Chapter

SOLUTION
9
9.0.0 CONCEPT OF A SOLUTION
Every sample of matter with uniform properties and a fixed composition is called a phase. For
example, water at room temperature and normal pressure exists as a single liquid phase, that is, all the
properties of water are uniform throughout this liquid phase. If a small amount of sugar is added to this sample
of water, the sugar dissolves but the sample remains as a single liquid phase. However, the properties and
composition of this new liquid phase, now the sugar solution, are different from those of pure water. As this
solution of sugar in water is containing two substances (binary solution), so it is a mixture and since its
properties are uniform, therefore, it is homogeneous in character.
A solution, on average, is a homogeneous mixture of two or more kinds of different molecular or
ionic substances.
The substance which is present in large quantity is called a solvent and the other component in small
quantity is called a solute. For a given solution, the amount of solute dissolved in a unit volume of solution (or a
unit amount of solvent) is termed as the concentration of the solution. Solutions containing relatively lower
concentrations of solute are called dilute solutions, whereas those containing relatively higher concentrations of
solutes are called concentrated solutions.
9.1.0 CONCENTRATION UNITS OF SOLUTIONS (L.Q)
There are various types of concentration units of solutions. They are discussed as follows.
9.1.1 Percentage composition
The amounts of solute and solvent can be expressed in percentage composition by four different ways.
a. Percentage weight/weight b. Percentage weight/volume
c. Percentage volume/weight d. Percentage volume/volume
S.Q1 What do you mean by percentage w/w composition of a solution? (MLT-2008, BHR-2015)
(a) Percentage weight / weight (S.Q)
It is the weight of a solute dissolved per 100 parts by weight of solution. 5% w/w sugar solution will
contain 5 g of sugar dissolved in 100 g of solution in water. This solution contains 95 g of water.
% by weight =
Example (1):
Calculate the percentage by weight of NaCl, if 2.0g of NaCl is dissolved in 20 g of water.
Solution:
Weight of NaCl = 2.0g
Weight of solvent = 20.0 g
Weight of solution = 20 + 2 = 22 g
% of NaCl by weight =  100
(b) Percentage Weight / Volume
It is the weight of a solute dissolved per 100 parts by volume of solution. 10 g of glucose dissolved
in 100 cm3 of solution is 10% w/v solution of glucose. The quantity of the solvent is not exactly known. In such
solutions, the total volume of the solution is under consideration.
(c) Percentage Volume / Weight
396 Chapter # 9 (Solution)
It is the number of cm3 of a solute dissolved per 100 g of the solution. If we dissolve 10 cm3 of
alcohol in water and the total weight of the solution is 100 g, then it is 10 % v/w solution of alcohol in water. In
such type of solutions, we don't know the total volume of the solution.
d. Percentage Volume / Volume
It is the volume of a solute dissolved per 100 cm 3 of the solution. This unit of concentration is best
applicable to the solutions of liquids in liquids, a 12 % alcohol beverage is 12 cm 3 of alcohol per 100 cm3 of
solution. In such solutions, the total volume of the solution may not be necessarily equal to the sum of volumes
of solute and the solvent.
S.Q2 Define molarity. Give examples? (MLT-2010, 2015, 2016, 2017, GUJ-2017, RWP-2015, 2017, SRG-
2015, FSD-2015, LHR-2016)
9.1.2 Molarity (symbol, M)
Molarity is the number of moles of solute dissolved per dm 3 of the solution. To prepare one molar
solution of glucose in water, we take 180 g of glucose and add sufficient water to make the total volume 1 dm 3
(1 litre) in a measuring flask.
In case of one molar solution of sucrose, 342 g of sucrose are dissolved in water to make it 1 dm 3. Since
the volume of 342 g of sucrose is greater than 180 g of glucose so the volume of water in 1 molar sucrose
solution is less than that of 1 molar glucose solution. Anyhow, to calculate the volume of the solvent, we need
to know the density of the solute. Following formula is used to prepare the solution of any molarity.
Molarity (M) = 
Or Molarity (M) =
Examples (2):
Calculate the molarity of a solution containing 20.7 g of K2CO3 dissolved in 500 cm3 of the given solution.
Solution:
Mass of K2CO3 = 20.7 g
Molar mass of K2CO3 = 138 gmol–1
Volume of solution = 500 cm3 = 0.5 dm3
Formula: Molarity = 
Molarity = 
= Answer
S.Q3 What is molality? Give its formula? (FSD-2009, 2015, 2016, LHR-2013, 2014, MLT-2016, D.G.K-
2017, RWP-2017, AZK-2017)
9.1.3 Molality (symbol, m)
Molality is the number of moles of solute in 1000 g (1 kg) of the solvent. In order to prepare molal
solutions, we don't have to take any flask. 180 g of glucose when dissolved in 1000 g of water gives one molal
solution of glucose. The total mass of the solution is 1180 g. We don't know the volume of the solution. In
order to know the volume we need the density of the solution. For one molal sucrose solution, 342 g of sucrose
are dissolved in 1000 g of H2O.
So, one molal solution of different solutes in water have their own masses and volumes. In order to get
the molality of any solution, we use the following equation.
Molality (m) = 
or Molality (m) =
Example (3):
What is the molality of a solution prepared by dissolving 5g of toluene (C7H8) in 250g of benzene.
Solution: Mass of toluene = 5 g
Mass of benzene = 250g = 0.25 kg
Professor CHEMISTRY - XI (Subjective) 397
Molar mass of toluene = 12  7+1  8 = 92
Formula used
Molality (m) = 
Molality (m) = 
= mole kg–1 = Answer
The molality of a solution is indirect expression of the ratio of the moles of the solute to the moles of the
solvent. The molal aqueous solution of a solute say glucose or NaOH is dilute in comparison to its molar
solution. The reason is that in molal solution the quantity of the solvent is comparatively greater.
The value of concentration given in the units of molality does not change with temperature but that of
molarity does. The reason is that the volume of liquids are affected by the variation in temperature.
S.Q4 Define mole fractions? (SHW-2016, 2017, SRG-2010, RWP-2014, 2016, D.G.K-2016)
9.1.4. Mole Fraction (symbol, x)
This unit of concentration may be for any type of solution i.e. gas in gas, liquid in liquid or solid in
liquid, etc. This unit is also applicable to a solution having more than two components.
The mole fraction of any component in a mixture is the ratio of the number of moles of it to the total
number of moles of all the components present.
Let there be three components A, B, C making a solution. The number of moles are n A, nB, nC
respectively. If the mole fraction of A, B and C are denoted by xA, xB, xC respectively, Then,
xA =
xB =
xC =
The sum of the mole fractions of all the components of a solution must be equal to one. There are no
formal units of mole fraction. Anyhow, we sometimes multiply mole fraction by 100 to get mole percent.
Example (4): (L.Q)
Calculate the mole fraction and mole percent of each component in a solution having 92 g of ethyl
alcohol, 96 g of methyl alcohol and 90 g of water.
Solution:
First of all get the number of moles of each component.
Number of moles of the substance =
Molar mass of ethyl alcohol (C2H5OH) = 46 gmol–1
Number of moles of ethyl alcohol = = 2 moles
Molar mass of methyl alcohol(CH3OH) = 32 gmol–1
Number of moles of methyl alcohol = = 3 moles
Molar mass of water (H2O) = 18 mol–1
Number of moles of water = = 5moles
The mole fraction of any components is ratio of its moles to total number of moles.
X ethyl alcohol = = = Answer
X methyl alcohol = = = Answer
X H2O = = = Answer
Now, multiply the mole fractions with 100, to getmole percent.
Mole % of ethyl alcohol = 0.2  100 = Answer
Mole % of methyl alcohol = 0.3  100 = Answer
Mole % of H2O = 0.5  100 = Answer
In the case of mixture of gases, one can determine the mole fraction from the partial pressure data of
the mixture. Hence
398 Chapter # 9 (Solution)
xA = , xB = , xC =
Where PA, PB, PC are the partial pressures of various gases in the mixture.
Generally, we can say that
Mole fraction of any gas =
9.1.5. Parts Per Million (symbol, ppm) (SHW-2014, 2015, 2017, BHR-2017, MLT-2007, LHR-2009,
D.G.K-2009, SHW-2015, SRG-2011)
It is defined as the number of parts (by weight or volume) of a solute per million parts (by weight or
volume) of the solution.
This unit is used for very low concentrations of solutions, e.g. to express the impurities of substances in
water.
Parts per million (PPM) =  106
Example (5):
Sea water has 5.65 x 103 g of dissolved oxygen in one kg of water. Calculate the concentration of oxygen
in sea water in parts per million
ppm of oxygen in sea water =  106 = Answer
S.Q5 100 g of 98% H2SO4 has a volume of 54.34 cm3 of H2SO4 because its density is 1.84 g/cm3. Prove it.
Ans. Density =
Or Volume of H2SO4 = = = 54.3 cm–3
S.Q6 What do you mean by solvent and solute?
Ans. The component of solution, which is present in a large quantity, is called a solvent. The component of
solution, which is present in smaller quantity, is called a solute.
Q.7 What do you mean by dilate and concentrated solution?
Ans. A solution, which contains relatively lower concentration of solute, is called a dilute solution and a
solution, which contains relatively higher concentration of solute, is called a concentrated solution.
S.Q8 How will you prepare 5% W/V urea solution in water. (RWP-2009: FSD-2011: SRG-2013) %W/N
means the weight of solute dissolved per 100 parts by volume of solution.
Ans. So 5 g of urea are taken in a 100 cm 3 flask and the volume of solution is made upto the mark (i.e.
100cm3 ) with distilled water. It will be 5% W/V urea solution.
S.Q9 How will you prepare 0.2 M NaOH solution? (D.G.K-2009)
Ans. Mass of NaOH = w = ?
Molar mass of NaOH =M = 23+16+l=40g mol–1
Volume of solution = V = 1 dm3
Molarity = 0.2 M
Molarity is given by
molarity = 
or w = molarity  M  V
= 0.2 x 40 x 1 = 8 g
Thus 8 g of NaOH are taken in a 1 dm 3 flask and the volume of solution is made upto the mark (i.e.
1dm3) with distilled water.
S.Q10 Justify that one molal solution of urea in water is dilute than one molar solution. (BHR-2009)
Ans. Both 1 molal and 1 molar urea solution contain 1 mole of urea. Hence both these solutions contain same
number of particles i.e. 6.02  1023.
For 1 molal solution. 1 mole of urea is dissolved in 1 kg of water i.e. 1 dm 3. However, for 1 molar
Professor CHEMISTRY - XI (Subjective) 399
solution. 1 mole of urea is first taken in a .measuring flask and then volume is made up to 1 dm 3. Hence.
1 molar solution contain less amount of H2O than 1 molal solution. Hence one molal solution is dilute
than one molar solution
S.Q11 Differentiate molarity and molality. (LHR-2008.2014.2016. MLT-2009. 2017: GUJ- 2010: RWP-
2013: FSD-2016)
Ans.
MOLARITY MOLALITY
(1) Number of moles of solute dissolved in 1 (1) Number of moles of solute dissolved in 1 kg.
dm3 of solution is called molarity. of solvent is called molality.
(2) It is volume based so it changes with (2) It is mass bases so it does not change with
temperature temperature
(3) It is denoted by M (3) It is denoted by m
(4) formula is mole/liter (4) formula is mole / Kg
(5) Is affected by change in temperature. (5) Is not affected by changes in temperature.
S.Q12 How will you prepare 10% W/V urea solution in water? (FSD-2011)
Ans. To prepare 10% W/V urea, take 10 g urea and dissolve it into solvent and make the total volume of
solution as 100 cm3 it will be 10% W/V solution of urea in water.
MCQ
1. The amount of NaOH required to prepare 250 cm3 of 1 M solution is (LHR-2010, FSD-2011)
(a) 1 g (b)  10 g (c) 2 g (d) 6g
2. 0.1 moles of a solute dissolved in 100 g of solvent will be: (LHR-2009) (GUJ-2010)
(a) 0.1 molal (b)  1.0 molal (c) 0.5 molal (d) 0.1 molar
3. The number of moles of solute per kilogram of solvent is called: (GUJ-2009)
(a) molality (b) molarity (c) mole-fraction (d) normality
3
4. The amount of NaOH required to prepare 250 cm of 1 N solution in grams is: (GUJ-2011)
(a) 10 (b) 15 (c) 20 (d) 25
5. Solutions containing relatively lower concentrations of Solutes are called: (BHR-2009)
(a)  Dilute solution (c) Concentrated solution (c) Saturated solutions (d) Ideal solutionis
3
6. 2 g of NaOH is dissolved in 500 cm of solution. The molarity of solutions is (RWP-2009)
(a) 2.0M (b) 1.0M (c) 0.2M (d) 0.1M
3
7. 10g NaOH dissolved per 250 cm of solution has molarity (LHR-2010)
(a) 0.5 M (b) 1.0 M (c) 1.5 M (d)2.0M
8. Amount of NaOH required to prepare 250 cm3 of 1 M solution is (FSD-2011)
(a) 10 g (b) 6 g (c) 2 g (d) 8 g
9. The number of moles of solute dissolved per dm1 of solution is called (D. G. K-2012)
(a) Molarity (b) molality (c) Normality (d) mole fraction
(a) 100 g (b) 3420 g (c) 1342 g (d) 342 g
10. Molarity of pure water is: (SRG-2012, LHR-2012, GRW-2014, FSD-2014, RWP-2015, LHR-2015,
SHW-2016, RWP-2016, GRW-2017, FSD-2017)
(a) 1 (b) 18 (c) 55.5 (d) 6
9.1.6 Interconversion of Various Concentration Units of Solutions
400 Chapter # 9 (Solution)
Sometimes, we get prepared solutions from the chemical supply houses. For example, we are working
with a solution whose molarity is given by the supplier, but we need to know its molality or w/w percentage.
For such purpose, we need to convert one unit of concentration into other. These conversions are usually done if
we know the formula masses and the densities of the solutes or solutions. Following table shows the five
important chemicals whose w/w%, molarities and densities are given. One should be able to interconvert these
concentration units into each other and moreover to molalities and mole fractions for laboratory work Let us do
some calculations in this respect.
Molarity (M Density
Name of Acid % (w/w)
dm–3) (gem–3)
H SO, 98 % 18 1.84
H3PO4 85.5 % 4.8 1.70
HNO3 70.4 % 15.9 1.42
HCl 37.2 % 12.1 1.19
CH2COOH 99.8 % 17.4 1.05
Example (6):
Calculate the molality of 8% w/w NaCl solution.
Solution:
Molarity is the number of moles of solute kg–1 of solvent
8% w/w NaCl solution means that 8g of NaCl are dissolved in l00g of solution
So, mass of water in the solution = 100 – 8 = 92 g
Number of moles of NaCl = = 0.1367
Mass of H2O in kg = = 0.092 kg
It means that 0.1367 moles of NaCl is dissolved in 0.092 kg of water.
Molality (m) = =
The given solution is 1.487 molal.
Example (7):
Hydrochloric acid available in the laboratory is 36% (w/w). The density of HCl solution is 1.19 g cm –3.
Determine the molarity of HCl solution.
Solution:
36% (w/w) HC1 solution means that 36g of HC1 dissolved in l00g of solution.
Mass of HCl = 36 g
Mass of solution = 100 g
In case of molarity, the final volume of solution is 1000 cm1. Convert this volume into mass, by using
density of 1.19 gem–3.
Mass of 1000 cm–3 of HCl solution = 1000  1.19 = 1190g
Since, (Mass = volume  density)
100g of solution has HCl = 36g
So, mass of HCl in 1190 g of solution = = 428.4g
Molar mass of HCl = 36.5 g mol–1
Number of moles of HCl, in 428.4 g of HC1 = =11.73
So, 1000 cm3 solution of HCl has 11.73 moles of HCl
Hence, molarity of HCl = [Answer
Professor CHEMISTRY - XI (Subjective) 401

