NCERT Solutions Chemistry Class XII

UNIT 2: SOLUTIONS
INTEXT QUESTIONS

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.
ANSWER:
Mass of solution = Mass of benzene + Mass of carbon tetrachloride
= 22 g + 122 g = 144 g

2.2 Calculate the mole fraction of benzene in solution containing 30% by mass in
carbon tetrachloride. (Intermediate)
ANSWER:
Let the total mass of the solution be 100 g and the mass of benzene be 30 g.

∴ Mass of carbon tetrachloride = (100 - 30) g = 70 g

Molar mass of benzene (C6H6) = (6 × 12 + 6 × 1) g mol - 1

= 78 g mol - 1
∴ Number of moles of C6H6 =30/78 mol
= 0.3846 mol

Molar mass of carbon tetrachloride (CCl4) = 1 × 12 + 4 × 35.5

= 154 g mol - 1
∴ Number of moles of CCl4 = 70/154 mol
= 0.4545 mol

Thus, the mole fraction of C6H6 is given as:

= 0.3846 / (0.3846 + 0.4545)

2.3 Calculate the molarity of each of the following solutions: (a) 30 g of Co(NO3)2.
6H2O in 4.3 L of solution (b) 30 mL of 0.5 M H2SO4 diluted to 500 mL.(Advanced)
ANSWER:

Molarity =

(a) Given, In 4.3 L of solution there is 30 g of Co(NO3)2. 6H2O

Molar mass of Co(NO3)2.6H2O = (1 × 59 + 2 × (1 × 14 + 3 × 16) + 6 × 18)
 = 291 g/mol.

∴ Moles = = 0.103 mol.

Now, Molarity =

= 0.023 M

(b) Given, 30 mL of 0.5 M H2SO4 diluted to500 mL.

In 1000 mL of 0.5 M H2SO4, number of moles present is 0.5 mol.

∴ In 30 mL of 0.5 M H2SO4, number of moles present = mol.

= 0.015 mol.

∴ Molarity =

= 0.03 M.

2.4 Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal
aqueous solution.
ANSWER:
2.5 kg of 0.25 molal aqueous solution.

Molar mass of urea (NH2CONH2) = (2 (1 × 14 + 2 × 1) + 1 × 12 + 1 × 16)

= 60 g/mol

1000 g of water contains 0.25 mol = (0.25 × 60) g of urea.

= 15 g of urea.

Means, 1015 g of solution contains 15 g of urea

Therefore,

2500 g of solution contains =

= 36.95 g

Hence, mass of urea required is 37 g (approx).

2.5 Calculate (a) molality (b) molarity and (c) mole fraction of KI if the density of 20%
(mass/mass) aqueous KI is 1.202 g mL-1 .

ANSWER:
(a) Molality, also called molal concentration, is a measure of the concentration of a
solute in a solution in terms of amount of substance in a specified amount of mass of
the solvent.
Molar mass of KI = 39 + 127 = 166 g/mol.

20% aqueous solution of KI means 200 g of KI is present in 1000 g of solution.

Therefore,

Molality =

= 1.506 m

∴ Molality of KI = 1.506 m

(b) Molarity is the concentration of a solution expressed as the number of moles of

solute per litre of solution.

Given,

Density of the solution = 1.202 g/mL

Volume of 100 g solution = mass/ density

= 100/1.202

= 83.19 mL

Therefore, molarity = mol/ 83.19 × 10 - 3 L

= 1.45 M

∴ Molarity of KI = 1.45M
(c) Molar mass of KI = 39 + 127 = 166 g/mol.

Moles of KI = 20/166 = 0.12 mol

Moles of water = 80/18 = 4.44 mol

Therefore,

Mole fraction of KI =

= 0.0263

∴ Mole fraction of KI = 0.0263

2.6 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 0.195 m, calculate Henry’s law constant.
ANSWER:
According to Henry's law,"At a constant temperature, the amount of a given gas that
dissolves in a given type and volume of liquid is directly proportional to the partial
pressure of that gas in equilibrium with that liquid."

Stated as,
p = KHx

Where, P = partial pressure of the solute above the solution

KH = Henry's constant
x = concentration of the solute in the solution

Given,

Solubility of H2S in water at STP is 0.195 m

We know,

At STP pressure p = 0.987 bar

0.195 mol of H2S is dissolved in 1000g of water

Moles of water =

= 55.56 g/mol
∴ the mole fraction of H2S =

= 0.0035

According to Henry's law, p = KHx

KH =

KH =

KH = 282 bar
∴ The Henry’s law constant is 282 bar

2.7 Henry’s law constant for CO2 in water is 1.67x108 Pa at 298 K. Calculate the
quantity of CO2in 500 mL of soda water when packed under 2.5 atm CO2pressure at
298 K.
ANSWER:
According to Henry's law,

"At a constant temperature, the amount of a given gas that dissolves in a given type
and volume of liquid is directly proportional to the partial pressure of that gas in
equilibrium with that liquid."

Stated as,

p = KH x

Where,

P = partial pressure of the solute above the solution

KH = Henry's constant

x = concentration of the solute in the solution

Given,

KH = 1.67x108 Pa

PCO2 2.5 atm = 2.5 × 1.01325 × 105Pa

According to Henry's law,

 p = KHx

x = 0.00152

In 500 ml of soda water there is 500 ml of water (neglecting soda)

Mole of water =

= 27.78 mol

Now,

x=

nCO2 = x nH2O

= 0.00152 × 27.78

= 0.042 mol

Hence, quantity of CO2 in 500mL of soda water 0.042 × 44 = 1.848 g

2.8 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.
ANSWER:
Given, PAo = 450 mm Hg

PBo = 700 mm Hg

ptotal = 600 mm of Hg

By using Rault's law,

ptotal = PA + PB

ptotal = PAoxA + PBoxB

ptotal = PAoxA + PBo( 1 - xA )

ptotal = (PAo- PBo)xA + PBo

600 = (450 - 700) xA + 700

-100 = -250 xA

xA = 0.4

∴ xB = 1 - xA

xB = 1 – 0.4

xB = 0.6

Now,

PA = PAoxA

PA = 450 × 0.4

PA = 180 mm of Hg

and

PB = PBox

PB = 700 × 0.6

PB = 420 mm of Hg

Composition in vapour phase is calculated by

Mole fraction of liquid,

= 0.30

Mole fraction of liquid,

= 0.70
2.9 Vapour pressure of pure water at 298 K is 23.8 mm 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.
ANSWER:

Given,

Vapour pressure of water, PIo = 23.8 mm of Hg

Weight of water, w1 = 850 g

Weight of urea, w2 = 50 g

Molecular weight of water, M1 = 18 g/mol

Molecular weight of urea, M2 = 60 g/mol

n1 = = 47.22 mol

n2 = = 0.83 mol

We have to calculate vapour pressure of water in the solution p1

By using Raoult's therom,

(relative lowering)

PI = 23.4 mm of Hg

Hence,

The vapour pressure of water in the solution is 23.4mm of Hg and its relative
lowering is 0.0173.
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.
ANSWER:
Given,

Mass of water, wl = 500 g

Boiling point of water = 99.63°C (at 750 mm Hg).

Molal elevation constant, Kb = 0.52 K kg/mol

Molar mass of sucrose (C12H22O11), M2 (11 × 12 + 22 × 1 + 11 × 16) = 342 g/mol

Elevation of boiling point ΔTb = (100 + 273) - (99.63 + 273) = 0.37 K

We know that,

ΔTb =

0.37 =

w2 =

w2 = 121.67 g

Hence,

121.67 g (approx) Sucrose is added to 500g of water so that it boils at 100°C.

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 = 3.9 K kg mol-1.
ANSWER:
Given

Mass of acetic acid, w1 = 75 g

Lowering of melting point, ΔTf = 1.5 K

Kf = 3.9 K kg/mol

Molar mass of ascorbic acid (C6H8O6), M2 6 × 12 + 8 × 1 + 6 × 16 = 176 g/mol[1]

We know that,
ΔTb =

1.5 =

w2 =

= 5.08 g

Hence,

5.08 g of ascorbic acid is needed to be dissolved.

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.
(Beginners)
ANSWER:
Given,

Volume of water, V = 450 mL = 0.45 L

Temperature, T (37 + 273)K = 310 K

1.0 g of polymer of molar mass 185,000

Number of moles of polymer, n = 1 / 185,000 mol

We know that,

Osmotic pressure, π =

= 30.98 Pa

= 31 Pa (approx)

Exercises QUESTIONS

2.1 Define the term solution. How many types of solutions are formed? Write
briefly about each type with an example.
ANSWER:
A solution is a homogeneous mixture of two or more than two substances on
molecular level whose composition can vary within certain limits.

The part or component of the mixture present in a lesser amount is called

the SOLUTE and the one present in larger amount is called the SOLVENT. For eg-
small amount of salt [solute] dissolved in water [solvent].

There are nine types of solutions formed. They are:

Sr.No. State of solute State of solvent Examples

1 GAS GAS Air

2 GAS LIQUID Oxygen in water, carbonated water

Smoke particles in air, dust particles

3 SOLID GAS
in air

4 LIQUID GAS Mist

5 LIQUID LIQUID Alcohol in water

6 LIQUID SOLID Mercury in silver

Adsorption of hydrogen over

7 GAS SOLID
palladium or platinum

8 SOLID LIQUID Sugar in water

9 SOLID SOLID Carbon in Iron(steel), Alloy

Out of these nine types solution, solid in liquid, liquid in liquid & gas in liquid are very
common. When the components of the solution are mixed, the resulting solution
may exist in any of the three possible states of matter that is solid, liquid or gaseous.

They are:

[i] Gaseous solution: In such solutions solvent is gas. Since the solvent is gas,
the solute can be solid, liquid or gas. For example, a mixture of oxygen and nitrogen
gas is a gaseous solution.

[ii] Liquid solution: In such type of solutions liquid acts as the solvent. The solute in
these solutions may be gas, liquid, or solid.

[iii] Solid solutions: As the name suggests, in such solutions solid acts as the solvent.
The solute in these solutions may be a gas, liquid or solid. For example, a solution of
copper in gold is a solid solution.

2.2 Give an example of a solid solution in which the solute is a gas.

ANSWER:
As the name signifies, a solid solution is one in which solvent is solid.

So considering this aspect absorption of hydrogen over platinum or palladium is an

example of such solution. Platinum or palladium is used as
a catalyst in hydrogenation processes.

2.3 Define the following terms: (i) Mole fraction (ii) Molality (iii) Molarity (iv) Mass
percentage.
ANSWER:
(i) Mole fraction - The mole fraction of a particular component in a solution is
the ratio of the number of moles of that component to the total number of moles of
all the components present in the solution.

Mathematically,

Mole Fraction of component

Mole Fraction is independent of temperature.

(ii) Molality - Molality of a solution is defined as the number of moles of solute

dissolved per 1000g [1kg] of the solvent. It is represented by m.

Molality actually represents the concentration of solution in mol / kg.

Mathematically,

Molality

It is represented by m.

(iii) Molarity- The number of moles of solute dissolved per litre of the solution at a
particular temperature is called the molarity of the solution at that temperature.

Molarity actually represents the concentration of a solution in mol / L.

Mathematically,

Molarity

(iv) Mass percentage - Mass percentage is defined as the mass of the solute in grams
dissolved per 100g of the solution. It is also referred to as weight percentage [w/w].

For example, 10% [by mass] urea solution means that 10 g of urea are present in 100
g of solution, the solvent being only 100-10 = 90 g.

Mathematically, the mass percentage of a solute in a solution is given by:

Mass Percentage of Solute

Or

Mass Percentage of Solute

2.4 Concentrated nitric acid used in 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–1?
ANSWER:
Given:

Concentration of Nitric Acid, HNO3 = 68%

Density of solution, d = 1.504 g/ml

To find: Molarity, Mo

Formula:

Density, d

Molarity, Mo

Solution:

68% of Nitric acid by mass in aqueous solution means that 68g [[68 × 100]/100] of
Nitric acid present in 100g of solution.

