Class XII

Chapter 2 : Solutions

Solution is a homogeneous mixture of two or more substances in same or different physical

phases. The substances forming the solution are called components of the solution. On the basis
of number of components a solution of two components is called binary 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.]

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 of 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

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 A and
nB respectively, the mole fraction of A will be

(iv) Parts per million (ppm)

It is defined as the parts of a component per million parts (106) of the solution. It is widely used
when a solute is present in trace quantities.
ppm = number of parts of the component / total number of parts of all the components × 106 (v)
Molarity (M) It is the number of moles of solute present in 1L(dm 3) of the solution.
M = number of moles of solute / volume of solution (L)
M = mass of solute (in gram) × 1000 / mol. wt. of solute × volume of solution (in mL)
Molarity varies with temperature due to change in volume of solution.
(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.
[When solvent used is water, a molar (1 M) solution is more concentrated than a molal (1 M)
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

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 = KH . x
Greater the value of KH, higher the solubility of the gas. The value of KH decreases with increase
in the temperature. Thus, aquatic species are more comfortable in cold water [more dissolved O 2]
rather than warm water.

Applications

1. In manufacture of soft drinks and soda water, CO2 is passed at high pressure to increase its
solubility.
2. To minimise the painful effects (bends) the tanks used by sea divers are filled with air diluted
with He gas as it is less soluble in blood.
3. At high altitudes, the partial pressure of O2 is less than that at the ground level. This leads to
low concentrations of O2 in the blood of climbers which causes ‘anoxia’.

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 χA= 1 then k = P°A,
the vapour pressure of pure liquid, hence
The composition of vapour phase in equilibrium with the solution is determined by the partial
pressure of components. If Y1 and Y2 are the component 1 and 2 respectively in the vapour phase
then, using Dalton’s law of partial pressure,
p1 = y1 × Ptotal
p2 = y2 × Ptotal

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,
ΔHmix ≠ 0
ΔVmix ≠ 0
(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 nonideal
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., C2H5OH (95.57%) +
H2O (4.43%)(by 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., H2O(20.22O%)+ HCl
(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 non-volatile 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, WB and WA = mass of Solute and solvent respectively. MB and MA = molecular
weight of solute and solvent respectively.

Elevation in Boiling Point (ΔTb)

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, its 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
ΔTb = Tb – T°b ΔTb = Kb m (where; m = molality)
Kb is molal elevation constant or ebullioscopic constant. Molecular mass of solute can be
calculated as

where, WB and WA = mass of solute and solvent respectively.

Kb has units of K / m or K kg mol-1, for water, Kb = 0.52 K kg mol-1

Depression in Freezing Point (ΔTf)

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 (ΔTf) = T°f – Tf
To find molecular mass of solute,

where, Kf is molal depression constant or cryoscopic constant.

Kf has units of K / m or K kg mol-1.
Ethylene glycol is usually added to water in the radiator to lower its freezing point. It is called
antifreeze solution.
[Common salt (NaCl) and anhydrous CaCl2 are used to clear snow on the roads because they
depress the freezing point of water.
Calculations of molal elevation constant (Kb) and molal depression constant (Kf)

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.
Some natural semipermeable membranes are animal bladder, cell membrane etc.
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, MB = molar mass of solute
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, 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 / MB
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 KCl 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 An and α is the degree of association then

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

Also refer to the link below:-

https://www.youtube.com/watch?v=1VElCP7_GFI&feature=youtu.be
 SOLUTIONS

Numericals

Question 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) Molar mass of KI = 39 + 127 = 166 g mol −1

20% (mass/mass) aqueous solution of KI means 20 g of KI is present in 100 g of solution.
That is,
20 g of KI is present in (100 − 20) g of water = 80 g of water

Therefore, molality of the solution

= 1.506 m
= 1.51 m (approximately)
(b) It is given that the density of the solution = 1.202 g mL−1

Volume of 100 g solution

= 83.19 mL
= 83.19 × 10−3 L

Therefore, molarity of the solution

= 1.45 M

(c) Moles of KI

Moles of water

fraction of KI
Therefore, mole

= 0.0263
 Question 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
It is given that the solubility of H2S in water at STP is 0.195 m, i.e., 0.195 mol of H2S is
dissolved in 1000 g of water.