Example (8):
9.2 molar HClO4 is available from the market. The density of this solution is 1.54gcm What is the
percentage by weight of HClO4.
Solution:
Molarity of HClO4 = 9.2g moles dm–3
Density of solution = 1.54 gem–3
Let us calculate the mass of solution which is l dm in volume and has 9.2 moles of HClO4 in it.
Since, Mass = volume  density
Mass of 1000 cm3 solution = 1000 cm  1.54 g cm–3 = 1540 g
Molar mass of HClO4 = 100.5 g mol–1
9.2 moles of HClO4 can be converted to its mass
Mass of HClO4 = 100.5 g mol–1  9.2 mol = 924.6 g
Mass of H2O = mass of solution – mass of HClO4 = 1540 – 924.6 = 615.4g
% of HClO4 by weights  l00  100 = 60.04
% of H2O by weight = 100 – mass of HClO4 = 100 – 60.04 = Answer
9.2 TYPES OF SOLUTIONS (L.Q)
Most commonly, we come across solutions, where solute is a solid and the solvent is. a liquid. As a
matter of fact, all the three states of matter i.e. solid, liquid or gas can act as solute or solvent. Examples for nine
possible types of solution are given in Table (9.2).
Table (9.2) Common types and examples of solutions
State of Solute State of Solvent Example
Gas Gas Air
Gas Liquid O2 in water, CO2 in water.
Gas Solid H2 adsorbed by palladium.
Liquid Gas Mist, fog, clouds, liquid air pollutants.
Liquid Liquid Alcohol in water, milk, benzene in toluene.
Liquid Solid Mercury in silver, butter, cheese.
Solid Liquid Sugar in water, jellies, paints.
Solid Gas Dust particles in smoke.
Solid Solid Metal alloys pearls, opals, carbon in iron (steel).
MCQs
1. Solid is alloy of:
(a) Cu + Zn (b) Cu + Sn (c) Cu + Ni + Zn (d) Pb + Sn
2. Cheese is type of solution.
(a) Solid in a gas (b) Gas in a solid (c) Liquid in a solid (d) Solid in a liquid
9.2.1 Solutions of Solids in Liquids (S.Q)
When a solid comes in contact with a suitable liquid, it dissolves forming a solution i.e. a homogeneous
mixture. This process of dissolution can be explained in terms of attraction between the particles of a solute and
that of a solvent. The molecules or ions in solids are arranged in such a regular pattern that the inter-molecular
or inter-ionic forces are at a maximum. The process of dissolution is to overcome these forces of attraction
holding together the solute molecules or ions in the crystal lattice, by the solute-solvent forces. In molecular
crystals, the inter-molecular forces of attraction are either dipole-dipole or London dispersion type. These forces
402 Chapter # 9 (Solution)
are relatively weak and can easily be overcome. Hence, non-polar or less polar molecular crystals usually
dissolve in non-polar solvents like benzene.
In the crystal lattice, the inter-molecular or inter-ionic forces of attraction between highly polar
molecules or ions are quite strong, hence the polar solids fail to dissolve in non- polar solvents. These strong
electrostatic forces cannot be overcome or shattered by the weak solute-solvent attractions. Take the case of
cane sugar. Due to hydrogen bonding, it has tightly bound molecules, so it will not be dissolved by solvents like
kerosene oil, petrol, benzene, etc. It will be dissolved readily in water, because water attracts sugar molecules
almost in the same way as the sugar molecules attract one another.
The inter-ionic forces of attraction are very strong in ionic solids so, equally strong polar solvents are
needed to dissolve them. Such solids cannot be dissolved by moderately polar solvents e.g. acetone. A
moderately polar solvent, fails to dissolve sodium chloride, which is an ionic solid. Thus the solubility principle
is that "like dissolves like".
9.2.2 Solutions of Liquids in Liquids (L.Q)
The solutions of liquids in liquids may be divided into three classes,
(i) Completely Miscible Liquids
Liquids like alcohol and water or alcohol and ether mix in all proportions. However, the properties of
such solutions are not strictly additive. Generally, the volume decreases on mixing but in some cases it
increases. Heat may be evolved or absorbed during the formation of such solutions. These types of solutions
can usually be separated by fractional distillation.
(ii) Partially Miscible Liquids
A large number of liquids are known which dissolve into one another up to a limited extent. For
example, ether (C2H5 — O — C2H5) dissolves water to the extent of about 1.2 % and water dissolves ether up to
the extent of about 6.5%.
As the mutual solubilities are limited, the liquids are only partially miscible. On shaking equal volumes
of water and ether, two layers are formed. Each liquid layer is a saturated solution of the other liquid. Such
solutions are called conjugate solutions. The mutual solubility of these conjugate solutions is affected by
temperature changes. Typical examples of such systems are:
a. Phenol-water system
b. Triethylamine-water system
c. Nicotine-water system
Phenol-Water System (H2O + C6H5OH)
The example of phenol in water is interesting. If equal volumes of water and phenol are mixed together,
they show partial miscibility. It has been observed that around room temperature, phenol will dissolve in a lot of
water giving us the upper layer and water will dissolve in a lot of phenol giving us the lower layer.
At 25o C the upper layer is 5% solution of phenol in water and the lower layer is 30% water in
phenol. These two solution are conjugate solutions to each other. The lower layer has a greater density due to
greater percentage of phenol. Water acts as a solute in the lower layer while phenol is a solute in the upper
layer. When the temperature of water-phenol system is increased, the compositions of both layers change.
Water starts travelling from upper to the lower layer and phenol travels from lower to the upper layer. When the
temperature of this system approaches 65.9° C, a homogeneous mixture of two components is obtained. This
homogeneous mixture contains 34% phenol and 66% water. The temperature of 65.9° C at which two
conjugate solutions merge into one another, is called critical solution temperature or upper consulate
temperature.
Some other partially miscible pairs of liquids have their own consulate temperatures with definite
compositions.
For example, water-aniline system has a single layer at 167.0° C with 15% water. Methanol-
cyclohexane system has consulate temperature of 49.1°C with 29% methanol.
Professor CHEMISTRY - XI (Subjective) 403
(iii)Liquids Practically Immiscible
Those liquids which do not dissolve into each other in any proportion are immiscible.
Examples: (i) Water and benzene (H2O + C6H6)
(ii) Water and carbon disulphide (H2O + CS2)
S.Q13 What is effect of temperature on the conjugate solution of water and phenol?
Ans. Water and phenol are partially miscible. They make two distinct solutions and two separate layers at
room temperature. By increasing the temperature, the composition of the two conjugate solution change
and at 65.9°C a homogeneous mixture of two components is formed.
S.Q14 What are conjugate solutions? Give examples. (LHR-2008)
Ans. When two liquids are mixed together such that two layers are produced and each layer is a saturated
solution of other liquid then such solutions are called conjugate solutions
Examples:
(1) Phenol-water system
(2) Triethylamine-water system
(3) Nicotine-water system
S.Q15 What is consulate temperature or critical solution temperature? Give example. (MLT-2007, 2015:
D.G.K-2010: D.G.K-2012. SRG-2012, 2013: LHR-2015: RWP-2016. FSD-2016)
Ans. The temperature at which two conjugate solutions merge into each other to form homogenous mixture is
called critical solution temperature or consulate temperature.
Different systems have their own consulate temperature and composition.
Examples: Water-Aniline system has upper consulate temperature of 167 °C with 15% H 2O Phenol-
Water system has upper consulate temperature of 65.9°C with 34% phenol and 66% water.
S.Q16 Give two statements of Raoult's law (GUJ-2008: FSD-2008, 2012, 2014: MLT-2016)
OR What is RaoultS law? (RWP-2013: GUJ-2015: BHR-2017)
Ans. The vapour pressure of a solvent above a solution, is equal to the product of the vapour pressure of pure
solvent and mole fraction of solvent in solution. Mathematically
P = P°x1
Lowering of vapour pressure of a solution, is directly proportional to the mole fraction of solute
Or Mathematically P  x2
S.Q17 One sugar cannot be dissolved in benzene. Give reason. (GUJ-2014: SHW-2017)
Ans. One-sugar with strong hydrogen bonding is polar. It does not dissolve in non-polar solvents such as
kerosine oil, petrol, benzene etc. because these solvents can not break H-bonding of cane-sugar.
S.Q18 Why glucose is soluble in water but insoluble in CCl4? (SRG-2007)
Ans. Solubility principle states
“Like dissolves Like " i.e. Polar substances are dissolved in polar solvents and vice versa.
Since glucose is a polar substance containing many OH group, therefore, it dissolves in water which is
also polar. They i hydrogen bonds with each other.
S.Q19 Give two examples of liquid-liquid solutions. (D.G.K-2014)
Ans. (i) Liquids which dissolve together in all proportion are called completely miscible liquids.
Example: Solution of alcohol in H2O
(ii) The liquids which dissolve together to some extent are called partially miscible liquids
Example: Mixture of phenol and water
404 Chapter # 9 (Solution)

MCQs
1. Upper consulate temperature for water-phenol system is: (SRG-2017)
(a) 150°C (b) 65.9°C (c) 120°C (d) 130°C
2. An aqueous solution of ethanol in water has vapour pressure (SRG,SHW-2014, D.G. Khan -2017)
(a) equal to that of water (b) equal to that of methanol
(c) more than that of water (d) less than that of water
3. The critical solution temperature of phenol-water system is. (D.G.K-2008)
(a) 33.6°C (b) 49.5°C . (c) 57.8°C (d)  65.9oC
9.3.0 Ideal and Non-Ideal Solutions (L.Q) (SRG-2010, BHR-2012, 2010)
When two or more than two liquid substances are mixed, the solutions may be ideal or non-ideal. To
distinguish between such solutions we look at the following aspects:-
i. If the forces of interactions between the molecules of different components are same as when they were
in the pure state, they are ideal solutions, otherwise non-ideal.
ii. If the volume of solution is not equal to the sum of the individual volumes of the components, the
solution is non-ideal.
iii. Ideal solutions have zero enthalpy change as their heat of solution.
iv. If the solutions obey Raoult's law, then they are ideal. This is one of the best criterion for checking the
ideality of a solution
Let us first study, the Raoults's law and then try to understand ideality of solutions, the process of
fractional distillation and the formation of azeotropes.
S.Q20 What is an ideal solution?
Ans. A solution that obeys Raoult's law exactly at all temperatures and pressures is called an ideal solution.
S.Q21 Give any two points which show the ideality of a solution. (LHR-2008)
Ans. (i) During formation of an ideal solution, heat is not evolved or absorbed.
(ii) Total volume of solution is equal to the sum of volume of components of solution.
S.Q22 Give two pairs of liquids which form ideal solution. (D.G.K-2012)
(i) Benzene - Toluene.
(ii) Benzene - Ether.
(iii) Chlorobenzene-Bromobenzene
S.Q23 Differentiate between ideal and non-ideal solutions. (BHR-2009. RWP-2011: LHR-2013,2014:
MLT-2016: SRG-2017, SHW-2014).
Ans.
Ideal Solution Non-Ideal solution
(1) A solution, which obeys Raoult's law. is called (1) A solution which does not obey Raoult's law
an ideal solution. is called a non-ideal solution.
(2) During formation of an ideal solution., heat is (2) During formation of a non-ideal solution, heat
not evolved or absorbed, i.e., enthalpy change may evolve or absorb, i.e.. enthalpy change is
is zero (H = 0) not zero (AH  O)
(3) Total volume of solution is equal to the sum of (3) Total volume of solution is not equal to the
volume of components of solution sum of volume of components of solution
(4) These solutions are Zeotropic Mixtures, which (4) These solutions are Azeotropic Mixtures,
Professor CHEMISTRY - XI (Subjective) 405

distil with change in composition. which distil without change in composition.

(5) Examples: (5) Examples:
(i) Solution of Benzene and Ether (i) Solution of Acetone and Water.
(ii) Solution of Benzene and toluene (ii) Ethanol and water
(6) Temperature is not change, when solution is (6) Temperature increases or decreases when
formed (T = 0) solution is formed (T  0)