⇒ Molecular mass of Nitric Acid, HNO3 = [1 × 1] + [1 × 14] + [16 × 3]

= 63g

⇒ Number of moles of Nitric Acid = [68/63]

= 1.079 moles

⇒ Given Density, d = 1.504 g/ml

⇒ Volume, v = [100/1.504]

= 66.489 ml

⇒ Molarity, Mo = [1.079/66.489] × 1000

= 16.23 M

Therefore the molarity of the sample is 16.24 M.

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 mL–1, then what shall be the molarity of the solution?
ANSWER:
Given:
10% w/w solution means that if solution is of 100g then 10g of glucose is present in
it [[10 × 100]/100] and the amount of water present in it is [100-10], Mw = 90g.

Density, d = 1.2g/ml

To find: Molality and Mole Fraction of Each component

Formula:

Density, d

Molality

Mole Fraction of component

Molarity, Mo

Solution:

Calculation of Molality:

⇒ Molecular mass of Glucose, [C6H12O6] = [6 × 12] + [12 × 1] + [6 × 16]

= 72 + 12 + 96

= 180g

⇒ Number of moles of Glucose, Ng = [10/180]

= 0.0556 moles

⇒ Molality

⇒ Molality

= 0.6177 m

≈ 0.62 m

Calculation of Mole Fraction:

⇒ Molecular Mass of Water, [H2O] = [2 × 1] + [16 × 1]

= 2 + 16
= 18g

⇒ Number of moles of water, Nw = [90/18]

= 5 moles

⇒ Mole Fraction of Glucose,

= 0.011

⇒ Mole Fraction of Water,

= 1 – 0.011

= 0.989

Calculation of Molarity:

From density we can find out volume.

⇒ Volume, V = [100/1.2]

= 83.33 ml

⇒ Molarity

Molarity, M = 0.667 M

≈ 0.67 M

Therefore the answers obtained in the numerical can be summarized in following

table:

Quantity Answer

Molality, m 0.62 m
Mole Fraction of Glucose 0.011

Mole Fraction of Water 0.989

Molarity, M 0.67 M

2.6 How many mL of 0.1 M HCl are required to react completely with 1 g mixture of
Na2CO3 and NaHCO3 containing equimolar amounts of both?
ANSWER:
Given:

Molarity of HCl, = 0.1 M

Mass of Mixture = 1g

To find: Volume of HCl to react completely with mixture

Formula:

Molarity, Mo

Solution:

Calculation of Amount of each component in mixture:

⇒ Let the amount of Na2CO3 be X g

⇒ And Let amount of NaHCO3 be [1-X] g

⇒ Molecular Weight of Na2CO3 = [23 × 2] + [12] + [3 × 16]

= 106 g

⇒ Molecular Weight of NaHCO3 = [23] + [1] + [12] + [3 × 16]

= 84 g

⇒ Number of moles of NaHCO3

⇒ Number of moles of Na2CO3

Now it is given in the question that the mixture is equimolar, so

⇒ Number moles of Na2CO3 = Number of moles of NaHCO3

106 – 106X = 84X

190X = 106

X = 0.5579

≈ 0.558

Amount of Na2CO3 = 0.558 g

⇒ Amount of NaHCO3 = 1- 0.558 g = 0.442 g

⇒ Number moles of Na2CO3 = [0.558/106]

= 0.00526 moles

⇒ Number of moles of NaHCO3 = 0.00526 moles …. [Mixture is equimolar]

Calculation of volume of HCl required:

⇒ In the question it is given that HCl reacts with the mixture.

Na2CO3 + 2HCl → 2NaCl + H2O + CO2

NaHCO3 + HCl → NaCl + H2O + CO2

From the above chemical equations it can be found that 2 moles of HCl is required to
react with one mole of Na2CO3 and 1 moles of HCl is required to react with one mole
of NaHCO3.

So total number of moles of HCl required to completely react with mixture is as

follows:

⇒ Total Number of Moles of HCl = [2 × 0.00526] + 0.00526

= 0.01578 moles
From Molarity Formula we have,

Molarity, Mo

⇒ Volume in litres, V = [0.01578/0.1]

= 0.1578 L

⇒ Volume in ml, V = 0.1578 × 1000

= 157.8 ml

Therefore the volume of 0.1 M HCl are required to react completely with 1 g mixture
of Na2CO3 and NaHCO3 containing equimolar amounts of both is 157.8 ml.

2.7 A solution is obtained by mixing 300 g of 25% solution and 400 g of 40%
solution by mass. Calculate the mass percentage of the resulting solution.
ANSWER:
Let the first solution be solution A and second solution be solution B.

Given:

⇒ Mass of Solute in solution A, Ma = [25 × 300]/100

= 75g

⇒ Mass of Solute in solution B, Mb = [40 × 400]/100

= 160g

To find: Mass Percentage of Solute

Formula:

Mass Percentage of Solute

Solution:

⇒ Total mass of Solute in mixture, M = Ma + Mb

= [75 + 160]

= 235g

⇒ Total mass of solution = 300 + 400

= 700g

⇒ Mass Percentage of Solute

= 33.5%

⇒ Percentage of Water in final solution = 100-33.5

= 66.5%

Therefore mass percentage of solute is 33.5% and that of water is 66.5%.

2.8 An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2 ) and
200 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?
ANSWER:
Given:

Mass of ethylene glycol (C2H6O2) = 222.6 g

Mass of water = 200 g

Density, d = 1.072 g/ml

To find: Molality and Molarity of solution

Formula:

Molality

Molarity, Mo

Density, d

Solution:

Calculation of Molality:

⇒ Molecular Mass of ethylene glycol (C2H6O2) = [12 × 2] + [6 × 1] + [16 × 2]

= 24 + 6 + 32

= 62 g

⇒ Number of moles of ethylene glycol (C2H6O2) = [222.6/62]

= 3.59 moles

⇒ Mass of water = 200 g

⇒ Molality

= 17.95 m

Calculation of Molarity:

⇒ Total mass of solution = [222.6 + 200]

= 422.6 g

From density formula we can find out the volume required.

