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Chemistry Notes Series SOLUTIONS

Time: Code: SOL/NT
Class –XII. M.M.

Solutions
 Brass is a mixture (Homogeneous solution of solid in solid) of copper and zinc.
 German silver mixture(Homogeneous solution of solid in solid) of copper Zinc and nickel.
Bronze mixture(Homogeneous solution of solid in solid) of copper and tin.
Types of Solutions:
 Solutions are homogeneous mixtures of two or more than two components.
 Homogenous mixture means that its composition and properties are uniform throughout the mix-
ture, generally, the components that are present in the largest quantify is known as solvent.
 Solvent determines the physical state in which other solution exists.
 One or more components present in the solution other than solvent are called solutes.

Type of solution Solute Solvent Common examples

Gas Gas Mixture oxygen and nitrogen gases

Gaseous solution
Liquid Gas chloroform mixed with nitrogen gas

Solid Gas camphor in nitrogen gas

Gas Liquid Oxygen dissolved in water

Liquid solutions Liquid Liquid Ethanol dissolved in water

Solid Liquid Glucose dissolved in water

Gas Solid Solution of hydrogen in palladium
Solid solutions Liquid Solid Amalgam of mercury with sodium
Solid Solid Copper dissolved in gold

Expressing Concentration of solution :

The are several ways by which we can describe the concentration of the solution quantitatively.
(i) Mass peracentage (w/w): The mass of solute (grams) present in each 100 grams of solu-
tion.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑖𝑛 𝑡𝑕𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
%w/w = × 100
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

For example. 10% glucose in water by mass, means the 10g of glucose is dissolved in
90g of water resulting in a 100g solution.

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 This method is generally used to express the concentration of SOLID IN SOLID & SOLID IN
LIQUID
(ii) Volume percentage (v/v): The volume of solute (ml) present in each 100 ml. of solution.
𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡𝑕𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
Volume % of a component = × 100
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

From examples, 10% ethanol solution in water means the 10 ml of ethanol is dissolved in
water such that the total volume of the solution in 100 mL .
 Solutions containing liquids are commonly expressed in this unit.
 A 35% (v/v) solution of ethylene glycol, antifreeze. is used in case for cooling the engine. At
this concentration the antifreeze lowers the freezing point of water to 255.4 K (-17.60C).
(iii) Mass by volume percentage (w/v): The mass of solute (grams) present in each 100 ml.
of solution.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
%(w/v) = × 100
𝑇𝑜𝑡𝑎𝑙 𝑣𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

 commonly used in medicine and pharmacy is mass by volume percentage.

(iv) Parts per million: The parts of a solute present in each one million parts of the solution-
Parts per million =
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑐𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡
= × 106
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑎𝑛𝑒𝑛𝑡𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑠𝑜𝑙𝑢𝑡𝑜𝑖𝑛

 commonly used when a solute is present in trace quantities such as pollutants.

Eg. (i) SO2 is 20 ppm by mass in air means that 20 gram of SO2 is present in 106 grams
of air.
(ii) SO2 is 20 ppm by volume in air means that 20 ml of SO2 is present in 106 ml of air.
(iii) SO2 is 20 ppm mass by volume in air means that 20 gram of SO2 is present in 106
ml. of air.
-1
 The concentration of pollutant in water or atmosphere is often expressed in terms of µg mL or
ppm.
(v) Mole fraction: The number of moles of a component of a solution present in the solu-
tion with respect to the total number of moles of the solution.
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑐𝑜𝑚𝑝𝑜𝑢𝑛𝑒𝑛𝑡
Mole fractions of a component =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑎𝑙𝑙 𝑐𝑜𝑚𝑝𝑎𝑛𝑒𝑛𝑡𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑠𝑜𝑙𝑢𝑡𝑜𝑖𝑛