S.Q24 Non-ideal solutions do not obey Raoult's law. Explain (SRG-2009: D.G.K-2009: RWP-2010. 2015:
FSD-2015: SRG-2017, GUJ-2014)
Ans. A solution, which does not obey Raoult's law, is called a non-ideal solution.
Non-ideal solutions show deviations from ideal behaviour due to difference in their molecular structure
i.e. size, shape and intermolecular forces. In non-ideal solution, forces of attraction among molecules of
components do not remain same just as they were in pure form. Hence, they do not obey Raoult's law.
MCQs
1. Which of the following will form an ideal solution? (D.G. K-2010)
(a) C2H5OH and H2O (b) C6H6 and CCl4
(c) CHCl3 and CH3COOCH3 (d) H2O and HBr
2. Benzene-ether can form (D. G. Khan Board, 2012)
(a) Ideal solution (b) Non-ideal solution (c) Buffer solution (d) none of these
3. Benzene-ether can form solution
(a)  ideal solution (b) non-ideal (c) buffer solution (d) none of these
4. Which of the following liquid pairs will obey the Raoult's law:
(a) C2H5OH + H2O (b) CH3COCH3 + CHCl3 (c) C2H5I + C2H5Br (d) HCl + H2O
5. A mixture of benzene and toluene form:
(a) Ideal solution (b) Non-ideal solution (c) Azeotropic mixture (d) Suspension
9.3.1 RAOULTS LAW (L.Q)
(BHR-10, D.G.K-12, RWP, SRG-14, 2015, LHR-2011, BHR-2015, 2016, GUJ-2008, 2016)
Raoult's law can be defined in these ways:
The vapour pressure of a solvent above a solution is equal to the product of the vapour pressure of
pure solvent and the mole fraction of solvent in solution.
Mathematically, it can be written in equation form as follows:
p = p°x1 ……. (1)
Where p is the vapour pressure of solvent in the solution, p° is the vapour pressure of pure solvent and x 1
is the mole fraction of solvent. We also known that
x1 + x2 = 1 (x2 is the mole fraction of solute)
or x1 = 1– x2
Putting the value of x, in equation (1)
p = p°(l – x2)
or p = p° – p°x2
or p°– p = p°x2
or p = p°x2 …… (2)
Equation (2) gives another definition of Raoult's law. "The lowering of vapour pressure is directly
proportional to the mole fraction of solute." Now rearrange equation (2) to get equation (3).
406 Chapter # 9 (Solution)
= x2
p /p° is called relative lowering of vapour pressure and it is more important than actual lowering of
vapour pressure (p). The equation (3) gives us another definition of Raoult's law.'The relative lowering of
vapour pressure is equal to the mole fraction of solute".
The relative lowering of vapour pressure:
(i) is independent of the temperature
(ii) depends upon the concentration of solute.
(iii) is constant when equimolecular proportions of different solutes are dissolved in the same mass of
same solvent.
Example (9): (L.Q)
The vapour pressure of water at 30° C is 28.4 torr. Calculate the vapour pressure of a solution containing
70g of cane sugar (C12H22O11) in l000 g of water at the same temperature. Also calculate the lowering of
vapour pressure.
Solution:
Molar mass of cane sugar dissolved Molar mass of cane sugar
Number of moles of a compound
Number of moles of sugar, C12H22O11 (n2) = = 0.20
Mass of H2O in solution = 1000 g
Number of moles of water, H2O (n1) = = 55.49
Total number of moles = 0.20 + 55.49 = 55.69
Mole fraction of sugar, C12H22O11 (x2) = = = 0.0036
Mole fraction of water, H2O (x1) = = = 0.9964
Vapour pressure of pure water = 28.4 torr
Applying the formula for vapour pressure of solution
p = p° x1 = (28.4) (0.9964) = 28.29 torr
So, vapour pressure of solution = Answer
Lowering of vapour pressure, p = 28.4 – 21.29 = Answer
9.3.1 Raoult's Law (when both components are volatile) (L.Q)
Raoult's law can be applied to understand the relationship between mole fractions of two volatile
components and their vapour pressures before making the solution and after making the solution. Consider two
liquids ‘A’ and ‘B’ with vapour pressures p° and p° in the pure state at a given temperature. After making the
solution, the vapour pressures of both liquids are changed. Let the vapour pressures of these liquids in solution
state be pA and pB with their mole fractions xA and xB respectively.
Applying Raoult's law to both components
PA = p° xA
PB = p° xB
Pt = pA + pB = p° xA + p° xB (where Pt is total vapour pressure)
since xA + xB = l
xB = 1 – xA
Pt = p° xA + p° (1 – xA)
Pt = p° xA + p° – p°xA
Pt = (p° – p°) xA + p° …….. (4)
The component A is low boiling and B is high boiling. The vapour pressure of A is more than B at a
Professor CHEMISTRY - XI (Subjective) 407
given temperature.
Equation (4) is a equation of straight line. If a graph is plotted between or mole % of B on x-axis and P.
on y-axis, a straight line will be obtained Fig (9.1)
Only those pairs of liquids give straight lines which form ideal solutions. So, Raoult's law is one of the
best criterion to judge whether a solution is ideal or not.
All the possible solutions of two components A and B
have their vapour pressures on the straight line connecting p°
with p°. All such solutions will be ideal. Each point on this
straight line represents the vapour pressure of a solution, at a
given temperature, with the corresponding contribution of both
the components A and B.
The two dotted lines represent the partial pressures of the
individual components of solution. They show the increase of
vapour pressure of a component with increase in its mole fraction
in solution.
In order to explain it, consider a point G on the straight
line. This point represents the vapour pressure of solution with
30% moles contribution of the component B and 70%.
Since, A is more volatile component, so its contribution towards the vapour pressure of solution is
represented by pA. The contribution of the less volatile component B is represented by pB. Similarly, we can
calculate the relative contributions of A and B towards the total vapour pressure of solution by taking other
points along the line joining p° to p°.
The total vapour pressure of the solution (Pt) corresponding to the point G will be equal to the sum of the
vapour pressures of the individual components (pA + pB) as shown in the Fig. (9.1).
S,Q25 Relative lowering of vapour pressure is independent of the temperature. Justify. (FSD 2008, SRG,
GUJ & RWP-2009)
Ans. Vapour pressure of pure solvent and lowering of vapour pressure both depend upon temperature, so
when the temperature of the solution is raised, then AIL and p° increase in such a way that the ratio
remains the same. Therefore, relative lowering of vapour pressure is independent of temperature.
Relative lowering of vapour pressure = = x2
S.Q26 Define Raoult's law
Ans. The vapour pressure of a solvent above a solution is equal to the product of the vapour pressure of pure
solvent and the mole fraction of the solvent in solution. Mathematically,
P = P°X
S.Q27 What is the relationship between the relative lowering of vapour pressure and the mole fraction of
the solute?
Ans. The relative lowering of vapour pressure is equal to the mole fraction of solute. Mathematically,
= x2
Where P/P° is called relative lowering of vapour pressure and x2 is the mole fraction of solute.
S.Q28 What is positive deviation from Raoult's Jaw? (LHR-2007)
Ans. The pairs of liquids which have greater value of vapour pressure for some of their compositions than
those of pure components show positive deviation from Raoult's law. They show a maximum point in
the composition vapour pressure curve.
MCQs
408 Chapter # 9 (Solution)
1. Raoult's law is represented as. (LHR-2009,2011)
(a) P = px2 (b) P = pox2 (c) p = Px1 (d) po = px1
2. Raoult's law is represented by (LHR-2007, 2009)
(a) P = P°X1 (b) P = P°X2 (c) P/P° = X2 (d)  all of these
3. Relative lowering of vapor pressure is equal to (LHR-2017)
(a) mole fraction of solvent (b) mole fraction of solute
(c) molarity (d) molality
4. Which of the following shows negative deviation from Raoult's law?
(a) CHCl3 and CO(CH3)2 (b) C6H6 and CH3OH
(c) C6H5CH3 and C6H6 (d) C6H6 and CCl
9.4 VAPOUR PRESSURES OF LIQUID-LIQUID SOLUTIONS (L.Q)
Binary mixtures of miscible liquids may be classified
as (i) ideal (ii) non-ideal or real solutions.
The vapour pressures of solutions provides a simple
picture about their behaviour. Let us discuss the vapour
pressures of ideal and real solutions one by one.
(i) Ideal solutions (Zeotropic mixture)
(D.G.K-2009, LHR-2012)
An ideal solution is that which obeys Raoult's law.
Some typical ideal solution forming liquid pairs are:
benzene-toluene, benzene-ether, chlorobenzene-
bromobenzene, ethyl iodide-ethyl bromide, etc.
Fractional Distillation of Ideal Mixture of Two Liquids
Let us have two liquids A and B which form a
completely miscible solution. A is a more volatile component so its boiling point is less than B. If we have
various solutions of these two components and a graph is plotted between compositions on x-axis and
temperature on y-axis, then two curves are obtained as shown in the Fig. (9.2). The upper curve represents the
composition of the vapours of different solutions while the lower curve represents the composition of the liquid
mixtures. The reason is that at any temperature the composition of vapours is different from the composition of
liquid mixture.
Consider the temperature, corresponding to the point G. It is the boiling point of solution corresponding
to composition I. It meets liquid curve at point H and the vapour curve at the point C. The composition of
liquid mixture corresponding to the point H is shown by the point I. At point I mixture has greater percentage of
B and less percentage of A. While at the same temperature the vapours of the mixture have the composition K.
At the point K, the percentage of A is comparatively greater than B when we compare it with composition of
liquid mixture corresponding to point I. Because A is a low boiling liquid, it is present in the vapour state in
greater percentage than at point I.
If the temperature of the mixture is maintained corresponding to point G, the distillate will have greater
percentage of A and the residue will have greater percentage of B. The reason is that the fraction going to
distillate is that which is in vapour state and it has greater % of A. The distillate of composition K is again
subjected to distillation. Its boiling point is X, and at this temperature the distillate of composition Z is obtained.
This distillate of composition Z is further distilled. In this way, the distillate becomes more and more rich in A
and residue is more and more rich in B. So, process of distillation is repeated again and again to get the pure
component A. Thus we can completely separate the components by fractional distillation. Such liquid mixtures,
which distil with a change in composition, are called zeotropic mixtures. For example, methyl alcohol-water
solution can be separated into pure components by distillation.
ii. Non-Ideal Solutions (azeotropic mixtures) (L.Q) (FSD-2007, GUJ, SRG-2013, D.G.K-2016)
Professor CHEMISTRY - XI (Subjective) 409
Many solutions do not behave ideally. They show deviations from Raoult's Law due to differences in
their molecular structures i.e. size, shape and intermolecular forces. Formation of such solutions is accompanied
by changes in volume and enthalpy. The vapour pressure deviations may be positive or negative in such
solutions.
Azeotropic mixtures are those which boil at constant temperature and
distil over without change in composition at any temperature like a pure
chemical compound. Such mixtures can not be regarded as chemical
compounds as changing the total pressure alongwith the boiling point changes
their composition. Whereas, for a chemical compound, the composition
remains constant over a range of temperature and pressure. The deviations of
solutions are of two types:
(a) Positive deviations
(b) Negative deviations
(a) Positive Deviations
If a graph is plotted between composition and vapour pressure of a
solution which shows positive deviation from Raoult's law, the total vapour
pressure curve rises to a maximum. The vapour pressure of some of solutions are above the vapour pressure of
either of the pure components.
Let us consider the mixture of A and B components at point C in Fig (9.3 ). At the point C Fig (9.3 ), the
mixture has the highest vapour pressure and, therefore, the lowest
boiling point. On distilling this type of solution, the first fraction will be a constant boiling point mixture
i.e., azeotropic mixture having a fixed composition corresponding to the maximum point. For this type of
solution, it is not possible to bring about complete separation of components by fractional distillation. Ethanol-
water mixture is an example of this type. It boils at 78.1°C with 4.5% water and 95.5 % alcohol. 78.1°C is lower
than the boiling point of ethanol (78.5°C) and water (100°C).
Negative Deviations
For this type of solution, the vapour pressure curve shows a minimum. Let us
consider a point E in Fig (9.3). Here, the more volatile component A is in excess. On distilling this solution, the
vapours will contain more of A and the remaining mixture becomes richer in less volatile component B'.
Finally, we reach the point D where vapour pressure is minimum and the boiling point is maximum. At this
point, the mixture will distill unchanged in composition.
Therefore, it is not possible to separate this type of solution completely into its components. We can
give the example of hydrochloric acid solution in water for this type of solutions. HCl forms an azeotropic
mixture with water, boiling at 110°C and containing 20.24% of the acid.
S.Q29 What do you mean by minimum boiling point mixture? (MLT-2009, 2011, LHR-2010)
Ans. This is an azeotropic mixture which shows positive deviation from Raoult's law. It boils at low
temperature than either of pure components.
S.Q30 What do you mean by maximum boiling point mixture? (MLT-2009, LHR-2010, MLT-2011)
Ans. This is an azeotropic mixture which shows negative deviations from Raoult's law. It boils at higher
temperature than either of the pure components.
S.Q31 Define Zeotropic mixtures. Give one example. (LHR-2014: FSD-2017: GUJ-2017)
Ans. Liquids which distils with change in composition are called zeotropic mixtures. Zeotropic mixture can
be easily separated into their components.
Example: Methyl alcohol - water solution can be separated by distillation.
S.Q32 What is positive deviation from Raoult's law? (LHR-2007)
Ans. Liquid solutions which have maximum in their vapour pressure curve show positive deviations from
410 Chapter # 9 (Solution)
Raoult's law. Such solutions form minimum boiling azeotrope. The azeotropic mixture boiling at lower
temperature than any of its component is called minimum boiling azeotrope.
S.Q33 Differentiate between zeotropic and azeotropic mixtures.(MLT-2011. D.G.K-2014. GUJ-2017)
Ans.
Zeotropic Mixtures Azeotropic Mixtures
(1) Mixtures which distil with change in (1) Mixtures which distil without change in
composition are called zeotropic mixtures. composition are called zeotropic mixtures.
(2) They don’t have constant boiling point (2) They have constant boiling point
(3) They obey Raoult’s law (3) They don’t obey Raoult’s law
(4) Its components can be completely separated by (4) Its components cannot be completely separated
distillation by distillation
(5) Example: Methanol-water. solution etc. (5) Example: Ethanol-Water. HCl-Water etc.
Benzene – toluene
S.Q34 Define azeotropic mixture. Give two examples (SRG-2016)
Ans. The liquid mixtures, which boil at constant temperature and distil over without change in composition
like a pure compound, at any temperature are called azeotropic mixtures.
Examples:
(i) Ethanol - water forms azeotropic mixture with ethanol 95.6%. It boils at 78.1°C. It is a minimum
boiling azeotrope.
(ii) HCl forms azeotropic mixture with water, which boils at 110°C. It contains 20.24 % HCl. It is a
maximum boiling azeotrope.
S.Q35 Differentiate between positive deviation and negative deviation?
Ans.
Positive deviation Negative deviation
(1) Temperature of solution increases. (1) Temperature of solution is less than ideal
solution.
(2) Vapour pressure of solution is greater than (2) Vapour pressure of solution is less than ideal
ideal solution. solution.
(3) Volume of solution slightly increases from the (3) Volume of solution slightly decreases from
individual volume of solute and solvent. the individual volume of solute and solvent.
(4) Example: Ethanol-water. (4) Example: HCl-water.

MCQs
1. Which one of the following is an ideal solution. (DGK-2016)
(a) C2H5OH and H2O (b) C6H6 and CCl4 (c) CHCl3 and (CH3)2CO (d) C6H6 and CCl4
2. Azeotropic mixture can be separated into pure components by (SRG-2005)
(a) simple distillation (b) fractional distillation
(c) vacuum distillation (d) none of these
3. Which of the following solutions has the highest boiling point? (D.G.K-2010)
(a) C2H3OH and H2O (b) C6HO and CCl4
(c) CHCl3 and (CH3)2CO (d) H2O and HCl
Professor CHEMISTRY - XI (Subjective) 411
4. The azeotropic mixture of solution showing positive deviation can be distilled at -------- boiling
point (FSD-2007)
(a) maximum (b) minimum (c) no sharp (d) none of these
5. The azeotropic mixture of solution showing positive deviation can be distilled at --------- boiling
point. (FSD-2007)
(a) Maximum (b)  Minimum (c) No sharp (d) None of these
9.5 SOLUBILITY AND SOLUBILITY CURVES (S.Q)
Whenever a solid solute is put in a liquid solvent then the molecules or ions break away from the surface
of the solid and pass into the solvent. These particles of solid are free to diffuse throughout the solvent to give a
uniform solution. The solute and solvent molecules are constantly moving about in the solution phase because
of kinetic energy possessed by them. In this way some of the particles of the solute may come back towards the
solid due to collisions. These molecules or ions are entangled in its crystal lattice and get deposited on it.
This is called re-crystallization or precipitation. If excess of solid is present in the solution then the rate of
dissolution and rate of crystallization become equal. This is a state of dynamic equilibrium.
The concentration of the solute at equilibrium with the solution is constant for a particular solvent and at
a fixed temperature. The solution thus obtained is called saturated solution of the solid substance and the
concentration of this solution is termed as its solubility.
So the solubility is defined as the concentration of the solute in the solution when it is in
equilibrium with the solid substance at a particular temperature. Solubility is expressed in terms of number
of grams of solute in l00g of solvent. At a particular temperature, saturated solution of NaCl in water at 0°C
contains 37.5g of NaCl in l00g of water. Similarly the solubility of CuSO4 in water at 0°C is 14.3g/100g,
while at 100°C it is 75.4g/100g.
To determine the solubility of substance, a saturated solution of a solid is prepared at a constant
temperature. Then this solution is filtered. A known volume of this solution is evaporated in a china dish and
from the mass of the residue, the solubility can be calculated.
Solubility Curves (L.Q) (FSD-2009, 2015, 2010, GUJ-2011)
Temperature has a marked effect on the solubility of many
substances. A graphical representation between temperature and
solubility of is solution is called solubility curves. There are two types
of solubility curves.
(a) Continuous solubility curves
(b) Discontinuous solubility curves
(a) Continuous Solubility Curves
Continuous solubility curves don't show sharp breaks
anywhere. According to Fig.(9.4). KClO3, K2Cr2O7, Pb(NO3)2 and
CaCl2, are showing continuous solubility curves. The solubility curves
of KCl, NaCl and NaNO3 give the straight lines. NaCl shows a very
small change of solubility from 0°C to 100°C increase of temperature.
Ce2(SO4)3 shows the exceptional behaviour whose solubility
decreases with the increase in temperature and becomes constant from 40°C onwards. Anyhow, it shows
continuous solubility curve.
(b) Discontinuous Solubility Curves
Sometimes, the solubility curves show sudden changes of
solubilities and these curves are called discontinuous solubility
412 Chapter # 9 (Solution)