⇒ Volume of solution, V = [422.6 /1.072]

= 394.216 ml

⇒ Molarity, Mo

⇒ Molarity, Mo

⇒ Molarity = 9.1067

⇒ Molarity ≈ 9.11 M

Therefore the Molality and Molarity of the solution is as follows:

Molality = 17.95 m

Molarity = 9.11 M

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.
ANSWER:
Given:

Level of contamination = 15 ppm [by mass]

To find: Mass Percentage and Molality

Formula:

Molality

Mass Percentage of Solute

Solution:

Calculation of Mass Percentage:

15 ppm means 15 parts of Chloroform in 106 parts of drinking water

⇒ Mass Percentage

= 1.5 × 10-3

Calculation of Molality:

⇒ Molecular Mass of Chloroform, CHCl3 = [12] + [1] + [35.5 × 3]

= 119.5 g

⇒ Number of Moles of Chloroform = [15 / 119.5]

= 0.1255 moles

Molality

= 1.255 × 10-4

Therefore the Mass Percentage is = 1.5 × 10-3 and the Molality of the solution is =
1.255 × 10-4 m.

2.10 What role does the molecular interaction play in a solution of alcohol and
water?

ANSWER:

The lower members of alcohols are completely miscible [highly soluble] with water
but the solubility decreases with increase in the molecular weight. The lower
members of the alcohol group have the capability to form intermolecular hydrogen
bonding with water molecules as alcohols are polar molecules in nature.

Alkyl groups are hydrophobic [prevents formation of hydrogen bonds with water] in
nature. In lower alcohols, the alkyl group is small and the –OH group of alcohol is
effective in making hydrogen bonds with water.

But with the increase in the size of alkyl group, the hydrophobic [water hating]
nature of alkyl group dominates over the hydrophilic [water liking] nature of –OH
group making the molecule less soluble in water. So solubility of alcohols decreases
with increase in its molecular mass.

Since molecular interaction is weaker between higher alcohols and water, as a result,
when alcohol and water are mixed, the intermolecular interactions become
weaker and the molecules can easily get liberated off. This increases the vapour
pressure of the solution, which in turn lowers the boiling point of the resulting
solution.

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

ANSWER:

Whenever a gas is dissolved in a liquid, a small amount heat is liberated in the

process. So dissolving a gas in liquid is overall an exothermic process.

So according to the LeChatelier principle, whenever the temperature is increased for

a reaction which is exothermic in nature, the equilibrium shifts backwards and the
reaction proceeds in backward direction that means the solution gets dissociated
and will give off gas and hence solubility of gas decreases.
So with the increase in temperature, the solubility of the gases in liquids decreases.

2.12 State Henry’s law and mention some important applications. )

ANSWER:

The solubility of a gas in water depends on following three parameters:

1. Nature of gas

2. Temperature

3. Pressure

The solubility decreases with increase in temperature. Temperature and pressure

follow inverse proportionality. So solubility increases with increase with pressure. A
quantitative relation between pressure and solubility of a gas in a solvent was given
by W. Henry [1803]. This relationship is known as Henry’s law.

Statement:

Henry’s law can be expressed as follows.

At constant temperature, the solubility of a gas in a liquid is directly proportional to

the pressure of the gas.

Mathematically,

Solubility ∝ Pressure of the gas

Some of the important applications of Henry’s law are as follows.

[i] Since the solubility of a gas in water increases with pressure, soft drink bottles are
sealed under high pressure to accommodate more CO2 in the soft drink making the
drink fizzier.

[ii] If deep sea divers [scuba divers] use air for respiration, they develop a medical
condition known as bends with involves the blocking of capillaries. This is because air
is mainly a mixture of oxygen and nitrogen. According to Henry’s Law, the solubility
of gases increases with increase in pressure. When diver breathes air under high
pressure in water, nitrogen dissolves in his blood. When the diver comes towards
surface, the pressure gradually decreases. This releases the dissolved gases and leads
to the formation of bubbles in the blood. This is quite painful and dangerous to life.
In order to avoid bends and toxic effects of dissolved nitrogen in blood, the tanks
used by sea divers are filled with air diluted with helium [ 11.7% He + 56.2% N2 +
32.1% O2 ].

[iii] The pressure of oxygen in air decreases in going up the mountains. At very high
altitudes the partial pressure of oxygen in air is much less than that at the ground
level. Therefore, people living at high altitude or climbers have low concentrations of
oxygen in the blood and tissues. This leads to weakness and loss in the clarity of
thinking. These symptoms create a condition known as anoxia.

[iv] Henry’s law is also related to biology as it explains the supply of inhaled oxygen
to tissues. When air is inhaled, it combines with haemoglobin [oxygen carrier of
RBCs] of the blood in lungs to form oxyhaemoglobin because in lungs the partial
pressure of oxygen is high. Partial pressure of oxygen is low in tissues. Hence, oxygen
is released from oxyhaemoglobin and is utilised by the cells to carry out their tasks.

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?

ANSWER:

Given:

Mass of ethane in solution A = 6.56 × 10–3 g

Partial pressure of solution A = 1 bar

Mass of ethane in solution B = 5.00 × 10–2 g

To find: Partial Pressure of gas

Formula:

By Henry’s law:

Mass of dissolved gas M = k × P

Where

k = proportionality constant

P = Partial Pressure

Solution:

⇒ M1 = k × P1 ……………… [1]

⇒ M2 = k × P2 …………….. [2]

Dividing the [2] by [1], we get

P2 = 7.62 bar

Therefore the partial pressure of the gas is 7.62 bar.

2.14 What is meant by positive and negative deviations from Raoult's law and how
is the sign of ∆mixH related to positive and negative deviations from Raoult's law?

ANSWER:

Raoult’s law states that at a given temperature, the vapour pressure of a solution
containing non volatile solute is directly proportional the mole fraction of the
solvent.

Non ideal solutions show positive and negative deviations from ideal behaviour.

Non ideal solutions showing positive deviations from Raoult’s law-

A solution is said to show positive deviation from Raoult’s Law when at any
composition, its vapour pressure is higher than that given by Raoult’s Law.

The positive deviation is shown by those liquid pairs in which the A-B molecular
interaction forces are weaker than the corresponding A-A or B-B molecular
interaction forces. When the A-B molecular interaction forces are weaker, then
molecules of liquid A find it easier to escape as compared to pure solution thereby
increasing the vapour pressure of solution.