For example, in a binary mixture , if number of moels of A and B are 𝑛𝐴 𝑎𝑛𝑑 𝑛𝐵 respec-
tively
𝑛𝐴
𝑥𝐴 =
𝑛𝐴 + 𝑛𝐴
𝑓𝑜𝑟 a solution containing i number of components, we have:
𝑛𝑖 𝑛𝑖
𝑥𝑖 = =
𝑛1 + 𝑛2 + ⋯ … . +𝑛𝑖 𝑛𝑖
𝒊𝒕 𝒄𝒏𝒂 𝒃𝒆 𝒔𝒉𝒐𝒘𝒏 𝒕𝒉𝒂𝒕 𝒊𝒏 𝒂 𝒈𝒊𝒗𝒆𝒏 𝒔𝒐𝒖𝒕𝒊𝒐𝒏 𝒔𝒖𝒎 𝒐𝒇 𝒂𝒍𝒍 𝒕𝒉𝒆 𝒎𝒐𝒍𝒆 𝒇𝒓𝒂𝒄𝒕𝒊𝒐𝒏𝒔 𝒊𝒔 𝒖𝒏𝒊𝒕𝒚
𝒙𝟏 + 𝒙𝟐 …… + 𝒙𝒊 = 𝟏
 The expression is used for the solutions having more than two components.
 Mole fraction can be calculated for each (all) i.e. solvent and all the solutes of a solution.
 Dimensionless quantity.
Examples calculate the mole fraction of ethylene glycol (C2H6O2) in a solution containing 20% of
C2H6O2 by mass.

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Solution Assume that we have 100g of solution (one can start with any amount of solution be-
cause that the results obtained will be that same). Solution will contain 20g of ethylene
glycol and 80g of water.
20𝑔
Moles of C2H6O2 = = 0.322 𝑚𝑜𝑙
62𝑔𝑚𝑜𝑙 −1
20𝑔
Moles of water = = 4.444 𝑚𝑜𝑙
18𝑔𝑚𝑜𝑙 −1
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶2 𝐻6 𝑂2
𝑥𝑔𝑙𝑦𝑐𝑜𝑙 =
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶2 𝐻6 𝑂2 +𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐻2 𝑂

0.322𝑚𝑜𝑙
= = 0.068
0.322𝑚𝑜𝑙 + 4.444 𝑚𝑜𝑙
4.44𝑚𝑜𝑙
𝑠𝑖𝑚𝑖𝑙𝑎𝑟𝑦 𝑥𝑤𝑎𝑡𝑒𝑟 = = 0.932
0.322 𝑚𝑜𝑙 + 4.444𝑚𝑜𝑙
Mole fraction of water can also be calculated as: 1- 0.068 = 0.932

(vi) Molarity: Molarity (M) defined as number of moels of solute dissolved in litre (or one
cubic decimetre or dm3) of solution.
𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
Molarity =
𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑒𝑟
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑡𝑒 𝑟

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 1000

=
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝒎𝒊𝒍𝒊𝒍𝒊𝒕𝒆𝒓

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 1000 𝑥 𝑑𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑛 𝒈𝒓𝒂𝒎𝒔
 Dimension in always Mole L-1
For example, 0.25 mol L-1 (or 0.25 M) solution of NaOH means that 0.25 mol (or 10
gram) of NaOH has been dissolved in one litre (or one cubic decimetre or 𝒅𝒎𝟑 ).
Examples Calculate the molarity of a solution containing 5 g of NaOH in 450 mL solution.
5𝑔
Solution moles of NaOH = = 0.125𝑚𝑜𝑙
40𝑔𝑚𝑜𝑙 −1

Volume of the solution in litres = 450 mL / 1000 mL L 1

0.125 𝑚𝑜𝑙 ×1000 𝑚𝐿 𝐿−1
Molarity = = 0.278 𝑀
450 𝑚𝐿

= 0.278 mol 𝑳−𝟏

= 0.278 mol 𝒅𝒎−𝟑
Examples Find the molarity of water ?
Molarity of water means that no. Of moles of water in 1 liter of water.
n(H2O) in 1000 ml of water
as the density of water is 1 g/ml or 1 Kg/L.
n(H2O) in 1000 grams of water
n(H2O) = given mass / molar mass = 1000/18 = 55.55 molL-1 or molKg-1
(vii) Molality: molality (m) is defend as the number of moles of the solute per kilogram (kg)
of the solvent and is expressed as:

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𝑀𝑜𝑙𝑒𝑠 𝑜𝑓 𝑠𝑜𝑙𝑡𝑒
Molality (m) =
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝐾𝑔
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 𝑚𝑎𝑠𝑠 𝑜𝑓 𝒔𝒐𝒍𝒗𝒆𝒏𝒕 𝑖𝑛 𝐾𝑔

𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 1000

𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑒 𝑥 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑖𝑛 𝑔𝑟𝑎𝑚𝑠

 Dimension in always Mole Kg -1

 Mass % ppm, mole fraction and molality are independent of temperature, whereas molarity
is function of temperature. This is because volume depends on temperature and the mass
does not.
Examples calculate molality of 2.5 g of Ethanoic acid (CH3COOH) in 75g of benzene.
Solution molar mass of C2H4O2: 12×2+1×4+16×2 = 60g mol-1
2.5𝑔
Moles of C2H4O2 = = 0.0417 𝑚𝑜𝑙
60𝑔𝑚𝑜𝑙 −1

Mass of benzene in kg = 75g / 1000 g kg-1 = 75×10-3 kg

𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝐶2 𝐻4 𝑂2
Molality of C2H4O2 =
𝑘𝑔 𝑜𝑓 𝑏𝑒𝑛𝑧𝑒𝑛𝑒

0.0417𝑚𝑜𝑙 × 1000𝑔 𝑘𝑔−1

=
75𝑔
= 0.556 𝑚𝑜𝑙 𝑘𝑔−1
 Molarity of dilution:
(Before dilution) M1 V 1 = M 2 V2 ( After dilution )
 Molarity of mixing: M1 V1 + M2V2 + M3 V3 = MR ( V1+ V2+ V3)
Where MR = Resultant molarity, V1 +V2 +V3 = Resultant volume after mixing
 If in any case i.e. moles, mass, volume, number etc. The solute is less than that of solvent or the
solution then its magnitude can be ignores and solution can be considered as a very dilute solution
and SOLUTION = SOLVENT can be considered.
 Relation between mole fraction and molality :
𝑛𝐴 𝑛𝐵
𝑋𝐴 = ,𝑋 =
𝑛𝐴 + 𝑛𝐵 𝐵 𝑛𝐴 + 𝑛𝐵
𝑋𝐵 𝑛𝐵 𝑊𝐵 𝑊𝐴
= = /
𝑋𝐴 𝑛𝐴 𝑀𝐵 𝑀𝐴
𝑋𝐵 𝑊𝐵 . 𝑀𝐴
→ =
𝑋𝐴 𝑀𝐵.𝑊𝐴