curves. The best examples in this reference are Na 2SO4.10H2O, CaCl2.6H2O. Actually, these curves are
combination of two or more solubility curves. At the break a new solid phase appears and another solubility curve
of that new phase begins. It is the number of molecules of water crystallization which changes and hence solubility
changes, Fig (9.5).
S.Q36 CaCl2.6H2O shows discontinuous solubility curve when plotted against temperature. Explain.
(RWP-2008)
Ans. The reason is that its curve are combination of two or more solubility curves. At the break, a new solid
phase begins due to change is no. of water molecules of crystallization and another solubility curve
begins of that new phase and solubility changes.
S.Q37 How does an increase in temperature may increase or decrease the solubility of a substance?
(LHR-2010, SRG-2010)
Ans. When the heat of solution is positive and such solutions are heated, they dissolve more solutes and the
solubility increases. When the heat of solution is negative, then the heat is being evolved during the
formation of solution. When such solutions are heated, " their solubilities decrease.
S.Q38 Define solubility curve. Name its two types. (FSD-2012: D.G.K-2016)
Ans. A graphical representation between temperature and solubility of a substance is called solubility curve.
tee may be of two types
(i) Continuous Solubility Curves: These are smooth curves and do not show any sharp break points.
These may be of two types
(a) Increasing Solubility Curve (b) Decreasing Solubility Curves
(ii) Discontinuous Solubility Curves: These are not smooth curves and show sharp break points.
S.Q39 Why substances show discontinuous curves? (D.G.K-2008)
OR What is discontinuous solubility curve? (BHR-2015: GUJ-2015: MLT-2017)
Ans. A discontinuous solubility curves are not smooth and shows sudden breaks due to sudden so changes in
solubilities
Example : Solubility curve of Na2SO4. 10H2O. CaCl2.6H2O etc.
S.Q40 Differentiate between continuous and discontinuous solubility curves. (LHR-2011: FSD-2014)
Ans.
Continuous solubility Discontinuous solubility
(1) A smooth curve and does not show any sharp (1) Is not smooth and shows sudden breaks due
break points to sudden changes in solubilities
(2) No new phase appear along the smooth curve. (2) New phases appear at the sharp break points.
(3) It is the curve of a single substance only (3) It is a combination of two or more
continuous solubility curves
(4) Example: Solubility curve of NaCl, KNO3 etc. (4) Example: Solubility curves of Na2SO4.10H2O,
CaCl2.6H2O etc

S.Q41 Na2SO4.10H2O shows discontinuous solubility curve. Give reason. (SRG-2014)

Ans. The solubility of Na2SO4.10H2O increases with increase in temperature upto 30°C. At this temperature,
Na2SO4.10H2O loses all its water molecules. It converts into anhydrous Na 2SO4 which shows a decrease
in solubility with rise in temperature. So, when solubility curves of Na 2SO4.10H2O and anhydrous
Professor CHEMISTRY - XI (Subjective) 413
Na2SO4 are combined it shows a sudden break at this temperature. Hence the curve becomes
discontinuous.
S.Q42 Define solubility with one example. (GUJ-2016: D.G.K-2016 BHR-2017)
Ans. It is the concentration of solute in solution when it is in equilibrium with the solid substance in its
saturated solution at a : given temperature.
Solubility is expressed as number of g. of solute in 100 g of solvent. Generally solubility increases with
increase in temperature.
Example: At 0°C, solubility of NaCl in H2O is 37.5 g /100 g of H2O
S.Q43 CaCl2.6H2O shows discontinuous solubility curve when plotted against temperature. Explain.
(Rwp 08)
Ans. The reason is that its curve are combination of two or more solubility curves. At the break, a new solid
phase begins due to change is no. of water molecules of crystallization and another solubility curve
begins of that new phase and solubility changes.
Hence; CaCl2. 6H2O show discontinuous solubility curve
S.Q44 The solubility of glucose in water is increased by increasing the temperature. Explain. (FSD-2011,
LHR-2012, SHW-2015)
Ans. Heat provide K.E to water molecule which move faster and heat of solution of glucose is +ve therefore
increase in temperature increase the solubility of glucose.
MCQs
1. Solubility of KClO3 gives
(a) continuous and failing solubility curve (b) discontinuous and failing solubility curve
(c) continuous and rising solubility curve (d) discontinuous and rising solubility curve
2. The solubility of NaCl in water at 0°C is:
(a) 25.4 g/100 (b) 37.5 g/100 g (c) 44.7g/100g (d) 62.3g'100g
o
3. The solubility of CuSO4 in water at 0 C is
(a)  14.3 g/100 g (b) 10.6g'100g (c) 12.6g/i00g , (d) 15g/100g
4. The solubility curve for NaCl is:
(a) Rising line (b) Falling ling (c) Straight line (d) Discontinuous line
5. What happens to solubility of NaCl on increasing temperature from 0°C to 100°C?
(a) Gradually increases (b) Gradually decreases
(c)  Increases to very small extent (d) Decreases to very small extent
9.5.2 Fractional Crystallisation (S.Q)
The curve in Fig (9.4) shows that the variation in solubility with temperature is different for different
substituances. For example, the change in solubility in case of KNO3 is very rapid with changing temperature,
while such a change is more gradual in other cases like KBr, KCl, alanine, etc. These differences in the
behavior of compounds provide the basis for fractional crystallisation, which is a technique for the separation of
impurities from the chemical products.
By using the method, the impure solute is dissolved in a hot solvent in which the desired solute is less
soluble than impurities. As the hot solution is cooled, the desired solute being comparatively less soluble,
separates out first from the mixture, leaving impurities behind. In this way, pure desired product crystallizes out
from the solution.
S.Q45 How does fractional crystallization help in removing the impurities from a solid substance?
(RWP-2011)
Ans. The impure substance is dissolved in hot solvent. The solute to be purified should be less soluble than
414 Chapter # 9 (Solution)
impurities. When cooling is done, this solute settles down in the form of crystals and impurities are left
behind in the solution. Filtration is done to get the crystals of the required substance.
S.Q46 Why fractional crystallization is carried out? (RWP-2010: BHR-2011. D.G.K-2016)
OR
Define fractional crystallization. How it is useful? (D.G.K-2011)
Ans. The separation of solid substances from a solution, one by one, on cooling is called fractional
crystallization. Importance: It is a technique for separation of impurities from chemical products. The
solubilities of substances depend upon temperature, e.g. solubility of KNO 3 rapidly changes with
temperature but solubility of KCl. KBr, Alanine etc changes gradually. Thus one substance may
precipitate earlier by cooling, leaving behind other in the solution.
S.Q47 KNO3 can be separated from KCl and KBr by the technique of:
(a) Distillation (b) Vacuum crystallization
(c) Fractional distillation (d) Fractional Crystallization
9.6 COLLIGATIVE PROPERTIES OF SOLUTIONS (L.Q)
(SHW-2015, FSD-2011, BHR-2009)
The colligative properties are the properties of solution that depend on the number of solute and
solvent molecules or ions. Following are colligative properties of dilute solution.
(i) Lowering of vapour pressure
(ii) Elevation of boiling point
(iii) Depression of freezing point
(iv) Osmotic pressure
The practical applications of colligative properties are numerous. The study of colligative properties has
provided us with methods of molecular mass determination and has also contributed to the development of
solution theory.
9.6.1 Why Some of the Properties are Called Colligative
The reason for these properties to be called colligative can be explained by considering three solutions.
Let us take 6 g of urea, 18 g of glucose and 34.2 g of sucrose and dissolve them separately in 1 kg of H2O.
This will produce 0.1 molal solution of each substance. Pure H 2O has certain value of vapour pressure at a given
temperature. In these three solutions, the vapour pressures will be lowered. The reason is that the molecules of a
solute present upon the surface of a solution decrease the evaporating capability. Apparently, it seems that
sucrose solution should show the maximum lowering of vapour pressure while urea should have the minimum
lowering of vapour pressure. The reality is that the lowering of vapour pressure in all these solutions will be
same at a given temperature. Actually, the number of particles of the solute, in all the solutions are equal. We
have added l/10th of Avogadro's number of particles (6.02  1022). The lowering of vapour pressure depends
upon the number of solute particles and not upon their molar mass and structures. Well, it should be kept in
mind that these three solutes are non-volatile and non-electrolyte.
The boiling points of these solutions are higher than that of pure solvent. It is observed that the boiling
point elevation of these three solutions is 0.052 °C. Similarly, freezing points will be depressed for these
solutions and the value of depression in these three cases is 0.186°C. The reason again is that the elevation of
boiling point and the depression of freezing point depend upon number of particles of solute.
Now, let us deduce the values of elevation of the boiling point and the depression of, the freezing point
of water for 1 molal solutions. For that purpose, try to dissolve 60 g of urea, 180 g of glucose and 342 g of sugar
separately in 1 kg of water. If, it is possible then the elevation of boiling point and depression of freezing
point of water will be 0.52°C and 1.86 C, respectively. All the three solutions will boil at 100.52 °C and freeze
at –1.86oC. These values of elevation of boiling point and depression of freezing point are called molal boiling
point constants and molal freezing point constants of H 2O denoted by Kb and Kf, respectively. These are also
Professor CHEMISTRY - XI (Subjective) 415
named as ebullioscopic and cryoscopic constants, respectively.
These constants depend upon the nature of solvent and not upon the nature of solute. Following Table
(9.3) give the values of Kb and Kf for some common solvents.
Table (9.3) Kb and K, values for some solvents
Solvent B.P.(°C) Ks (°C/m) F.P (°C) Kf(°C/m)
H2O 100 0.52 0 1.86
Ether 34.4 2.16 –116.3 1.79
Acetic acid 118 3.07 17 3.90
Ethanol 79 1.75 –114.5 1.99
Benzene 80 2.70 5.5 5.10
To observe the colligative properties, following condition should be fulfilled by the solutions.
(i) Solution should be dilute
(ii) Solute should be non-volatile
(iii) Solute should be non-electrolyte
Now, let us discuss these colligative properties one by one. (We will not discuss osmotic pressure over
here)
S.Q48 Boiling points of solvents increase due to the presence of solutes. Why? (Federal -2006, FSD-2007,
GUJ-2008, 2010, LHR-2012)
Ans. The surface of the solution has molecules, of solute as well. They do not allow the solvent to leave the
surface as rapidly as in pure solvent. To boil the- solutions, we have to increase the temperature of
solutions in comparison to pure solvents.
S.Q49 Define colligative properties. Name some important colligative properties. (D.G.K-2010: LHR-
2011, 2015, 2017, FSD-2013, SRG-2014, 2015, 2016, RWP-2009, 2014, GUJ-2015, MLT-2016)
Ans. The properties, which depend upon number of solute and solvent particles in solution and not on their
chemicals nature, are called colligative properties
Examples: Lowering of Vapour pressure. Elevation in boiling point, Depression in freezing point,
Osmotic pressure.
S.Q50 Define ebullioscopic constant (or molal elevation constant or molal boiling point constant) with
one example. (LHR-2012,2014: GUJ-2015: BHR-2016)
Ans. The elevation in boiling point when 1 mole of non-volatile, non-electrolyte solute is dissolved in 1 kg o
solvent is called molal boiling point constant. It is also called ebullioscopic constant. It is denoted by K b.
e.g. Kb of water = 0.52oC
Kb of benzene = 2.70oC
S.Q51 Molal freezing point constant, (Define cryoscopic constant) (BHR-2008) (SRG-2007: Azad
Kashmir-2016. D.G.Khan -2015.2017)
Ans. The depression in freezing point, when 1 mole of non-volatile, non-electrolyte solute is dissolved in 1 kg
of solvent is called molal freezing point constant. It is also called cryoscopic constant. It is denoted by
Kf. e.g. Kf of water = 1.86oC
Kf of benzene = 5.1oC
S.Q52 Give the conditions of colligative properties. (SRG-2011)
Conditions For Normal Colligative Properties
416 Chapter # 9 (Solution)
• Solution must be dilute
• Solute must be non-volatile
• Solute must be non-electrolyte
S.Q53 Why colligative properties of solutions are obeyed when solute is non-electrolyte and also when the
solutions are dilute? (GUJ-2016)
Ans. (i) Colligative properties depend upon number of particles and not on their nature. So, when an
electrolyte is dissolved in a solvent it ionizes in water and thus increases the number of particles.
Hence, normal colligative properties are not observed.
(ii) Colligative properties are obeyed when there are no forces among solute particles. In concentrated
solution, for solute particles are very close to each other so they develop forces for each other.
Hence, normal colligative properties are not observed.
S.Q54 Why is the vapour pressure of a solution less than pure solvent? (LHR-2014)
Ans. In pure solvent, all the surface of solvent is covered by solvent molecules. However, when a non-
volatile, not electrolyte solute is added to it to form solution, some surface is occupied by solute
particles. Therefore, escape tendency of solvent molecules is decreased, thus its vapour pressure is
lowered.
S.Q55 Lowering of vapour pressure is a colligative property. Explain. (GUJ-2014)
Ans. The properties, which depend upon number of solute and solvent particles in solution and not on their
chemical nature, are called colligative properties
Lowering of vapour pressure depends upon the number of particles and not on their nature. Therefore, It
is colligative property.
e.g. If 60 g of urea 180 g of glucose and 342g of sucrose are dissolved in 1 kg of H 2O. Each of this is a 1
molal solution and contain equal number of solute particles, i.e. 6.02  1023. In all these cases, lowering
of vapour pressure is same.
S.Q56 Depression in freezing point is a colligative property. Justify. (LHR-2013)
Ans. The properties, which depend upon number of solute and solvent particles in solution and not on their
chemical nature, are called colligative properties .
Depression of freezing point depends upon the number of particles and not on their nature. Therefore, it
is a colligative property.
e.g. If 60 g of urea, 180 g of glucose and 342g. of sucrose are dissolved in 1 kg of H 2O. Each of this is a
1 molal solution and contain equal number of solute particles, i.e. 6.02  1023. In all these cases,
depression of freezing point is same (i.e. 1.86°C).
S.Q57 Colligative properties are obeyed when the solute is non-electrolyte and also when the solutions
are dilute. Explain (RWP-2012, GRW-2016)
Ans. Lowering of vapour pressure is a colligative property so when solute is electrolyte the lowering of
vapour pressure will increase due to increasing number of particle of electrolyte a volatile solute will
also take part in vapour pressure of solution along with vapour pressure of solute.
S.Q58 One molal solution of urea, in water is dilute as compare to one molar solution of urea but the
number of particles of the solute are same of both the cases. Explain with reason. (FSD-2010,
SRG-2016)
Ans. In one molal solution of urea, 60 g of urea is dissolve in 1000 g of water which is approximately 1 dm 3
(litre) of water. In molar solution 60 g of urea is added to water to make the total volume as 1 dm 3 (litre).
So the volume of water in molar solution is less than 1000 cm 3 (litre). Hence molar solution is
concentrated than molal solution.
MCQs
Professor CHEMISTRY - XI (Subjective) 417
1. The molal boiling point constant depends upon (FSD-2008)
(a)  nature of solvent (b) vapour pressure of solution
(c) nature of solute (d) temperature of solution
2. Colligative properties are the properties of (RWP-2008)
(a) dilute solutions which behave as nearly ideal solution
(b) both a & c
(c) dilute solutions which behave as nearly non ideal solutions
(d) neither (a) nor (c)
3. Molal boiling point constant is the ratio of the elevation in boiling point to (SRG-2009)
(a) Molarity (b) Mole of fraction of solvent
(c) mole fraction of solute (d) molality
4. Which is a colligative property? (FSD-2010)
(a) Change in vapour pressure of a solution. (b) change in free energy of a solution.
(c) Heat of vaporization of solvent in the solution (d) Lowering of vapour pressure of a solution.
5. Elevation of boiling point is (Sahiwal Board, 2014)
(a) an additive property (b) a constitutive property
(c)  a colligative property (d) a substitutive property
6. The molal boiling point constant depends upon (Fsd 08)
(a) nature of solvent (b) vapour pressure of solution
(c) nature of solute (d) temperature of solution
7. Collegative properties are the properties of (RWP-2009)
(a) Dilute solutions which behave as nearly ideal solution
(b) both a & c
(c) dilute solutions which behave as nearly non ideal solutions
(d) neither (a) nor (c)
8. Molal boiling point constant is the ratio of the elevation in boiling point to (SRG-2009)
(a) molarity (b) Mole fraction of solvent
(c) mole fraction of solute (d)  molarity
9.6.2 Lowering of Vapour Pressure (L.Q)
The particles can escape from all over the surface of a pure solvent Fig. (9.6a). When the solvent is
containing dissolved non-volatile solute particles, the escaping tendency of solvent particles from the surface of
the solution decreases and its vapour pressure is lowered Fig (9.6 b)

