.8 mm Hg respectively. Assuming that they form
ideal solution over the entire range of composition, plot Ptotal,
Pchlroform and Pacetone as a function of χacetone. The experimental
data observed for different compositions of mixtures is:

Plot this data also on the same graph paper. Indicate whether it has
positive deviation or negative deviation from the ideal solution.

Solution:

It can be observed from the graph that the plot for the ptotai of the
solution curves downwards. Therefore, the solution shows negative
deviation from the ideal behaviour.

2.38. Benzene and toluene form ideal solution over the entire range of
composition. The vapour pressure of pure benzene and toluene at 300
K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate the mole
fraction of benzene in vapour phase if 80g of benzene is mixed with
100g of toluene.
Solution:
Molar mass of benzene (C6H6) = 6 × 12 + 6 × 1 = 78g mol-1
Molar mass of toluene (C6H5CH3 ) = 7 × 12 + 8 × 1 = 92 g mol-1
No. of moles present in 80 g of benzene = 8078 mol = 1.026 mol
No. of moles present in 100 g of toluene = 10092 mol = 1.087 mol
Mole fraction of benzene, χC6H6, = 1.0261.026+1.087 = 0.486
∴ Mole fraction of toluene,χC6H5CH35013 = 1 – 0.486 = 0.514
It is given that vapour pressure of pure benzene, p0C6H6 = 50.71 mm Hg
Vapour pressure of pure toluene, p0C6H5CH3 = 32.06 mm Hg
Therefore, partial vapour pressure of benzene,
Ptotal = χC6H6 × p0C6H6
= 0.486 × 50.71
= 24.645 mm Hg
Partial vapour pressure of toluene, PC6H5CH3 =
χC6H5CH3 × P0C6H5CH3
= 0.514 × 32.06
= 16.479 mm Hg
Total vapour pressure of solution (p) = 24.645 + 16.479
= 41.124 mm Hg
Mole fraction of benzene in vapour phase
= χC6H6×p0C6H6ptotal
= 0.486×(50.71)mm(41.124)mm
= 0.599 ≅ 0.6

2.39. The air is a mixture of a number of gases. The major components

are oxygen and nitrogen with an approximate proportion of 20% is to
79% by volume at 298 K. The water is in equilibrium with air at a
pressure of 10 atm. At 298 K if Henry’s law constants for oxygen and
nitrogen are 3.30 x 107 mm and 6.51 x 107 mm respectively, calculate
the composition of these gases in water.

Solution:
Percentage of oxygen (O2) in air = 20%
Percentage of nitrogen (N2) in air = 79%
Also, it is given that water is in equilibrium with air at a total pressure of
10 atm that is, (10 × 760) mm = 7600 mm
Therefore, partial pressure of oxygen,
PO2 = 20100 x 7600 mm
= 1520 mm Hg
Partial pressure of nitrogen, pN2 = 79100 x 7600 mm
= 6004 mm Hg
Now, according to Henry’s law,
p = KH.χ
For oxygen:

6004 mm6.51×107 mm
(Given KH = 6.51 × 107 mm)
= 9.22 × 10-5
Hence, the mole fractions of oxygen and nitrogen in water are 4.61 × 10-
5 and 9.22 × 10-5 respectively.

2.40. 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.

Solution:
We know that,
π = i RT
⇒ π = i RT
⇒w=
Given,
π = 0.75 atm
V = 2.5L
i = 2.47
T = (27 + 273)K = 300K
R = 0.0821 L atm K-1mol–
Molar mass of CaCl2(M) = 1 × 40 + 2 × 35.5 = 111 g mol -1
Therefore, w = 0.75×111×2.52.47×0.0821×300 = 3.42g
Hence the required amount of CaCl2 is3.42g
2.41. 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. (C.B.S.E. 2013)
Solution:
Step I. Calculation of Van’t Hoff factor (i)
K2SO4 dissociates in water as :