Moles of water
= 55.56 mol

Mole fraction of H2S, x

= 0.0035
At STP, pressure (p) = 0.987 bar
According to Henry’s law: p =
KHx

= 282 bar
Question 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
It is given that:

= 450 mm of Hg

= 700 mm of Hg
ptotal = 600 mm of Hg
From Raoult’s law, we have:

Therefore, total pressure,

 Therefore,

= 1 − 0.4

= 0.6

Now,
= 450 × 0.4 = 180 mm of Hg

= 700 × 0.6

= 420 mm of Hg Now, in the vapour phase: Mole fraction of liquid A

= 0.30
And, mole fraction of liquid B = 1 − 0.30
= 0.70

Question 2.9:
Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50 g of urea (NH 2CONH2) is
dissolved in 850 g of water. Calculate the vapour pressure of water for this solution and
its relative lowering.
 Answer

It is given that vapour pressure of water, = 23.8 mm of Hg

Weight of water taken, w1 = 850 g
Weight of urea taken, w2 = 50 g

Molecular weight of water, M1 = 18 g mol−1

Molecular weight of urea, M2 = 60 g mol−1

Now, we have to calculate vapour pressure of water in the solution. We take vapour
pressure as p1.
Now, from Raoult’s law, we have:

Hence, the vapour pressure of water in the given solution is 23.4 mm of Hg and its relative
lowering is 0.0173.
Question 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. Molal elevation constant for water is 0.52 K kg mol −1.

Answer

Here, elevation of boiling point ∆Tb = (100 + 273) − (99.63 + 273)

= 0.37 K
Mass of water, wl = 500 g
Molar mass of sucrose (C12H22O11), M2 = 11 × 12 + 22 × 1 + 11 × 16
= 342 g mol−1

Molal elevation constant, Kb = 0.52 K kg mol−1 We

know that:

= 121.67 g (approximately)
Hence, 121.67 g of sucrose is to be added.
Question 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.
Answer
It is given that:
Volume of water, V = 450 mL = 0.45 L
Temperature, T = (37 + 273)K = 310 K

Number of moles of the polymer,

We know that:

Osmotic pressure,

= 30.98 Pa
= 31 Pa (approximately)
Question 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
Here,
Vapour pressure of the solution at normal boiling point (p1) = 1.004 bar

Vapour pressure of pure water at normal boiling point

Mass of solute, (w2) = 2 g
Mass of solvent (water), (w1) = 98 g

Molar mass of solvent (water), (M1) = 18 g mol−1 According

to Raoult’s law,

= 41.35 g mol−1

Hence, the molar mass of the solute is 41.35 g mol −1.

 Question 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

Let the vapour pressure of pure octane be

Then, the vapour pressure of the octane after dissolving the non-volatile solute is

Molar mass of solute, M2 = 40 g mol−1

Mass of octane, w1 = 114 g

Molar mass of octane, (C8H18), M1 = 8 × 12 + 18 × 1
= 114 g mol−1

Applying the relation,

Hence, the required mass of the solute is 8 g.

Question 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
(i) Let, the molar mass of the solute be M g mol −1

Now, the no. of moles of

solvent (water),

And, the no. of moles of solute,

Applying the relation:

After the addition of 18 g of water:
Again, applying the relation:

Dividing equation (i) by (ii), we have:

Therefore, the molar mass of the solute is 23 g mol −1.

(ii) Putting the value of ‘M’ in equation (i), we have:

Hence, the vapour pressure of water at 298 K is 3.53 kPa.