A quantitative relationship between the change of vapour pressure of a solvent due to addition of non-
volatile and non-electrolyte solute and the mole fraction of solute has been given by Raoult law.
According to equation (3), Raoult says that relative lowering of vapour pressure is equal to the mole
fraction of solute.
= x2
418 Chapter # 9 (Solution)
If n2 and n1 are the number of moles of a solute and solvent respectively, then
x2 =
So, =
For a dilute solution, n2 can be ignored in denominator
Hence, =
The number of moles of solute and solvent are obtained by dividing their masses in grams with their
respective relative molecular masses. If W 1 and W2 are the masses of solvent and solute while M 1 and M2 are
their relative molecular masses respectively, then
n2 = and n2 =
=
=  …….. (5)
or M2 =  ……… (6)
The molecular mass (M2) of a non-volatile solute can be calculated from the equation (6).
S.Q59 How the relative lowering of vapour pressure can help us to calculate the molar mass of a non-
volatile, non-electrolyte solute?
Ans. According to the third definition of the Raoult's law, the relative lowering of vapour pressure is equal to
the mole fraction of the solute.
= X2
Since X2 = = (n1 >> n2)
So, =
Or M2 = M1 .
From this equation molar mass can be calculated
S.Q60 Why a non-volatile solute in a volatile solvent lowers the vapour pressure of solution?
Ans: The vapour pressure of a liquid is decreased, when a non-volatile solute is dissolved in a volatile solvent
due to following reasons.
(i) Due to presence of solute particles, the escaping tendency of solvent particles from the surface fo the
solution decreases and its vapor pressure is lowered.
(ii) Forces of attraction are produced between solute and solvent particles, which also hinders the
evaporation of solvent molecules and its vapour pressure decreases. ' . :
MCQs
1. When a non-volatile solute is added to a solvent, its vapour pressure
(a) increases (b)  decreases
(c) remains constant (d) many increase or decrease.
2. The lowering of vapour pressure depends upon
(a)  Number of solute particles (b) molar mass of solute
(c) Structure of solute particles (d) none of these
3. The relative lowering of vapour pressure is
(a) equal to the mole fraction of solvent (b) equal to the mole fraction of solute
(c) directly proportional to the mole fraction of solute (d) both b & c
4. The relative lowering of vapour pressure is directly proportional to morality if the solution is
(a) concentrated dilute (b) dilute (c) saturated (d) all of the above
5. Molarity of pure water is (RWP-2010)
(a) l.0 (b) 18.0 (c) 55.5 (d) 6.0
Professor CHEMISTRY - XI (Subjective) 419

Example 10: (L.Q)

Pure benzene has a vapour pressure of 122.0 torr at 32°C. When 20g of a non- volatile solute were
dissolved in 300g of benzene, a vapour pressure of 120 torr was observed. Calculate the molecular mass
of the solute. The molecular mass of benzene being 78.1.
Solution
Let the molecular mass of the solute be = M2
Mass of solute dissolved (W2) = 20 g
Vapour pressure of pure solvent (p°) = 122.0 torr
Vapour pressure of solution (p) = 120.0 torr
Lowering of vapour pressure (p) = 122.0 – 120.0 = 2.0 torr
Mass of solvent (W) = 300 g
Molar mass of solvent (M3) = 78.1
Formula applied
= 
M2 = 
Putting the values
M2 =  = Answer
9.6.3 Elevation of Boiling Point (L.Q)
(LHR, SRG-09, 16, D.G.K-07, BHR-11, RWP-2017, LHR-2010, MLT-2009, 2011, 2012, GUJ-2011)
The presence of a non-volatile solute in the solution decreases the vapour pressure of the solvent.
Greater, the concentration of solute, greater will be the lowering of vapour pressure. Therefore, the
temperature at which a solvent in the solution state boils is increased.
In order to understand it, determine the vapour pressures of a
solvent at various temperatures. Plot a graph between temperatures on x-
axis and vapour pressures on y-axis. A rising curve is obtained with the
increase of temperature. The slope of the curve at high temperature is
greater, which shows that at high temperature the vapour pressure
increases more rapidly. Temperature T1 on the curve AB which is for the
pure solvent, corresponds to the boiling point of the solvent. The solvent
boils when its vapour pressure becomes equal to the external pressure
represented by p°.
When the solute is added in the solvent and vapour pressures are
plotted vs temperatures, then a curve CD is obtained. This curve is lower
than the curve AB because vapour pressures of solution are less than those
of pure solvent. Solution will boil at higher temperature T 2 to equalize its
pressure to p°. The difference of two boiling points gives the elevation of
the boiling point Tb.
The higher the concentration of solute, the greater will be the lowering in vapour pressure of solution
and hence higher will be its boiling point. So, elevation of boiling point Tb is directly proportional to the
molality of solution.
Tb = Kb m ….(8)
Where Kb is called the ebullioscopic constant or molal boiling point constant.
According to equation (8), molality of any solute determines the elevation of boiling point of a solvent.
You may dissolve 6 g of urea in 500 g of H2O or 18 g of glucose in 500 g of H2O both give 0.2 molal solution
and both have same elevation of boiling points i.e. 0.1°C, which is l/5th of 0.52°C. We say that Tb (not T) is a
colligative property.
420 Chapter # 9 (Solution)
We know that,
Molality (m) = 
or m= =
Putting the value of m from equation (9) into equation (8)
Tb = Kb ……… (10)
Rearranging equation (10)
Molecular mass (M2) =  1000 ……….. (11)
Equation (11) can be used to determine the molar mass of a non-volatile and non- electrolyte solute in a
volatile solvent.
9.6.4 Measurement of Boiling Point Elevation (L.Q)
Landsberger's Method (LHR-2007, D.G.K-2017, SHW-2017)
This is one of the best methods for the measurement of boiling point elevation of a solution. The
apparatus consists of four major parts.
(a) An inner tube with a hole in its side. This tube is graduated.
(b) A boiling flask which sends the solvent vapours into the graduated tube through a rosehead.
(c) An outer tube, which receives hot solvent vapours coming from the side hole of the inner tube.
(d) A thermometer which can read up to 0.01K.
The solvent is placed in the inner tube. Some solvent is also
taken in a separate flask and its vapours are sent into this tube. These
vapours cause the solvent in the tube to boil by its latent heat of
condensation. This temperature is noted which is the boiling point of the
pure solvent.
The supply of the vapours is temporarily cut off and a weighed
pellet of the solute is dropped in the inner tube. The vapours of the
solvent are again passed through it until the Fig(9.8) Landsberger
method for solution is boiled. This temperature is again noted. Fig
(9.8).
Now, the supply of the solvent vapours is cut off. The
thermometer and the rosehead are removed and the volume of the
solution is measured. The difference of the two boiling points gives the
value of Tb. The following formula is used to calculate the molecular
mass of solute.
M2 = ……… (11)
S.Q61 What are the names of four major parts of apparatus used in Landsberger's method for elevation
of boiling point? (LHR-2016)
Ans. It consists of
• An inner boiling graduated tube with a hole in the side
• A boiling flask, which sends vapours of solvent to the inner tube through a rose head.
• An outer tube, which receive vapours of hot solvent through the hole of inner tube.
• A Beckmann thermometer that can read upto 0.01 K.
MCQs
1. The molal boiling point elevation depends upon (FSD 2008)
(a) nature of solvent (b) vap. pressure of solution
(c) nature of solute (d) H of solution
2. A thermometer used in Lands Berger's method can read (RWP-2013)
Professor CHEMISTRY - XI (Subjective) 421
(a) 0.1 K (b) 0.01 F (c ) 0.01 K (d) 0.01°C
3. The molal boiling point elevation depends upon: (FSD-2008)
(a) Nature of solvent (b) Vapour pressure of solution
(c) Nature of solute (d) H solution
4. Elevation of boiling point is: (SHW-2014)
(a) Additive property (b) Constitutive property
(c) Colligative property (d) Substitutive property
5. In the Landsberger's method, the solvent is boiled by
(a) Latent heat of sublimation (b) Latent heat of vaporization
(c)  Latent heat of condensation (d) None of these
Example 11:
The boiling point of water is 99.725 °C. To a sample of 600g of water are added 24.0 g of a solute having
molecular mass of 58 g mol1, to form a solution. Calculate the boiling point of the solution.
Solution
Boiling point of pure H2O = 99.725 °C
Mass of solvent (H2O) W1 = 600 g
Mass of solute (W2) = 24.00 g
Molar mass of solute (M2) = 58 g mol–1
The molal boiling point constant of H2O (Kb) = 0.52 °C
Formula
Tb = Kb 
=
Boiling point of solution = boiling point of pure solvent + elevation of boiling point
= 99.725 + 0.358 = Answers
9.6.5 Depression of the Freezing Point of a Solvent by a Solute (L.Q)
The freezing point of a substance is the temperature at which the solid and liquid phases of the substance
co-exist. Freezing point is also defined as that temperature at which its solid and liquid phases have the same
vapour pressures. When a non-volatile solute is added to a solvent, its vapour pressure is decreased. At the
freezing point, there are two things in the vessel i.e. liquid solution and the solid solvent. The solution will
freeze at that temperature at which the vapour pressures of both liquid
solution and solid solvent are same. It means that a solution should
freeze at lower temperature than pure solvent.
In order to understand it, plot a graph between vapour pressure
temperature for pure solvent and that of solution. The curve ABC is for
the pure solvent. The solvent freezes at temperature T corresponding to
the point B when the vapour pressure of freezing solvent is p°. The
portion of the curve BC is for the solid solvent. This portion has a greater
slope showing that the change of vapour pressure with the change of
temperature is more rapid Fig (9.9)
The curve DEC for the solution will meet the curve BC at the
point E. This is the freezing point of solution T 2, and corresponds to the
vapour pressure p which is lower than p°. The reason is that vapour
pressure of solution is less than the pure solvent.
Depression of freezing point = freezing point of pure solvent – freezing point of solution.
So, Tf = T1 – T2
This depression in freezing point Tf, is related to the molality (m) of the solution. The relationship is
422 Chapter # 9 (Solution)
similar to that of elevation of the boiling point.
Tf  m
Tf = Kf m …….. (12)
Kf is called the molal freezing point constant or the cryoscopic constant and m is the molality of the
solution. To get the final expression, let us put the following expression (9) of molality into the equation (12)
i.e.
m = ……… (9)
We get Tf = Kf  ……… (13)
Where W2 = mass of solute and M2 = molar mass of the solute, W1 = mass of solvent in kg Rearranging
equation (13)
Molar mass of solute (M2) = …….. (14)
9.6.6 Measurement of Freezing Point Depression (L.Q)
Beckmann's Freezing Point Apparatus:
There are many methods but Beckmann's method is easy to perform. The apparatus consists of three
major parts. Fig.(9.10).
Fig (9.10) Beckmann's freezing point apparatus (LHR-2014, SRG-2017, GUJ-2009, 2014, LHR-2014,
FSD-2016)
a. A freezing tube with a side arm. It contains solvent or solution and is fitted with a stirrer and a
Beckmann's thermometer.
b. An outer larger tube into which the freezing tube is adjusted. The air jacket in between these tubes help
to achieve a slower and more uniform rate of cooling.
c. A large jar containing a freezing mixture. Around 20 to 25g of the
solvent is taken in the freezing tube. The bulb of the thermometer,
is immersed in the solvent. First of all, approximate freezing point
of the solvent is measured by directly cooling the freezing point
tube in the freezing mixture.
The freezing tube is then put in the air jacket and cooled slowly.
In this way, accurate freezing point of the solvent is determined. Now, the
solvent is re-melted by removing the tube from the bath and weighed
amount of 0.2 to 0.3 g of the solute is introduced in the side tube. The
freezing point of the solution is determined while stirring the solution. The
difference of the two freezing points gives the value of Tf and the
following formula is used to calculate the molar mass of solute.
M= ………. (14)
S.Q62 Why the boiling point of a solution of a non-volatile solute in a volatile solvent is always greater
than the boiling point of a pure solvent? (GUJ-2008)
Ans. The elevation of the boiling point of the solution is due to the lowering of vapour pressure of the
solution as compared to the pure solvent. In the case of solution the vapour pressure becomes less. In
order to equalize the vapour pressure of the solution to the external pressure more temperature is
required than that in the pure state o solvent, which causes elevation of boiling point.
S.Q63 Why Beckmann thermometer is used to note the depression of freezing point? (RWP-2007, MLT-
2009, BHR-2011)
Ans. Beckmann thermometer can measure up to 1/20 th of the degree. The elevation of boiling points and the
depressions of freezing points for dilute solutions are very small quantities. Hence, can measure these
very small increase or decrease of temperatures.
S.Q64 Why Beckmann’s thermometer is used to find increase in the boiling point?(Rwp 07)
Professor CHEMISTRY - XI (Subjective) 423
Ans. As elevation of boiling points or depression of freezing point is very small in magnitude so a sensitive
thermometer was developed by “Beckmann”., It can read upto 1 /100 th of a degree Celsius or 0.01 K. It
can detect a very little change in boiling point or freezing point much accurately. Therefore Beckmann
thermometer is used to note the increase in the boiling point.
MCQs
1. Which has the minimum freezing point?
(a) One molar NaCl (b) One molar KC1 solution
(c) One molar CaCl2 (d) One molal urea solution
2. The temperature at which the substance co-exist in both liquid and solid phases is called
(a) freezing point (b) boiling point (c) both a & b (d) none of these
3. Depression of freezing point is directly proportional to (Mirpir-2004, LHR-20G5)
(a) molarity of solution (b) molarity of solvent
(c)  molality of solution (d) molality of solvent
4. Bedkmann's apparatus is used to measure
(a) boiling point elevation (b) depression in freezing point
(c) lowering of vapour pressure (d) lowering of osmotic pressure
5. Depression of freezing point of a solvent in one molal solution is called
(a)  Cryoscopic constant (b) Ebullioscopic constant
(c) Plank's constant (d) Avogadro's constant
6. The cryoscopic constant of water is 1.86°C. The elevation of b.p for 0.1 m solution of a solute in
water is
(a) 18.6°C (b) 1.86°C (c) 0.186°C (d) 1.086
7. The molal freezing point constant is also called as:
(a) Arrhenius constant (b) ebllioscopic constant
(c) Boltzmann constant (d)Cryoscopiq constant
8. Beckman's thermometer reads upto:
(a) 1.0 K (b) 0.1 K (c) 0.01 K (d) 0.02 K
Example 12: (L.Q)
The freezing point of pure camphor is 178.4°C. Find the freezing point of a solution containing 2.0 g of a
non-volatile compound, having molecular mass 140, in 40g of camphor. The molal freezing point constant
of camphor is 37.7 °C kg mol1.
Solution:
Freezing point of camphor = 178.4 °C
Mass of solute (W2) = 2.00 g
Mass of solvent (W2) = 40 g
Molar mass of solute (M2) = 140
Molal freezing point constant of solvent = 37.7° C kg mol–1
Freezing point of solution =?
Applying the equation
Tf = Kf
We have to calculate, the freezing point of solution, so first we get the depression in freezing point
AT( then subtract it from freezing point of pure solvent.
= 13.46oC
Freezing point of solution = 178.4 – 13.46 = Answer
424 Chapter # 9 (Solution)
9.6.7 Applications of Boiling Point Elevation and Freezing Point (S.Q)
Apart from the molecular mass determination, the presence of a solute increases the liquid range of the
solution both by raising the boiling point and lowering the freezing point. The most important application of this
phenomenon is the use of an antifreeze in the radiator of an automobile. The solute is ethylene glycol, which is
not only completely miscible with water but has a very low vapour pressure and non-volatile in character. When
mixed with water, it lowers the freezing point as well as raises the boiling point. During winter it protects a car
by preventing the liquid in the radiator from freezing, as water alone, if it were used instead. In hot summer, the
antifreeze solution also protects the radiator from boiling over.
Another, common application is the use of NaCl or KNO3 to lower the melting point of ice. One can
prepare a freezing mixture for use in an ice cream machine.
S.Q65 Why the freezing point of the solution is always less than the freezing point of the pure solvent?
(Mirpure-2004, LHR, FSD-2009)
Ans. The depression of freezing point of the solution is due to lowering of vapour pressure of the solution as
compared to the pure solvent. A graph between temperature and vapour pressure shows that the curve
for the solution lies below the curve for the pure solvent. The curve for the solution touches the curve for
the solid phase of the pure solvent at a lower temperature, than the freezing point of the pure solvent.
S.Q66 Why the freezing points are depressed due to presence of solutes?(LHR-2007, FSD-2010, RWP-
2011, GUJ-2012)
Ans. The lowering of vapour pressure compels the solutions, to freeze at those temperatures, which are below
the freezing point of pure solvent. The reason is that the vappur pressure temperature curve meets the
solid phase of pure solvent at lower temperature than the pure solvent.
S.Q67 summer the antifreeze solutions protect the radiator from boiling over. Why? (RWP-2007, MLT-
2008, D.G.K-2012)
Ans. Water boils at 100°C. It is used in the radiators to decrease the temperature of the working engine. If we
add some suitable solutes which increase the boiling point of water, above 100°C, then easy boiling over
of water is avoided.
S.Q68 Ethylene glycol may be used in radiator of an automobile. Give two aspects of its use (MLT-2008:
GUJ-2013: D.G.K-2015. 2017)
Ans. The ethylene glycol is added to water in radiators of automobile. It is completely miscible with H 2O and
almost non-volatile. Thus it depresses the freezing point of H2O and elevates its boiling point. Hence,
(i) in winter, it prevents the freezing of water in winter.
(ii) in summer, it protects the liquid of radiator from boiling over.
S.Q69 Describe that NaCl and KNO3 are used to lower melting point of ice. (GUJ-2008)
Ans. At freezing point the vapour pressure of liquid and solid phases are same. However, when NaCl or
KNO3 is added to H2O, some surface is occupied by solute particles. So. the escaping tendency of water
is decreased. Thus vapour pressure is decreased. Due to lowering of vapour pressure, the freezing point
of water (or melting point of ice) is decreased.
MCQs
1. In ice cream formation mechanism, freezing mixture consists of ice and
(a) KCI (b) Na2SO3 (c) MgCl2 (d) NaCl
2. Chemical used to protect a car by preventing a liquid in the radiator from freezing is (FSD-2009)
(a) phenol (b) ethylene glycol (c) KNO3 (d) methanol
3. Use of antifreeze in the automobile is an important application of
(a) Constitutive property (b) Additive property
(c) Collegiate property (d) Intensive property
4. Chemical used to protect a car by preventing the liquid in the radiator from freezing is. (FSD-09)
Professor CHEMISTRY - XI (Subjective) 425
(a) Phenol (b)  Ethylene glycol (c) KNO3 (d) Methanol
5. Which is a colligative property?
(a) Change in vapour pressure of a solution (b) Change in free energy of a solution
(c) Heat of vaporization of solvent in the solution (d) Lowering of vapour pressure of a solution