As a result, each component of solution has a partial vapour pressure greater than
expected on the basis of Raoult’s law. This is called positive deviations from Raoult’s
law, that is PA>PAoXA and PB>PBoXB

∆mixH [Change in Enthalpy] is positive because energy is required to break A-A & B-B
attractive forces. Hence it is an endothermic process.

Examples of liquid Pairs:

1. Water + methanol

2. Water + ethanol

3. Acetone + benzene

4. Carbon tetrachloride + benzene

The graph of vapour pressure and mole fraction for liquids showing positive
deviation from Raoult’s Law is shown below:

From the diagram it is clear that the composition curve of such a solution lies above
the composition curve obtained on basis of Raoult’s Law

Non ideal solutions showing Negative deviations from Raoult’s law –

When the vapour pressure of the solution is lower than that calculated on the basis
of Raoult’s Law, the solution is said to show negative deviation from Raoult’s Law.
Even the vapour pressure of individual components show negative deviation from
Raoult’s Law

The negative deviation is shown by those liquid pairs in which the A-B molecular
interaction forces are stronger than the corresponding A-A or B-B molecular
interaction forces. When the A-B molecular interaction forces are stronger, then
molecules of liquid A find it easier to escape from pure solution as compared to the
mixture thereby decreasing the vapour pressure of solution.

Consequently, each component of solution has a partial vapour pressure less than
expected on the basis of Raoult’s law. This is called negative deviations from Raoult’s
law, i.e. PA<PAoXA & PBoXB.

Examples of liquid pairs:

1. Water + hydrochloric acid

2. Water + nitric acid

3. Chloroform + benzene

4. Acetone + aniline

∆mixH is negative because energy is released due to increase in attractive

forces. Hence it is an exothermic process.
The graph of vapour pressure and mole fraction for liquids showing negative
deviation from Raoult’s Law is shown below:

2.15 An aqueous solution of 2% non-volatile solute exerts a pressure of 1.004 bar

at the normal boiling point of the solvent. What is the molar mass of the solute?
ANSWER:
Given:

2% non-volatile solute in an aqueous solution means that if the solution is of mass

100 g then the mass of solute in the solution is,

Mass of solute = [2 × 100]/100

=2g

∴ Mass of Solvent = 100-2

= 98 g

Vapour pressure of solution at normal boiling point, P1 = 1.004 bar

Vapour pressure of pure water at normal boiling point, P1° = 1 atm = 1.013 bar

To find: Molar mass of solute

Formula:

From Raoult’s Law, we have,

………….. [1]

Now we know that number of moles of solute is given by the following relationship,

⇒ Number of moles
Using the above relationship the equation [1] can be modified as follows:

Where

W1 = mass of solvent

W2 = mass of solute

M1 = molecular mass of solvent

M2 = molecular mass of solute

Solution:

M2 =

M2 = 41.3469 g

∴ M2 ≈ 41.35 g

Therefore the molar mass of the solute is 41.35 g.

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 g of octane?
ANSWER:
Given: Temperature = 373k

Vapour pressure of pure heptane (p01) = 105.2kpa and that of octane (p02) = 46.8kpa

Mass of heptane = 26 g

Mass of octane = 35 g

Molecular weight of heptane = C7H16 = 12 × 7 + 1 × 16 = 100 gmol-1

Molecular weight of octane = C8H18 = 114 gmol-1

Moles of heptane, n1 = given mass /molecular weight = 26/100

⇒ n1 = 0.26mol

Moles of octane, n2 = given mass /molecular weight = 35/114

⇒ n2 = 0.307mol

∴ Mole fraction of heptane,

⇒ χ1 = 0.456

Now, Mole fraction of octane,

⇒ χ2 = 0.544

∴ Partial pressure of heptane, p1 = χ1 × p01

⇒ p1 = = 0.456 × 105.2 = 47.97kpa

∴ Partial pressure of octane, p1 = χ2 × p02

⇒ p2 = = 0.544 × 46.8 = 25.46 kpa

∴ Total pressure exerted by solution = p1 + p2

= 47.97 + 25.46

= 73.43kpa

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.
ANSWER:
Given: 1 molal solution means 1 mole of solute present in 1000g of water solvent)

Molecular weight of water = H2O = 1 × 2 + 16 = 18g/mol

No. of moles of water, n = given mass /molecular weight

⇒ n = 1000/18 = 55.56 gmol-1

Mole fraction of solute in solution,x2 = moles of solute/(moles of solute + moles of

water)
⇒ x2 = 1/(1 + 55.56)

⇒ x2 = 0.0177

Given vapour pressure of pure water at 300k is 12.3 kpa

Apply the formula:

⇒ P1 = 12.0823kpa

which is the vapour pressure of the solution.

2.18 Calculate the mass of a non-volatile solute (molar mass 40 g mol–1) which
should be dissolved in 114 g octane to reduce its vapour pressure to 80%.
ANSWER:
Given:

Molar mass of non-volatile solute = 40g

Let no. of moles of solute be n.

Mass of octane = 114g

Molar mass of octane(C8H18) = 12 × 8 + 1 × 18 = 114g/mol

Moles of octane = given mass/molar mass

⇒ n = 114/114 moles

⇒ n = 1 mole

Molar fraction of solute,

⇒ x2 = n/n + 1

Let the vapour pressure of original solvent(without solute) be p1⁰

Accordingly after addition of solute vapour pressure of solution reduces to 80% i.e.
0.8 p1⁰ = p1

Applying the formula:

⇒

⇒ n/n + 1 = 0.2

⇒ 0.2n + 0.2 = n

⇒ n = 0.25 moles

Hence, mass of solute is:

moles = given mass/molar mass

⇒ 0.25moles = mass/40g

⇒ mass = 10g.