Question 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.
Answer
Here, ∆Tf = (273.15 − 271) K
= 2.15 K
Molar mass of sugar (C12H22O11) = 12 × 12 + 22 × 1 + 11 × 16
= 342 g mol−1
5% solution (by mass) of cane sugar in water means 5 g of cane sugar is present in (100
− 5)g = 95 g of water.

Now, number of moles of cane sugar

= 0.0146 mol

Therefore, molality of the solution,

= 0.1537 mol kg−1
Applying the relation,
∆Tf = Kf × m

= 13.99 K kg mol−1

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

180 g mol−1

5% glucose in water means 5 g of glucose is present in (100 − 5) g = 95 g of water.

Number of moles of glucose

= 0.0278 mol

Therefore, molality of the solution,

= 0.2926 mol kg−1

Applying the relation,

∆Tf = Kf × m
= 13.99 K kg mol−1 × 0.2926 mol kg−1

= 4.09 K (approximately)
Hence, the freezing point of 5% glucose solution is (273.15 − 4.09) K= 269.06 K.
Question 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 Kwhereas 1.0 g of AB4
lowers it by 1.3 K. The molar depression constant for benzene is 5.1 Kkg mol −1.

Calculate atomic masses of A and B.

Answer
We know that,

Then,
= 110.87 g mol−1

= 196.15 g mol−1

Now, we have the molar masses of AB 2 and AB4 as 110.87 g mol−1 and 196.15 g mol−1

respectively.

Let the atomic masses of A and B be x and y respectively.

Now, we can write:

Subtracting equation (i) from (ii), we have

2y = 85.28
⇒ y = 42.64
Putting the value of ‘y’ in equation (1), we have x
+ 2 × 42.64 = 110.87
⇒ x = 25.59
Hence, the atomic masses of A and B are 25.59 u and 42.64 u respectively.
Question 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 K−1 mol−1
Applying the relation, π =
CRT

= 0.061 mol
Since the volume of the solution is 1 L, the concentration of the solution would be 0.061
M.
 Question 2.30:
Calculate the amount of benzoic acid (C6H5COOH) required for preparing 250 mL of 0.15
M solution in methanol.
Answer
0.15 M solution of benzoic acid in methanol means,
1000 mL of solution contains 0.15 mol of benzoic acid

Therefore, 250 mL of solution contains =

mol of benzoic acid

= 0.0375 mol of benzoic acid

Molar mass of benzoic acid (C6H5COOH) = 7 × 12 + 6 × 1 + 2 × 16
= 122 g mol−1

Hence, required benzoic acid = 0.0375 mol × 122 g mol −1

= 4.575 g

Question 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

Among H, Cl, and F, H is least electronegative while F is most electronegative. Then, F can
withdraw electrons towards itself more than Cl and H. Thus, trifluoroacetic acid can easily
lose H+ ions i.e., trifluoroacetic acid ionizes to the largest extent. Now, the more ions
produced, the greater is the depression of the freezing point. Hence, the depression in the
freezing point increases in the order:
Acetic acid < trichloroacetic acid < trifluoroacetic acid
 Question 2.32:
Calculate the depression in the freezing point of water when 10 g of CH 3CH2CHClCOOH is
added to 250 g of water. Ka = 1.4 × 10−3, Kf = 1.86 K kg mol−1.

Answer

Molar mass of

No. of moles present in 10 g of

It is given that 10 g of is added to 250 g of water.

Molality of the solution,

undergoes dissociation according to the following equation:

Since α is very small with respect to 1, 1 − α ≈ 1

Now,
 Again,

Total moles of equilibrium = 1 − α + α + α

=1+α

Hence, the depression in the freezing point of water is given as:

 Question 2.33:
19.5 g of CH2FCOOH is dissolved in 500 g of water. The depression in the freezing point of
water observed is 1.0°C. Calculate the van’t Hoff factor and dissociation constant of
fluoroacetic acid.
Answer
It is given that:

We know that:

Therefore, observed molar mass of

The calculated molar mass of

Therefore, van’t Hoff factor, is:

Let α be the degree of dissociation of

Now, the value of Ka is given as:

 Taking the volume of the solution as 500 mL, we have the concentration:

Therefore,

Question 2.34:
Vapour pressure of water at 293 K is 17.535 mm Hg. Calculate the vapour pressure
of water at 293 Kwhen 25 g of glucose is dissolved in 450 g of water.
Answer

Vapour pressure of water, = 17.535 mm of Hg

Mass of glucose, w2 = 25 g
Mass of water, w1 = 450 g
We know that,
Molar mass of glucose (C6H12O6), M2 = 6 × 12 + 12 × 1 + 6 × 16 =
180 g mol−1

Molar mass of water, M1 = 18 g mol−1

Then, number of moles of glucose,

= 0.139 mol

And, number of moles of water,

= 25 mol
We know that,

⇒ 17.535 − p1 = 0.097
⇒ p1 = 17.44 mm of Hg
Hence, the vapour pressure of water is 17.44 mm of Hg.

Question 2.35:
Henry’s law constant for the molality of methane in benzene at 298 Kis 4.27 × 10 5 mm
Hg. Calculate the solubility of methane in benzene at 298 Kunder 760 mm Hg.
Answer Here, p = 760
mm Hg kH = 4.27 × 105
mm Hg According to
Henry’s law,
p = kHx

= 177.99 × 10−5

= 178 × 10−5 (approximately)

Hence, the mole fraction of methane in benzene is 178 × 10 −5.
Question 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

Number of moles of liquid A,

= 0.714 mol

Number of moles of liquid B,

= 5.556 mol

Then, mole fraction of A,

= 0.114
And, mole fraction of B, xB = 1 − 0.114
= 0.886

Vapour pressure of pure liquid B, = 500 torr

Therefore, vapour pressure of liquid B in the solution,

= 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,
= 280.7 torr
Hence, the vapour pressure of pure liquid A is 280.7 torr.

Question 2.37:
Vapour pressure 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 11.8 23.4 36.0 50.8 58.2 64.5 72.1

pacetone /mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1

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

Answer
From the question, we have the following data

100 ×xacetone 0 11.8 23.4 36.0 50.8 58.2 64.5 72.1

pacetone /mm Hg 0 54.9 110.1 202.4 322.7 405.9 454.1 521.1

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

ptota(mm Hg) 632.8 603.0 579.5 562.1 580.4 599.5 615.3 641.8
 It can be observed from the graph that the plot for the ptotal of the solution curves
downwards. Therefore, the solution shows negative deviation from the ideal behaviour.

Question 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 Kif the
Henry’s law constants for oxygen and nitrogen are 3.30 × 107 mm and 6.51 × 107 mm

respectively, calculate the composition of these gases in water.

Answer
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 Hg = 7600 mm Hg
Therefore,
 Partial pressure of oxygen,
= 1520 mm Hg

Partial pressure of nitrogen,

= 6004 mmHg
Now, according to Henry’s law:
p = KH.x
For oxygen:

For nitrogen:

Hence, the mole fractions of oxygen and nitrogen in water are 4.61 ×10 −5and 9.22 × 10−5

respectively.
 Question 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
We know that,

Here,
R = 0.0821 L atm K-1mol-1

M = 1 × 40 + 2 × 35.5
= 111g mol-1

Therefore, w

= 3.42 g
Hence, the required amount of CaCl 2 is 3.42 g.
 Question 2.41:
Determine the osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2
liter of water at 25° C, assuming that it is completely dissociated.
Answer

When K2SO4 is dissolved in water, ions are produced.

Total number of ions produced = 3

i =3 Given, w = 25 mg = 0.025

g
V=2L
T = 250C = (25 + 273) K = 298 K Also,
we know that:

R = 0.0821 L atm K-1mol-1

M = (2 × 39) + (1 × 32) + (4 × 16) = 174 g mol -1

Appling the following relation,