9.7.0 ENERGETICS OF SOLUTION (L.Q)

In a solution, the distances between solute and solvent molecules or ions increase somewhat as
compared with their pure states. This increase in the distance of solvent molecules requires energy to overcome
the cohesive intermolecular forces. Hence, it is an endothermic process. Similarly, the separation of solute
molecules also needs energy so it is also an endothermic process. The intermixing of solute with solvent
molecules is to establish new intermolecular forces between unlike molecules. It releases energy and thus is an
exothermic phenomenon. The strengths of the two type of forces will decide whether the process of
dissolution will be endothermic or exothermic.
Thus, the process of dissolution occurs with either an absorption or release of energy. This is due to
breakage and re-establishment of intermolecular forces of attraction between solute and solvent molecules.
When potassium nitrate is dissolved in water, the temperature of the solution decreases. It shows it to
be an endothermic process. The solution of lithium chloride in water produces heat, showing that the process of
dissolution is exothermic. The quantity of heat energy, that is absorbed or released when a substance forms
solution, is termed as heat of solution.
So, the enthalpy or heat of solution of a substance is defined as the heat change when one mole of
the substance is dissolved in a specified number of moles of solvent at a given temperature. It is given the
symbol Hsoln. The Hsoln gives the difference between the energy possessed by the solution after its formation
and the original energy of the components before their mixing i.e.
Table (9 4) Heats of solution of some ionic solids
Heats of solution
Substance
(kJ mol–1)
NaCl 4.98
NH4NO3 26.0
KC1 17.8
KI 21.4
NHJCL 16.2
LiCl –35.0
Li2CO3 –12.8
Here, Hsoln is the energy content of solution after its formation, while H components represents the
energy contents of components before their mixing. However, both these factors can not actually be measured,
only their difference i.e. the change Hsoln is practically measurable. If the value of Hsoln is negative, it would
mean that the solution is having less energy than the components from which it was made, hence the dissolution
process is an exothermic one. On the other hand, an endothermic process would have a positive Hsoln value. In
Table (9.4) are given values of heats of solution of different ionic solids in water at infinite dilution.
The magnitude of heat of solution gives information regarding the strength of intermolecular forces of
attraction between components which mix to form a solution.
When one mole of sodium chloride (58.5g) is dissolved in 10 moles of water (180g), then 2.008 kJ of
energy is absorbed.
NaCl + 10 H2O  NaCl (10H2O) H = + 2.008 kJ
9.7.1 Hydration Energy of Ions (S.Q)
426 Chapter # 9 (Solution)
When an ionic compound, say potassium iodide is dissolved in water, the first step, is the separation
of K and I– ions from solid. In the second step, these separated ions are surrounded by solvent molecules. The
+

first step breaks the lattice to separate the ions. Since, energy is required to accomplish this step, so this step is
endothermic. The amount of energy needed to separate a crystalline compound into isolated ions (or
atoms) is known as lattice energy. The lattice energy of ionic solids is always higher than molecular solids.
In the second step, the ions are brought into water and get hydrated (solvated) Fig.(9.11). A hydrated
ion is attracted by the solvent dipoles and energy is released, so this step is exothermic. The energy given out
by this step is known as the hydration energy (or solvation energy).
K+ + I– + xH2O  K+(aq) + I–(aq)
Fig (9.11) Interaction between water molecules and cations and anions provide the energy necessary to
overcome both the intermolecular forces between water molecules and the ionic bond in a potassium iodide.
The final equation will be as follows:
Table (9.5) Hydration energies of common ions
Ion H° (ion mole–1)
H+ –1075
Li + – 499
Na+ – 390
Ag+ – 464
K+ – 305
M g 2+ – 1891
Cu2+ – 1562
NH4+ – 281
F– – 457
Cl– – 384
Br– – 351
OH – 460
KI(s) + xH2O  K+(aq) + I–(aq)

The values of hydration energies of individual ions, i.e. cations and anions are given in Table(9.5). It is
Professor CHEMISTRY - XI (Subjective) 427
interesting to compare these values with the ionic radii of the ions. Greater the size of monovalent cation,
lesser is the heat of hydration. Divalent and trivalent cations have higher values due to high charge densities.
Anions also show a definite trend of heat of hydration, depending upon their sizes.
On diluting a concentrated solution, there is a further heat change. This heat change depends on the
amount of water used for dilution. The heat of dilution gradually decreases, so that eventually increasing the
dilution produces no further heat change. This occurs when there are 800-1000 moles of water to one mole of
solute. This stage is called infinite dilution and the heat of solution is expressed as:
NaCl(s) + H2O  NaCl(aq) Na+(aq) + Cl–(aq) Hsoln = + 4.98 kJ mol–15

S.Q70 What is meant by hydration?

Ans. The process in which water molecules surrounds and interact with solutions or molecules is called
hydration, e.g.
When ionic compounds are dissolved in water, they are dissociate into ion. The partial positively
charged hydrogen atoms of water surround and attract the anions with ion-dipole forces and the partial
negatively charged oxygen atoms of water molecules surround and attracts the cations of solute. In this
way, all the ions in the aqueous solution are hydrated.
S.Q71 When the heat of solution is negative, then increase in temperature decreases the solubility and
vice versa. Why? (SRG-2008)
Ans. When the heat of solution is negative, it means that the vessel is heated up during the solution formation.
So, when heat is supplied from outside, then the system will go to that side where greater amount of heat
can be stored and that is the side of low solubility.
S.Q72 Heat of solution of a substance is measured at infinite dilution. Why? (LHR-2006-07, SRG-2008,
GUJ-2008)
Ans. Actually the maximum amount of heat is evolved or absorbed, when each particle of one mole of solute
is completely solvated by the solvent molecules. These solvated particles of the solute should be far
away from each other in the solution. This is only possible when this solution is very dilute.
MCQs
1. Hydration is a process in which
(a) Molecules are surrounded by solvent molecules
(b) Ions are surrounded by solvent molecules
(c) Both ions and molecules are surrounded by solvent molecules
(d) Both ions and molecules are surrounded by water molecules
2. Water molecules surrounds more around
(a) +ve ion (b) complex ion (c) –ve ion (d) neutral atom
3. Which cation has least heat of hydration?
(a) Li+ (b) Na+ (c)  K+ (d) Mg++
__________________
9.8 HYDRATION AND HYDROLYSIS
9.8.1 Hydration (S.Q)
When ionic compounds are dissolved in water, they are dissociated into ions. Negative ions are
surrounded by water molecules. The partial positively charged hydrogen atoms of water surround and attract the
anions with electrostatic forces of attraction. Similarly positive ions of solute create attractions with partial
negative oxygen atoms of water molecules. In this way, all the ions in the aqueous solution are hydrated.
428 Chapter # 9 (Solution)
The process in which water molecules surround and interact with solute ions or molecules is called
hydration.
The ions, which are surrounded by water molecules, are called hydrated ions. The number of water
molecules, which surround a given ion depends upon the size of the ions and the magnitude of its charge
(charge/area). If the size of the ion is small and is highly charged positive ion, it has high charge density. Hence,
greater number of water molecules will surround it. Negatively charged ions have low charge density, and have
smaller number of water molecules surrounding them. Hence, the ion with high charge density has a greater
ability to attract polar water molecules than ions with smaller charge density.
9.8.2 Hydrates (S.Q)
The crystalline substances, which contain chemically combined water in definite propagations is
called a hydrate. Hydrates are mostly, produced when aqueous solution of soluble salt is evaporated. The
formation of hydrates is not limited to salts but is common with acids, bases and elements.
The water molecules are attached with cations in the hydrates. Anyhow, in CuSO 4.5H2O, four water
molecules, are attached with Cu 2+ and one with SO. The reason is that Cu 2+ has a greater charge density. The
size of Cu2+ is much smaller than SO, which has same amount of charge.
Water of Crystallization
Those water molecules, which combine with substances as they are crystallized from aqueous
solutions, are called water molecules of crystallization or water of hydration. Some familiar examples are
as follows:
(COOH)2.2H2O(oxalic acid), BaCl2.2H2O, Na2CO3.10H2O, MgCl2.6H2O, Na2B4O7.10H2O (borax), CaSO4.2H2O
(gypsum), MgSO4.7H2O (epsom salt) and AlCl3.6H2O.
9.8.3 Hydrolysis (L.Q) (RWP-2010, SRG-2013, D.G.K-2010, AZK-2012, LHR-2016)
When NaCl is dissolved in water, the resulting solution is neutral i.e. the concentration of each of H + and
OH– ions are equal to 10–7 M, as in pure water. But this balance between H + and OH– ions can be disturbed with
resulting change in the pH of solution when other salts are dissolved in water.
It is commonly, observed that different salts, upon dissolving in water, do not always form neutral
solutions. For example, NH4Cl, AlCl3, CuSO4 give acidic solutions in water. On the other hand, Na2CO3 and
CH3COONa form basic solutions in water. These interactions between salts and water are called
hydrolytic reactions and the phenomenon is known as hydrolysis. It involves the reactions of the ions of
different salts to give acidic or basic solutions. It is the decomposition of compounds with water, in which
water itself is decomposed.
The hydrolysis of the salts mentioned above are shown as follows:
NH4Cl + H2O NH4OH + H+ + Cl–
AlCl3 + 3H2O Al(OH)3 + 3H+ + 3Cl–
CuSO4 + 2H2O Cu(OH)2 + 2H+ + SO
These hydrolytic reactions, produce weak bases Al(OH) 3, NH4OH and Cu(OH)2. But, Cl– and SO are
weak conjugate bases of HCl and H2SO4. They are not hydrolysed in water. H+ ions remain free in solution and
so their solution are acidic in character.
The Ka Values of HCl and H2SO4 are very high as compared to Kb values of Al(OH)3, NH4OH and
Cu(OH)2.
For CH3COONa the reaction with water is
CH3COONa + H2O CH3COOH + Na+ + OH
The acetate ion is hydrolyzed in water to give CH 3COOH and OH– becomes free. Na+ is not hvdrolysed.
The result is that the solution becomes basic in nature. Similarly, Na3PO4, Na3AsO4 etc give basic solutions in
water due to the formation of a Na+ ,OH and weak acids H3PO4 and H3AsO4, which are least dissociated.
The dissolution of KCl, Na2SO4, KBr, etc in water give neutral solutions. Because these salts are not
hydrolysed in water. Their positive ions K+, Na+ are not hydrolysed by water. Similarly, their negative ions Cl –,
Professor CHEMISTRY - XI (Subjective) 429
Br– , SO are also not hydrolysed. It means that the salts of strong bases and strong acids are not hydrolysed by
water.
Anyhow, the salts derived from weak acids and weak bases may not give neutral solutions. It depends
upon the pKa and pKb values of acid and base produced.
S.Q73 What are hydrates? How are they formed? Give examples. (LHR-2007: BHR-2008, 2009. RWP-
2010, D.G.K-2012, MLT-2010, FSD-2013, GUJ-2013,
Ans. The crystalline substance, containing chemically combined H 2O in definite proportions is called hydrate
Examples
CuSO4.5H2O, Na2SO4.10H2O
Hydrates are prepared by evaporating their aqueous solutions.
S.Q74 What is meant by water of crystallization? Give two examples. (LHR-2010,2014: SHW-2015)
Ans. The water molecules, which are attached with compound when crystallized from aq. solution, are called
water of crystallization.
Example: (COOH)2.2H2O (Oxalic acid) CaSO4.2H2O (Gypsum)
S.Q75 Define hydrolysis and give its examples. (RWP-2010: GUJ-2011. LHR-2015. SHW- 2016)
Ans. The process in which water reacts chemically with the added solute is called hydrolysis .
Example 1:
Consider hydrolysis of CuSO4 .It ionizes as
CuSO4 Cu2+ + SO
Cu2+ + 2H – OH Cu(OH)2 + 2H+
Due to formation of H+ ions, the aq. solution of CuS04 is acidic.
S.Q76 Differentiate between hydration and hydrolysis with one example each. (LHR-2008. SRG-202011,
MLT-2012, 2016: D.G.Khan-2016, 2017: LHR-2017: FSD-2017)
HYDRATION HYDROLYSIS
(1) The process in which water molecules (1) The process in which water reacts
surround and interact with the solute particles chemically with the added solute is called
without breaking any bond is called hydrolysis
hydration
(2) It forms saturated compounds from (2) It forms hydrated compounds from
unsaturated compounds. dehydrated compounds.
(3) Largely physical interactions occur between (3) Chemical reaction occurs between solute
solute and water molecules particles and water molecules.
S.Q77 Dissolve of KCl and Na2SO4 in water give neutral solution. Why? (LHR-2011)
Ans. KCl ionizes as KCl K+ + Cl–
Both K+ and Cl– are not hydrolyzed by H2O. Therefore, it’s solution will be neutral.
Thus salts of strong acids and strong bases are not hydrolyzed by water. Similarly the solution of
Na2SO4 is also neutral.
S.Q78 The solution of Na2CO3 in water is basic in nature. (D.G.K-2007, 2008, RWP-2017)
Ans. Na2CO3 ionizes as
Na2CO3 2Na+ + CO
CO hydrolyze in water to produce basic solution.
CO + 2H – OH H2CO3 + 2OH–
430 Chapter # 9 (Solution)
So due to formation of OH-ions, the aq. Solution of Na2CO3 is basic.
MCQs
1. Number of H2O molecules of crystallization in oxalic acid is
(a) 5 (b) 4 (c) 3 (d) 2
2. Water of crystallization can be removed by
(a) drying (b) heating (c) evaporation (d) all of the above
3. Salts of weak acids with strong bases react with water to produce
(a) neutral solution (b) acidic solution (c) basic solution (d) all of these
4. Which one of the following substances when dissolved in water give acidic solution (MLT-2007,
BHR-2008)
(a) NaCl (b) Na2SO4 (c) NH4Cl (d) NH4COOCH3
5. Upon hydrolysis CH3COONa solution shows
(a) Basic character (b) acidic character
(c) amphoteric character (d) none of these
6. Solution of Na2SSO4 will be
(a) basic (b) acidic (c) neutral (d) cannot be predicted
7. Which one of the following salt does not hydrolysed
(a) Na2SO4 (b) AlCl3 (c) CuSO4 (d) NH4C1
8. Which one of the following aqueous solutions will be basic?
(a) NaCl (b) Na2SO4 (c)  Na2CO3 (d) FeCl3
9. Which one of the following gives acidic solution when dissolved in H2O (RWP-2011)
(a) NaCl (b) Na2SO4 (c) NH4Cl (d) CH3COONH4
10. The hydration energy of Br–1 ion in comparison of F–1 ion.
(a) less (b) Greater (c) Equal (d) None of these
11. Hydration and hydrolysis are
(a) same (b) Different (c) Both a and b (d) None of these
12. Hydrolysis of CH3COOK will produce:
(a) Acidic solution (b) Basic solution (c) Neutral solution (d) None of these
_______________