2.19 A solution containing 30 g of non-volatile solute exactly in 90 g of water has a

vapour pressure of 2.8 kPa at 298 K. Further, 18 g of water is then added to the
solution and the new vapour pressure becomes 2.9 kPa at 298 K. Calculate: (i)
molar mass of the solute (ii) vapour pressure of water at 298 K.
ANSWER:
Given: mass of solute = 30g

Let the molar mass of solute be x g and vapour pressure of pure water at 298k be P1⁰

Mass of water(solvent) = 90g

Molar mass of water = H2O = 1 × 2 + 16 = 18g

Moles of water = mass of water/molar mass

⇒ n = 90/18 moles

⇒ n = 5moles

Molar fraction of solute,

⇒
Vapour pressure of solution (p1) = 2.8kpa

Applying the formula:

⇒ ………………………(1)

According to second condition when we add 18g of water to solution vapour

pressure becomes 2.9kpa

Moles of water = mass/molar mass

⇒ n = 90 + 18/18

⇒ n = 6moles

Molar fraction of solute,

Applying the formula:

⇒ ……………………..(2)
Solving 1 and 2:

Dividing (2) by (1) we get

0.8631(30 + 6x) = 30 + 5x

25.9 + 5.18x = 30 + 5x

0.18x = 4.1

X = 22.78g

Substituting value of x in 1 we get

i. molar mass of the solute = 22.78g

ii. vapour pressure of water at 298 K = 3.537kpa

2.20 A 5% solution (by mass) of cane sugar in water has freezing point of 271K.
Calculate the freezing point of 5% glucose in water if freezing point of pure water is
273.15 K.
ANSWER:
5% solution means 5g of cane sugar is present in 100g of solution

Freezing point of solution = 271k

Freezing point of pure water = 273.15k

Molar mass of cane sugar(C12H22O11) = 12 × 12 + 1 × 22 + 16 × 11 = 342g

Moles of cane sugar = mass/molar mass = 5/342

⇒ n = 0.0146mol

Molality of solution = moles of solute/mass of solvent(in kg)

⇒ M = 0.0146/0.095

⇒ Molality = 0.154M

Depression in freezing point = ΔTf = 273.15-271 = 2.15k

Applying the formula: ΔTf = Kf × M

Where

ΔTf = depression in freezing point

Kf = molal depression constant

M = molality of solution

⇒ Kf = 2.15/0.154

⇒ Kf = 13.96k kg mol-1

Second condition: mass of glucose = 5g

Molar mass of glucose(C6H12O6) = 12 × 6 + 1 × 12 + 16 × 6 = 180g

Moles of glucose = mass/molar mass

⇒ n = 5/180moles

⇒ n = 0.0278mol

Molality of solution = moles of solute/mass of solvent(in kg)

⇒ molality = 0.0278/0.095

⇒ M = 0.2926M

Applying the formula: ΔTf = Kf × M

Where
ΔTf = depression in freezing point

Kf = molal depression constant

M = molality of solution

⇒ ΔTf = 13.96 × 0.2926

⇒ ΔTf = 4.08k

Freezing point of solution = 273.15 + 4.08 = 277.234k

2.21 Two elements A and B form compounds having formula AB2 and AB4 . When
dissolved in 20 g 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.
ANSWER:
let the molar masses of AB2 and AB4 be x and y respectively.

Molar mass of benzene(C6H6) = 12 × 6 + 1 × 6 = 78 g/mol

Moles of benzene = mass/molar mass = 20/78

n = 0.256mol

⇒ ΔTf = 2.3 K

Kf = 5.1K kg mol-1

For AB2

Applying the formula: ΔTf = Kf × M

Where

ΔTf = depression in freezing point

Kf = molal depression constant

M = molality of solution

⇒ 2.3 = 5.1 × M1

⇒ M1 = 0.451mol/kg

For AB4

Applying the formula: ΔTf = Kf × M

Where
ΔTf = depression in freezing point

Kf = molal depression constant

M = molality of solution

⇒ 1.3 = 5.1 × M2

⇒ M2 = 0.255mol/kg

M1 = moles of solute/mass of solvent(in kg)

⇒ X = 110.86g

M2 = moles of solute/mass of solvent(in kg)

⇒ y = 196.1g

atomic mass of A be a and that of B be b g respectively.

So, AB2 : a + 2b = 110.86

AB4 : a + 4b = 196.1

⇒ a = 25.59g

⇒ b = 42.64g

2.22 At 300 K, 36 g of glucose present in a litre of its solution has an osmotic

pressure of 4.98 bar. If the osmotic pressure of the solution is 1.52 bars at the
same temperature, what would be its concentration?
ANSWER:
Here,

T = 300 K

π = 1.52 bar

R = 0.083 bar L

Applying the relation, π = CRT

Where
π = osmotic pressure of solution

C = concentration of solution

R = universal gas constant

T = temperature

⇒ C = 0.061mol/L

Concentration of the solution is 0.061mol/L

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) NaClO4 and water
(iv) methanol and acetone (v) acetonitrile (CH3CN) and acetone (C3H6O)
ANSWER:
(i) Both the compounds are non-polar and they do not attract each other because
they do not form any polar ions. Vanderwaals forces of attraction will be dominant in
between them as vanderwaals forces of attraction are not a result of any chemical or
electronic bond.

(ii) now here both the compounds are non-polar because in I2 both the atoms are
same so they have same electronegativity and hence there will be no displacement
of electron cloud, it will be in the centre. In case of CCl4 molecule, it has tetrahedral
shape so two Cl atoms will cancel the attraction effect from two opposite Cl atoms,
hence molecule as a whole is non polar. Therefore they will also have vanderwaals
forces of attraction.

(iii) NaClO4 is ionic in nature as Na, Cl and O all have different electronegativity and
their shape is also not symmetric. So molecular will be ionic in nature and we know
that water is polar because O will attract the electron cloud towards it(more
electronegative) hence there will be formation of dipole(two oppositely charged ions
separated by a short distance). Therefore there will be ion-dipole interaction
between them.

(iv) methanol and acetone are both polar molecules because of the presence of
electron withdrawing O atom in methanol and ketone group in acetone. So they will
have dipole-dipole interaction.

(v) acetonitrile is polar compound due to presence of electronegative N atom and

acetone due to ketone group. So, dipole-dipole interaction.

2.24 Based on solute-solvent interactions, arrange the following in order of

increasing solubility in n-octane and explain. Cyclohexane, KCl, CH3OH, CH3CN.
ANSWER:
Now n-octane is non-polar solvent due to long chain saturated structure. We know
that “like dissolves like” so a non-polar compound will be more soluble in non-polar
solvent as compared to polar compound.