KEY POINTS
 A solution, on average, is a homogeneous mixture of two or more kinds of different molecular or ionic
substances. The substance, which is present in a large quantity, is called a solvent and the other in
small quantity is, called a solute.
 Solutions containing relatively lower concentrations of solute are called dilute solutions, whereas
those containing relatively higher concentrations of solutes are called concentrated solutions.
Solubility is the concentration of a solute in a solution, when the solution is at equilibrium with the
solute at a particular temperature.
 The concentration of a solution may be expressed in a number of ways.
(i) percentage composition, ii) molarity, iii) molality, iv) mole fraction, v) parts per million.
 Solutions may be ideal or non-ideal. Those solutions, which obey Raoult's law are ideal solutions.
Raoult's law tells us that the lowering of vapour pressure of a solvent by a solute, at a constant
temperature, is directly proportional to the concentration of solute.
 Many solutions do not behave ideally, as they show deviations from Raoult's law. A solution may
show positive or negative deviation from Raoult's law. Such liquid mixtures, which distill without
Professor CHEMISTRY - XI (Subjective) 431

change in composition, are called azeotropic mixtures.

 Colligative properties of a solution are those properties, which depend on the number of solute and
solvent molecules or ions and are independent of the nature of solute. Lowering of vapour pressure,
elevation of boiling point and depression of freezing point and osmotic pressure are the important
colligative properties of solutions.
 Elevation of boiling point of a solvent in one molal solution is called molal boiling point constant or
ebullioscopic constant. Depression of freezing point of a solvent in one molal solution is called molal
freezing point constant or cryoscopic constant.
 The enthalpy or heat of solution of a substance is the heat change when one mole of the substance is
dissolved in a specified number of moles of splvent at a given temperature.
 The process in which water molecules surround and interact with solute ions or molecules is called
hydration. The crystalline substances, which contain molecules of water in their crystal lattices, are
called hydrates. They are mostly produced, when aqueous solutions of soluble salts are evaporated.
 Salts of weak acids with strong bases react with water to produce basic solutions, whereas salts of
weak bases with strong acids react to give acidic solutions. Such reactions are called hydrolytic
reactions, and the salts are said to be hydrolysed. Salts of strong acids and strong bases do not
hydrolyse and give neutral solution.

EXERCISE
Q1. Choose the correct answer for the given ones.
i) Molarity of pure water is (FSD-14,17, GUJ-14,15,17, BHR-14,15,16,17), MLT-11,12,16, LHR-
14,17, AZK-16, SHW-16, RWP-10, 15, 16, D.G.K-09, 12, 17.
(a) 1 (b) 18 c)  55.5 (d) 6
ii) 18 g glucose is dissolved in 90 g of water. The relative lowering of vapour pressure is equal to
(AZK-16, MLT-14, 15, 16, RWP-12, FSD-15, 16, LHR-15, 16)
(a) (b) 5.1 (c)  (d) 6
iii) A solution of glucose is 10% w/v. The volume in which 1 g mole of it is dissolved will be
(RWP-17, MLT-16, SRG-12, D.G.K-12, 14, 16)
(a) ldm 2
(b) 1.8 dm 2
(c) 200 cm3 (d) 900 cm5
iv) An aqueous solution of ethanol in water may have vapour pressure
(a) equal to that of water (b) equal to that of ethanol
(c) more than that of water (d) less than that of water
v) An azeotropic mixture of two liquids boils at a lower temperature than either of them when:
(a) it is saturated
(b) it shows positive deviation from Raoult's law
(c) it shows negative deviation from Raoult's law (d) it is metastable
(vi) In azeotropic mixture showing positive deviation from Raoult's law, the volume of the mixture is
(a) slightly more than the total volume of the components
(b) slightly less than the total volume of the components
(c) equal to the total volume of the components (d) none of these
(vii) Which of the following solutions has the highest boiling point?
(D.G.K-09, MLT-10, SRG-10, LHR-10)
(a) 5.85 % solution of sodium chloride (b) 18.0 % solution of glucose
(c) 6.0 % solution of urea (d) All have the same boiling point
(viii) Two solutions of NaCl and KCl are prepared separately by dissolving same amount of the solute
432 Chapter # 9 (Solution)
in water. Which of the following statements is true for these solutions?
(a) KC1 solution will have higher boiling point than NaCl solution
(b) Both the solutions have different boiling points
(c) KCl and NaCl solutions possess same vapour pressure
(d) KCl solution possesses lower freezing point than NaCl solution
(ix) The molal boiling point constant is the ratio of the elevation in boiling point to
(SRG-09,14, GUJ-14,16, D.G.K-16)
(a) molarity (b) molality
(c) mole fraction of solvent (d) mole fraction of solute
(x) Colligative properties are the properties of (RWP-09, BHR-09)
(a) dilute solutions which behave as nearly ideal solutions
(b) concentrated solutions which behave as nearly non-ideal solutions
(c) both (i) and (ii) d) neither (i) nor (ii)
Q 2. Fill in the blanks with suitable words
(i) Number of molecules of sugar in 1 dm of 1M sugar solution is ______ .
(ii) 100 g of a 10 % aqueous solution of NaOH contains 10 g of NaOH in ______ g of water.
(iii) When an azeotropic mixture is distilled, its ______ remains constant.
(iv) The molal freezing point constant is also known as ______ constant.
(v) The boiling point of an azeotropic solution of two liquids is lower than either of them because the
solution ______ shows from Raoult's law.
(vi) Among equimolal aqueous solutions of NaCl, BaCL, and FeCl,, the maximum depression in freezing
point is shown ______ by solution.
(vii) A solution of ethanol in water shows ______ deviations and gives azeotropic solution ______ with
boiling point than other components.
(viii) Colligative properties are used to calculate ______ of a compound.
(ix) The hydration energy of Br ion is ______ than that of F– ion.
(x) The aqueous solution of NH4Cl is while that of Na2SO4 is.
Answers
(i) 6.02  1023 (ii) 90 g (iii) composition (iv) cryoscopic (v) positive deviations
(vi) FeCl3 (vii) positive lower (viii) molar mass (ix) less (x) acidic neutral
Q 3. Indicate True or False from the given statements
(i) At a definite temperature the amount of a solute in a given saturated solution is fixed.
(ii) Polar solvents readily dissolve non-polar covalent compounds.
(iii) The solubility of a substance decreases with increase in temperature, if the heat of a solution is negative.
(iv) The rate of evaporation of a liquid is inversely proportional to the intermolecular forces of attraction.
(v) The molecular mass of an electrolyte determined by lowering of vapour pressure is less than the
theoretical molecular mass.
(vi) Boiling point elevation is directly proportional to the molality of the solution and inversely proportional
to boiling point of solvent.
(vii) All solutions containing 1g of non-volatile non-electrolyte solutes in some solvent will have the same
freezing point.
(viii) The freezing point of a 0.05 molal solution of a non-volatile non-electrolyte in water is-0.93 °C.
(ix) Hydration and hydrolysis are different process for Na2SO4.
Professor CHEMISTRY - XI (Subjective) 433
(x) The hydration energy of an ion only depends upon its charge.
Answers
(i) True (ii) False (iii) True (iv) True (v) True (vi) True (vii) False
(viii) False (ix) False (x) False
Q4. Define and explain the fallowing with one example in each case.
(a) A homogeneous phase (f) Zeotropic solutions
(b) A concentrated solution (g) Heat of hydration
(c) A solution of solid in a solid (h) Water of crystallization
(d) A consulate temperature (i) Azeotropic solution
(e) A non-ideal solution (j) Conjugate solution
Ans. See chapter text
Q5. (a) What are the concentration units of solutions. Compare molar and molal solutions
Ans. See article.
(b) One has one molal solution of NaCl and one molal solution of glucose.
(i) Which solution has greater number of particles of solute?
(ii) Which solution has greater amount of the solvent?
(iii) How do we convert these concentrations into weight by weight percentage?
Ans. (i) NaCl dissociates in H2O, while glucose is not ionized. NaCl produces Na+ and Cl– ions. Thus number
of particles are increased. Hence, 1 molal NaCl solution contain greater number of particles than 1 molal
glucose solution.
(ii) Both solution has greater amount of the solvent.
Both are 1 molal solution i.e. 1 mole of solute is dissolved in 1 kg of solvent. Therefore, both will have
same amount of solvent.
(iii) How do we convert these concentrations into weight by weight percentage?
For 1 molal NaCl solution For 1 molal glucose solution
Moles of NaCl =1 Mass of glucose dissolved = 180 g
Mass of NaCl = 58.5 g Mass of solvent (water) = 1000 g
Since 1 mole of NaCl is dissolved in 1 kg of Total mass of solution = 1000 + 180 = 1180 g
solvent, therefore % of glucose =  100
Mass of solvent (water) = 1000 g % of glucose = =
Total mass of the solution = 1000 + 58.5 = 1058.5
% of NaCl =  100
% of NaCl = =
Q6. Explain the following with reasons
(i) The concentration in terms of molality is independent of temperature but molarity depends upon
temperature. (RWP-2007; GUJ-2009: FSD-2007, 2011: MLT-2011: Azad Kashmir-2015. D.G.K-
2016: LHR-2016. 2017: SRG-2017)
OR
Why the concentration of a molar solution is changed by uariation of temperature. (D.G.K-2008)
Ans. Molality is defined as the number of moles of solute dissolved in 1 kg of solvent, while
Molarity is defined as the number of moles of solute dissolved in 1 dm3 of solution.
434 Chapter # 9 (Solution)
Since molality is based upon mass, therefore, it is independent of temperature. While molarity is based
upon volume, therefore, it varies with temperature due to change in volume.
(ii) The sum of mole fractions of all the components is always equal to unity for any solution. (FSD-
2008. 2013 LHR-2010: D.G.K-2012: MLT-2012: GUJ-2015 SHW-2015)
OR
Prove that sum of mole fractions of all components is always equal to one. (RWP- 2008. 2017)
Ans. Consider a solution of two components A and B
Let moles of A are nA and that of B are nB
Their mole fractions are given by
xA = …. ( 1 )
xB = …. ( 2 )
Their sum of mole fractions will be
xA + xB …(3)
Put eq (1 ) and ( 2 ) in eq ( 3 )
+
Or =1
Hence, sum of mole fractions of different components in a solution is equal to one.
(iii) 100 g of 98% H^O, has a volume of 54.38 cm3
Ans. 98% H2SO4 has a density = d = 1.84 g/cm3
Mass of H2SO4 = m 100 g
Volume of H2SO4 = V = ?
Since d =
Or V = = = 54.38 cm3
(iv) Relative lowering of vapour pressure is independent of the temperature. (FSD-2008: SRG-2009 RWP-
2009: GUJ-2012)
Ans. According to Raoult's law
Relative lowering of vapour pressure is equal to the mole fraction of solute
i.e., = x2
where = Relative lowering of vapour pressure
while X2 = = mole fraction of solute
Since number of moles are not changed with temperature. Hence, relative lowering of vapour pressure
independent of temperature.
(v) Colligative properties are obeyed when the solute is non-electrolyte and also when the solution
are dilute. (GUJ-2009: RWP-2012: MLT-2012)
Ans. Colligative properties depend upon number of solute particles. If solute is electrolyte, then it will ionize
change the number of particles in the solution. Hence, value of colligative properties will be different
fror. :--: expected values and thus abnormal colligative properties are observed
Colligative properties require that solution should be dilute so that every solute particle behave
independently. In concentrated solution, solute particles don't behave independently. Hence, coiligative
properties are obeyed only when the solute is non-electrolyte and also when the solutions are dilute
(vi) The total volume of the solution by mixing 100 cm 3 of water with 100 cm3 of alcohol may not be
equal to 200 cm3 . Justify it. (SRG-2015)
Ans. During ideal solution formation volume1 is not changed. However, alcohol and water form a non-ideal
Professor CHEMISTRY - XI (Subjective) 435
solution. Forces of attraction between water and alcohol in pure state are greater than in solution. Thus,
it shows positive deviation from Raoults law. During the formation of this solution heat is absorbed and
volume decreases.
Hence 100 cm3 of H2O and 100 cm3 of alcohol may not be equal to 200 cm3.
(vii) One molal solution of urea in water is dilute as compared to one molar solution of urea, but
number of particles of the solute is same. Justify it. (FSD-2007, 2010, 2016: Azad Kashmir 2012,
MLT-2014: SRG-2016: BHR-2014, 2016: LHR-2015. 2016: D.G. Khan -2014, 2015
OR One molal glucose solution is dilute as compared to one molar solution of glucose. Why? (MLT-
2008: FSD-2009 RWP-2011: GUJ-2011: LHR-2013: SRG-2014)
OR Why a molar solution is more concentrated than a molar solution? (MLT-2010: D.G.Khan-2015)
Ans. Both 1 molal and 1 molar urea solution contain 1 mole of urea. Hence both these solutions contain same
number of particles i.e. 6.02  1023.
For 1 molal solution, 1 mole of urea is dissolved in 1 kg of water i.e. 1 dm3
However,
For 1 molar solution, 1 mole of urea is first taken in a measuring flask and then volume is made up to 1
dm3.
Therefore, 1 molar solution contains less amount of H 2O than 1 molal solution. Hence, 1 molal solution
of urea in water is dilute as compared to its on? molar solution.
(viii) Non-ideal solutions do not obey the Raoult's law
Ans. A solution, which does not obey Raoult's law, is called a non-ideal solution.
Non-ideal solutions show deviations from ideal behaviour due to difference in their molecular structure
i.e. size.; shape and intermolecular forces. In non-ideal solution, forces of attraction among molecules
of components do not remain same just as they were in pure form. Hence, they do not obey Raoult's
law.
Q7. What are norjrideal solutions? Discuss their types and give three example of each.
Ans Please see article
Q8. (a) Explain fractional distillation. Justify the two curves when composition is plotted against boiling
point of solutions.
Ans. Please see article
(b) The solutions showing positive and negative deviations cannot be fractionally distilled at their specific
compositions. Explain it.
Ans. Please see article
Q9. (a) What are azeotropic mixtures? Explain them with the help of graphs? OR What are azeolropes
(or azeotropic mixture)? Give one example. (D.G.K-2007: MLT-2009: LHR-2010: BHR-2012:
SRG-2012, 2014)
Ans. Please see article
(b) Explain the effect of temperature on phenol-water system.
Ans. Please see article
Q10. (a) What are the colligative properties? Why are the called so? (D.G.K-2007: LHR-2009: MLT-
2010: RWP-2012)
OR Why some properties are called colligative? (SRG-2010 D.G.K-2011: BHR-2012)
Ans. Please see article
(b) What is the physical significance of Kb and Kf values of solvents?
436 Chapter # 9 (Solution)
Ans. Please see article
Q11. How do you explain that the lowering of vapour pressure is a colligative property? How do you
measure the molar mass of a non volatile, non-electrolyte solute in a volatile solvent?
Ans. Please see article
Q12 How do you justify that
(a) Boiling points of the solvents increase due to the presence of solutes (FSD-2007: CUJ- 2010: MLT-
2013: LHR-2014: D.G.Khan- 2014) (RWP-2017) (SRG-2017)
OR Why the boiling points of a solution of a non-volatile solute in a volatile solvent is always greater
than the boiling point of pure solvent? (GUJ-2008)
Ans. In pure solvent, all the surface of solvent is occupied by solvent molecules. However, when a non-
volatile, non-electrolyte solute is added to it, some surface is occupied by solute particles. So. the
escaping tendency of solvent is decreased. Therefore vapour pressure of solution becomes less than
solvent. Thus, to boil solution more heat is required to bring its vapour pressure equal to external
pressure. Hence, boiling point of solution is increased.
(b) Freezing points are depressed due to the presence of solutes (LHR-2007, 2009: FSD-2010. 2011:
RWP- 2011: GUJ-2012. 2016: MLT-2015)
OR Why the freezing point of the solution is always less than the freezing point of pure solvent? (FSD-
2009)
Ans. At freezing point the vapour pressure of liquid and solid phases are same. However, when a non-
volatile, non-electrolyte solute is added to pure solvent, some surface is occupied by solute particles. So,
the escaping tendency of solvent is decreased. Therefore vapour pressure of solution becomes less than
solvent. Due to lowering of vapour pressure, the freezing point of solution is decreased.
(c) The boiling point of one molal urea solution is 100.52 °C but the boiling point of two molal urea
solution is less than 101.04oC.
Ans. Elevation of boiling point is a colligative property. Normal colligative properties are observed when the
solution is dilute so that each solute particle behaves independently.
Two molal urea solution is concentrated than one molal solution. In concentrated two molal solution,
solute particles do not behave independently. They have attractions for each other. Thus solution
becomes non-ideal. Hence one molal solution boils at 100.52 oC. While two molal solution boils below
than expected value of 101.04oC.
(d) Beckmann thermometer is used to note the depression in freezing point. ((RWP-2007. 2015: MLT-
2009: LHR-2013: BHR-2011)
Ans. There is very small difference between freezing point of pure solvent and its dilute solution. Ordinary
thermometer can read upto 0.5 K (upto one decimal place). Hence, these cannot differentiate between
freezing point of pure solvent and solution.
Beckmann thermometer can read upto 0.01 K (upto two decimal places). Hence, it can exactly measure
freezing point of pure solvent and solution.
(e) In summer the antifreeze solutions protect the liquid of the radiator from boiling over.
(RWP-2007) MLT-2014) (LHR-2015) (Azad Kashmir -2017) (MLT-2017)
Ans. Antifreeze solution consists of solution of ethylene glycol in H20. Since ethylene glycol is non-volatile
therefore, vapour pressure of this solution is lowered and boiling point is increased.
In summer, due to large heat in engine. H 2O may boil over in radiator. However, due to lower pressure
of solution, it requires much greater heat to boil. Hence, this mixture prevents boiling over of H 2O
(f) NaCl or KNO3 are used to lower the melting point of ice. (SRG-2007: GUJ-2008 : (LHR-2013,
Professor CHEMISTRY - XI (Subjective) 437

2015. 2017: SRG-2013 MLT-2013, 2015: Azad Kashmir- 2017: FSD-2017)

Ans. When NaCl or KNO3 is added to H2O, its vapour pressure is lowered. Due to lowering of vapour
pressure solution freezes below the freezing point of H2O. so it will have more cooling effect. Hence,
this mixture is used as freezing mixture e.g. in an ice-cream machine.
Q13. What is Raoult's law. Give its three statements. How this law can help us to understand the ide of
a solution.
Ans. Please see article
Q14. Give graphical explanation for elevation of boiling point of a solution. Describe one meth:
determine the boiling point elevation of a solution.
Ans. Please see article
Q15. Freezing points of solutions are depressed when non-volatile solutes are present in volatile sola- J
Justify it. Plot a graph to elaborate your answer. Also, give one method to record the depress
freezing point of a solution.
Ans. Please see article
Q16. Discuss the energetics of solution. Justify the heats of solutions as exothermic and endothermic
properties.
Ans. Please see article

Q.17 (a) Calculate the molarity of glucose solution when 9 g of it is dissolved in 250 cm3 of solution.
Solution:
Mass of glucose =w=9g
Mol. Mass of glucose = M = 180 g
Volume of solution = V = 250 cm3 = dm3 = 0.25 dm3
Molarity of solution = ?
Molarity of solution is given by
Molarity = 
Molarity =  =
(b) Calculate the mass of urea in 100 g of water in 0.3 molal Solution
Solution
Mass of water (solvent) = W = 100 g = = 0.1 kg
Molality of solution = m = 0.3
Molar mass of urea = M = 60 g/mol
Mass of urea dissolved = w = ?
Molality is given by m = 
0.3 =
or w = 0.3  60  0.1=
(c) Calculate the conc. of a solution in molality which is obtained by mixing 250 g of 20% solution of
NaCl with 200 g of 40% solution of NaCl. Solution
Solution
For 1st solution
438 Chapter # 9 (Solution)
100 g of solution contain NaCl = 20 g
250 g of solution contain NaCl =  250 = 50 g
nd
For 2 solution
100 g of solution contain NaCl = 40 g
200 g of solution contain NaCl =  200 = 80 g.
Hence after mixing
Total mass of NaCl = w = 50 + 80 = 130 g
Formula mass of NaCl = M = 58.5 g/mol
Mass of total solution = 200 + 250 = 450 g,
Mass of Water = W = 450 – 130 = 320 g = 0.32 kg
Molality = m = ?
Molality is given by
m = 
m= =
Q.18 (a) An aq. solution of sucrose has been labelled as one molal. Find the mole fraction of solute and
the solvent.
Solution
1 molal aq. sucrose solution means that 1 mole of sucrose (342 g) has been dissolved in 1 kg ( 1000 g )
of H20. Hence
Moles of sucrose = nsuc = 1 mole
Mass of H20 = 1000 g
Mol. Mass of H2O = 18 g/mol
Moles of H2O = nH2O = = 55.55 moles
Therefore
Xsuc =
and xH2O = = 0.9823
(b) You are provided with 80% sulphuric acid having density 1.8 g/cm 3. How much volume of this
sulphuric acid sample is required to obtain 1 dm3 of 20% H2SO4 whose density is 1.25 g/cm3.
Solution
For 80% sulphuric acid
% of sulphuric acid = 80 %
Density of sulphuric acid =1.8 g/cm3
Thus Mass of 1 cm3 of solution = 1.8 g
Mass of 1000 cm3 of solution = 1.8  1000 =1800 g
Therefore
100 g of solution contain sulphuric acid = 80 g
1800 g of solution contain sulphuric acid =  1800 = 1440 g.
Hence. 1440 g of H2SO4 are present in 1000 cm3 of solution.
Mass of H2SO4 / cm3 = w = 1440 g
Molar Mass of H2SO4 = M = 98 g/mol
Volume of solution = V= 1000 cm3 = 1 dm3
Therefore, molarity is given by
Molarity =  = 14.7 M
Professor CHEMISTRY - XI (Subjective) 439
For 20% sulphuric acid
% of sulphuric acid = 20 %
Density of sulphuric acid = 1.25 g/cm3
Thus Mass of 1 cm3 of solution = 1.25 g
Mass of 1000 cm3 of solution = 1.25  1000 = 1250 g
Therefore
100 g of solution contain sulphuric acid = 20 g
1250 g of solution contain sulphuric acid =  1250 =250 g.
Hence, 250 g of H2S04 are present in 1000 cm3 of solution.
Mass of H2SO4 / cm3 = w = 250g
Mol. Mass of H2SO4 = M = 98 g/'mol
Volume of solution = V = 1000 cm3 = 1 dm3
Therefore, molarity is given by
Molarity = 
Molarity =  = 2.55 M
To prepare 1 dm3 ( 1000 cm3) of 2.55 M H,£04from 14.7 M H2SO4
Cone. H2SO4 (given) Dil. H2SO4 (required)
M1 V1 = M2V2
or V1 =  V2
V1 =  1000 =
Therefore 173.47 cm3 of conc. H2SO4 are token in a measuring flask and volume of the solution is made
upto 1 dm3 (1000 cm3)
Q.19 250 cm3 of 0.2 molar K2SO4 solution is mixed with 250 cm3 of 0.2 molar KCl solution. Calculate the
molar conc. of K+ ions in the solution.
Solution:
1 mole of K2SO4 produce 2 moles of K+ ions
Therefore, 0.2 moles of K2SO4 produce 0.4 moles of K+ ions
Hence conc. of K+ ions = 0.4 moles/dm3
1 mole of KCI produces 1 moles of K+ ions
Therefore. 0.2 moles of KCl produces 0.2 moles of KT ions
Hence, conc. of K+ ions = 0.2 moles/dm3
After mixing two molar solutions
Conc. of K+ ions = 0.2 + 0.4 = 0.6 moles in 2 dm3.
If 250 cm3 of each solution is mixed then
Total Volume = 250 + 250 = 500 cm3 = = 0.5 dm3
Hence 2 dm3 of solution contain K+ ions = 0.6 moles
0.5 dm3 of solution contain K+ ions = = 0.15 moles/dm3
1 dm3 of solution contain K+ ions = 0.3 moles/dm3
Q.20 5 g of NaCl is dissolved in 1000 g of water. The density of resulting solution is 0.997 g/cm 3.
Calculate the molality, molarity and mole fractions of this solution. Assume that the volume of the
solution is equal to that of the solvent.
Molality
Mass of NaCl = w = 5 g
440 Chapter # 9 (Solution)
Formula mass of NaCl = M = 58.8 g/mol
Mass of H2O = W = 1000 g = 1 kg
Molality = 
Molarity =  =
Molarity
Mass of NaCl = w = 5 g
Formula mass of NaCl = M = 58.8 g/mol
Mass of H2O = W = 1000 g = 1 Kg
Density of solution = d = 0.997 g cm–3
d =
Since
So V = = = 1003 cm3 = 1.003 dm3
Molarity is given by
Molality = 
Molarity =  =
Mole Fraction
Mass of NaCl = w = 5 g
Formula mass of NaCl = M = 58.8 g'mol
Moles of NaCl = = 0.0854 moles
Mass of H2O = w = 1000 g
Mol. Mass of H2O = M = 18 g/mol
Hence XNaCl = =
XH2O = =
Q.21 4.675 g of a compound with empirical formula C 3H3O, was dissolved in 212.5 g of pure benzene.
The freezing point of the solution was found 1.02°C less than that of benzene. The molar freezing
point constant of benzene is 5.1°C. Calculate
(i) The relative molar mass of the compound
Mass of solute compound = w2 = 4,675 g
Mass of solvent benzene = w1 = 212.5 g
Freezing point depression = Tf = 1.02
Molal F.P. constant of benzene = kf = 5.1°C
Molecular Mass of compound = M2 = ?
Molecular Mass of the compound is given by
M2 = 
M2 =  =
(ii) The molecular formula of the compound
Empirical Formula of the compound = C3H3O
Empirical formula mass of the compound = (3  12) + (3  1)
+ (1x16)
= 55 g mol–1
Thus n = =
Hence Molecular formula = n ( Empirical formula)
= 2 (C3H3O) = C6H6O2
Professor CHEMISTRY - XI (Subjective) 441

Q.22 The boiling point of a solution containing 0.2 g of a substance 'A' in 20 g of ether is 0.17 K higher
than that of pure ether. Calculate the molar mass of 'A'. Boiling point constant of ether is 2.16 K
Solution:
Mass of solute 'A' = w2 = 0.2 g
Mass of solvent ether = w1 = 20 g
Elevation in BP. = Tb = 0.17 K
Molal B.P. constant of ether = kb = 2.16 K
Molar Mass of A = M2 =?
Molar Mass of solute 'A' is given by
M2 = 
M2 =  =
Q.23 3 g of non-volatile, non-electrolyte solute 'X' is dissolved in 50 g of ether (molar mass 74) at 293 K.
The vapour pressure of ether falls from 442 torr to 426 torr at these conditions. Calculate the
molecular mass, of the solute X.
Solution:
Mass of solute 'X' = w2 = 3 g
Mass of solvent ether = w1 = 50 g
Molar Mass of ether = M1= 74 g/mol
Vapour pressure of pure ether = P° = 442 torr,
Vapour pressure of solution = P = 426 torr
Lowering of vapour pressure = P = P° – p=442 – 426 = 16 torr
Molar Mass of 'X' = M2 = ?
Molar Mass of solute is given by
M2 =  =  =

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