So cyclohexane is non-polar due to symmetric structure. KCl is ionic in nature as it

will dissociate into K + and Cl- ions. CH3CN is polar as mentioned above and CH3OH is
also polar in nature.

The order of increasing polarity is:

Cyclohexane < CH3CN < CH3OH < KCl (O is more electronegative than N)

Therefore, the order of increasing solubility is:

KCl < CH3OH < CH3CN < 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.
ANSWER:
Water is a polar compound (due to electronegativity difference between O and H) .
We know that “like dissolves like”. So, a non-polar compound will be more soluble in
non-polar solvent as compared to polar compound.

(i) Phenol has the polar group -OH and non-polar group –C6H5 and it can not form H
bonding with water(presence of bulky non-polar group) . Thus, phenol is partially
soluble in water.

(ii) Toluene has no polar groups. Thus, toluene is insoluble in water.

(iii) Formic acid (HCOOH) has the polar group -OH and can form H-bond with water.
Thus, formic acid is highly soluble in water.

(iv) Ethylene glycol(OH-CH2-CH2-OH) has polar -OH group and can form H-bond with
water. Thus, it is highly soluble in water.

(v) Chloroform is partly soluble as CHCl3 is polar in nature due to high

electronegativity of Cl atoms, there will be production of partial + charge on H atom
so it can form H bonding with water but it is also surrounded by 3 Cl atoms, so partly
soluble.

(vi) Pentanol(C5H11OH) has polar -OH group, but it also contains a very bulky non-
polar group –C5H11. Thus, pentanol is partially soluble in water.

2.26 If the density of some lake water is 1.25g mL–1 and contains 92 g of Na+ ions
per kg of water, calculate the molarity of Na+ ions in the lake.
ANSWER:
Mass of ions = 92g

Molar mass of ions = Na+ = 23g(neglect the mass lost due to absence of a electron)
Moles of ions = mass of ions/molar mass

⇒ n = 92/23 moles

⇒ n = 4moles

Molality of solution = moles of solute/mass of solvent(in kg)

Molality = 4/1 = 4M

2.27 If the solubility product of CuS is 6 × 10–16, calculate the maximum molarity of
CuS in aqueous solution.
ANSWER:
The Solubility product of CuS (ksp) = 6 × 10-16

CuS → Cu + + + S2-

Let the s be solubility of CuS in mol/L

Ksp = [ Cu + + ][S2]

Ksp = solubility product

6 × 10-16 = s × s = s2

⇒ S = 2.45 × 10-8 mol/L

Hence, the maximum molarity of CuS in an aqueous solution is 2.45 × 10-8 mol/L

2.28 Calculate the mass percentage of aspirin (C9H8O4 ) in acetonitrile (CH3CN)

when 6.5 g of C9H8O4 is dissolved in 450 g of CH3CN.
ANSWER:
Total mass of solution = 6.5g + 450g = 456.5g

Therefore mass percentage of aspirin in solution = (mass of aspirine/total mass of

solution) = 6.5/456.5

⇒ mass % of aspirine = 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 × 10–3 m aqueous solution required for the above dose.
ANSWER:
molar mass of Nalorphene = 311g/mol

Now 1000g of solution contains 1.5 × 10-3 moles of Nalorphene(Molality of solution =

moles of solute/mass of solvent (in kg)

⇒ 1.5 × 10-3 moles of Nalorphene = 1.5 × 10-3 × 311 = 0.4665g of Nalorphene

Therefore, total mass of the solution = (1000 + 0.4665) g

⇒ total mass = 1000.4665 g

This implies that the mass of the solution containing 0.4665 g of nalorphene is
1000.4665 g.

Therefore, mass of the solution containing 1.5 mg of nalorphene is:

⇒ mass of solution containing required ions = 3.22 g

Hence, the mass of aqueous solution required is 3.22 g.

2.30 Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250
mL of 0.15 M solution in methanol.
ANSWER:
Volume of the solution = 250mL = 0.25L

Let the no. Of moles of solute be n

Molarity = No. of moles of solute/volume of solution

⇒ 0.15 = n/0.25

⇒ n = 0.0375moles

Molar mass of C6H5OH = 6×12 + 5×1 + 16 + 1 = 94g

Moles = mass/molar mass

⇒ 0.0375 = m/94

Mass of benzoic acid required = 3.525g.

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.
ANSWER:
The depression in freezing point of water observed for the same amount of acetic
acid, trichloroacetic acid and trifluoroacetic acid increases in the pattern,

Acetic acid< trichloroacetic acid< trifluoroacetic acid.

This is because fluorine is more electronegative than chlorine. So, trifluoracetic acid
is a stronger acid in comparison to trichloroacetic acid and acetic acid. And also,
acetic acid is the weakest of all.
Explanation: Stronger acid produces more number of ions, therefore it has more
ΔTf(depression in freezing point), hence lower freezing point. As the acidic strength
increases, the acid gets more and more ionised.

Trifluoracetic acid ionizes to the largest extent. Hence, in this case, trifluoracetic acid
being the strongest acid produces more number of ions(extent of ionisation and
concentration of ions are more), high ΔTf(depression in freezing point)and lower
freezing point and vice versa.

2.32 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 .
ANSWER:
Given: Mass of CH3CH2CHClCOOH = 10 g

Mass of water = 250g

Ka = 1.4 × 10–3,

Kf = 1.86 K kg mol–1

Molar mass of CH3CH2CHClCOOH = 12 + 3 + 12 + 2 + 12 + 1 + 35.5 + 2 + 16 + 16 + 1

= 122.5 g mol–1

Number of moles of solute =

→ No. of moles =

∴ No. of moles = mol

Now, Molality is given as,

M = 0.3264 kg/mol

CH3CH2CHClCOOH CH3CH2CHClCOO- + H +
Initial moles 1 0 0

Equilibrium moles α α
(1-α)

Total moles at equilibrium = (1-α) + 2 α

=1+α

In order to find out the depression in freezing point, f f values of i(vant

Hoff’s factor) and α(degree of dissociation) are to be found out.

To find out degree of dissociation, α

Here, the value of α is negligible as compared to 1, and hence 1- = 1, giving,

To find out Vant Hoff’s factor,

∴
Now, to find out the depression in freezing point,

f f

Thus, the depression in freezing point is f = 0.650C

2.33 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.
ANSWER:
Given- w1 = 500g

W2 = 19.5g

Kf = 1.86 K kg mol-1

Molar mass of CH2FCOOH = 12 + 2 + 19 + 12 + 16 + 16 + 1

= 78 g mol-1

The depression in freezing point is calculated by,

→ f f (where, m is the molality)

∴ f (calculated) = 0.93

To find out the vant Hoff’s factor, we use the formula,

→
∴

CH2FCOOH → CH2FCOO- + H +

To find out the degree of dissociation α, we use

With degree of dissociation, known to us, we can easily calculate the dissociation
constant, Ka using the formula,

Thus, the vant Hoff’s factor is 1.07 an the dissociation constant is 2.634x10-3

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.
ANSWER:
Given- Vapour pressure of water, = 17.535 mm Hg

= 25 g of glucose

= 450g of water

Molar mass of water, H2O = 1 + 1 + 16 = 18 g mol-1

Molar mass of glucose, C6H12O6 = (12×6) + (1×12) + (16×6) = 180 g mol-1

Using Raoult’s law for solution of non-volatile solute,

→ Equation 1

where is the mole fraction of the solute

Substituting the value of in equation 1, we get,

Thus, the vapour pressure of water at 293 K at the given conditions is 17.437 mm Hg

2.35 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.
ANSWER:
Given-

Henry’s law constant KH = 4.27X 105 mm Hg,

p = 760mm Hg,

Using Henry’s law,

∴
Using the formula of lowering vapour pressure,

→ Equation 1

Since, <<< , the Equation 1 is rewritten as,

where and = molarity of benzene

Thus, the solubility of methane in benzene is 0.023 moles

2.36 100 g of liquid A (molar mass 140 g mol–1) was dissolved in 1000 g of liquid B
(molar mass 180 g 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.
ANSWER:
Given-

Mass of liquid A, WA = 100g, Molar mass, MA = 140 g mol-1

Mass of liquid B, WB = 1000 g, Molar mass, MB = 180 g mol-1

Using the formula below calculate the no. of moles in liquid A and B.

Number of moles of liquid A, MA = 100/140 = 0.714 mol-1

Number of moles of liquid B, MB = 1000/ 180 = 5.556 mol-1

Using the formula,

 ,

we calculate the mole fraction of liquids A and B.

→ Mole fraction of A,

→ Mole fraction of B,

Vapour pressure of pure liquid B, PoB = 500 torr (given)

According to Henry`s law,

Having given the total vapour pressure of the solution, Ptotal = 475 torr,

Using Henry`s law again to get the vapour pressure of pure liquid A,

Thus, the vapour pressure of pure liquid A = 280.7 torr and

vapour pressure of liquid A in the solution = 32 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, pchloroform, and pacetone as a function of xacetone.
The experimental data observed for different compositions of mixture is:

100 xacetone 0 3.4.8 23.4 36.0 50.8 58.2 64.5 72.1

pacetone /mm 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1

Hg

pchloroform /mm 632.8 548.1 469.4 359.7 257.7 193.6 161.2 120.7
Hg

Plot this data also on the same graph paper. Indicate whether it has positive
deviation or negative deviation from the ideal solution.
ANSWER:
The Ptotal for the values given in the graph is found out and plotted in the graph.

ptotal(mm 632.8 603.0 579.5 562.1 580.4 599.5 615.3 641.8

Hg)
It can be observed from the graph that the plot for the p total 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 80 g of benzene is mixed with 100 g of toluene.
ANSWER:
Given-

of benzene = 50.71 mm Hg

of naphthalene = 32.06 mm Hg

Using the formula of lowering vapour pressure to calculate mole fraction of benzene
and naphthalene in solution,
Thus,

Using formula for vapour pressure,

Mole fraction of benzene in vapour phase is calculated by,

Thus, mole fraction of benzene in vapour phase is 0.6744

2.39 The air is a mixture of a number of gases. The major components are oxygen
and nitrogen with 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 the Henry’s
law constants for oxygen and nitrogen at 298 K are 3.30 × 107 mm and 6.51 × 107
mm respectively, calculate the composition of these gases in water.
ANSWER:
Given-

KH for O2 = 3.30 × 107 mm Hg,

KH for N2 = 6.51 × 107 mm Hg

Percentage of oxygen (O2) = 20 %

Percentage of nitrogen (N2) = 79%

Total pressure = 10 atm

Using Henry’s law,

→

where, p is the partial pressure of gas in the solution and KH is Henry’s constant.

Now, to determine the mole fraction of oxygen in solution, , we use

To determine the mole fraction of nitrogen in solution, ,

Thus, the mole fraction of oxygen in solution, xoxy = 4.61x10-5

and the mole fraction of nitrogen in solution, xnit is 9.22x10-5

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.
ANSWER:
Given-

Vant Hoff’s factor, i = 2.47

osmotic pressure, = 0.75 atm

Volume of solution = 2.5L.

To determine the amount of CaCl2, we use vant Hoff’s equation for dilute solutions,
given as,

where, n is the number of moles of solute, R is solution constant which is equal

to the gas constant and T is the absolute temperature.

where, the molecular mass of CaCl2 is 111, t = 300 K (270C + 273 K) and R = 0.082,

Hence, the amount of CaCl2 dissolved is 3.425g

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.

ANSWER:

Given-

Mass of K2SO4, w = 25 mg = g,

Molar mass of K2SO4 = (39×2) + (32×1) + (16×4) = 174 g mol-1

Volume V = 2 liter

T = 250C + 273 = 298 K (add 273 to convert in Kelvin)

The reaction of dissociation of K2SO4 is written as,

K2SO4 → 2K + + SO42-

Number if ions produced = 2 + 1 = 3, hence vant Hoff’s factor, i = 3

Here, we use vant Hoff’s equation for dilute solutions, given as,

where, n is the number of moles of solute, R is solution constant which is equal to

the gas constant(0.082) and T is the absolute temperature (298 K).
Hence, the osmotic pressure of a solution is 5.27x10-3atm