𝑋𝐵 𝑊𝐵 1
→ = ×
𝑋 𝐴 .𝑀 𝐴 𝑀𝐵 𝑊𝐴

1000 𝑋 𝐵 1000 𝑊 𝐵
→ = =𝑚
𝑋 𝐴 𝑀𝐴 𝑀𝐵 𝑊𝐴

1000 𝑋 𝐵
→ =𝑚
𝑋 𝐴 𝑀𝐴

1000 𝑋 𝐵
→ =𝑚
( 1 − 𝑋 𝐵 ). 𝑀𝐴

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 Why one molar is more concentrated then one molal in an aqueous solution?
Ans: One molal means one mole of solute is present in 1000 grm or 1000 ml (as D water = 1 gram
/ ml.) of water in one solution.
One molar solution = 1000 ml of solution = amount of solute + amount of solvent. So solvent I.e.
water is less than 1000 ml.
Intext Questions
1. Calculate the mass percentage of benzene (C6H5) and carbon tetrachloride (CCl4) if 22g of ben-
zene is dissolved in 122g of carbon tetrachloride.
2. Calculate the mole fraction of benzene in solution containing 30% by mass in carbon tetrachloride.
3. Calculate the molarity of each or the following solutions: (a) 30 g of CO(NO3)2. 6H2O in 4.3 L of
solution (b) 30 mL of 0.5 M H2SO4 diluted to 500 mL .
4. Calculate the mass of urea (NH2CONH2) required in making 2.5 kg of 0.25 molal aqueous solu-
tions.
5. Calculate (a) molality (b) molarity and (c) molar fraction of KI if the density of 20% (mass /
mass) aqueous KI is 1.202 g mL-1
Solubility:
 Solubility of a substance is its maximum amount that can be dissolved in a specified amount
of solvent at specified temperature.
 It depends upon the nature of solute and solvent as well as temperature and pressure.
Solubility of a Gas in a Liquids:

 Effect of temperature
GAS (Solute) + LIQUID(Solvent) ⇋ GAS/LIQUID ( Solution ) + HEAT
Solubility of gases in liquids decrease with rise in temperature. When dissolved, the gas molecules are
present in liquid phase and the process of dissolution can be considered similar to condensation and
heat is evolved in this process. Dissolution process involves dynamic equilibrium and an exothermic
process, so according to Le Chatelier’s principle the solubility should decrease with increase of tem-
perature.
 Oxygen dissolves only to a small extend in water.
 Hydrogen chloride gas (HCl) is highly soluble in water solubility of gases in liquid is greatly af-
fected by pressue and temperature.
 Effect of Pressure:
 The solubility of gases increase with increase of pressure. Assume a system to be in a state of dy-
namic equilibrium. i.e., under these conditions rate of gaseous particles entering and leaving the
solution phase is the same. Now increase the pressue over the solution phase by compressing the
gas to a smaller volume this well increase the number of gaseous particles per unit volume over
the solution and also the rate at which the gaseous particles are striking the surface of solution to
enter it. The solubility of the gas will increase until a new equilibrium is reached, resulting in an
increase in the pressure of gas above the solution and thus its solubility increases.
Henry’s Law :
 It states that at a constant temperature. The solubility of gas in a liquid is directly propor-
tional to the pressures of the gas.
 Dalton, a contemporary of Henry, also concluded independently that the solubility of a gas in a
liquid solution is a direct function of partial pressure of the gas.
 If we use the mole fraction of a gas in the solution as a measure of its solubility. Then it can be
said that the mole fraction of gas in the solution is proportional to the partial pressure of the
gas over the solution.

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 The most commonly used form of Henry’s laws states that ‘the partial pressure of the gas in
vapour phase (p) is proportional to the mole fraction of the gas in the solution’ and ex-
pressed as:
P = KH X
Here KH is the Henry’s law constant.
 Different gases have different KH values at the same temperature.
 A gas has different KH values at different temperatures.
 Higher the value of KH at a given pressure. The lower is the solubility of the gas in the liquid.
 The solubility of gases increases (or KH decreases) with decrease of temperature. It is due to this
reason that aquatic species are more comfortable in cold waters rather than in warm waters.
Values of Henry’s Law constant for some selected Gasses in Water

Gas Temperature /K KH / kbar

N2 293 76.48
N2 303 88.64
O2 293 34.86
O2 303 46.82

Examples If gas is bubbles through water at 293 K, how many mill moles of N2 gas would dissolve in
1 litre of water. Assume that N2 exerts a partial pressure of 0.987 bars. Given that Heronry’s
law constant for N2 at 293 K is 76.48 bar.
Solution The soluubity of gas is related to the mole fraction in aqueous solution. the moels fraction of
the gas in the solution is calculated by applying Henry’s law thus:
𝑝(𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛 ) 0.987 𝑏𝑎𝑟
X (Nitrogen) = = = 1.29 × 10−5
𝐾𝐻 76.480 𝑏𝑎𝑟

As 1 litre of water contains 55.5 mol of it, therefore if n represent number of moels of N 2 in
solution,
𝑛 𝑚𝑜𝑙 𝑛
X (Nitrogen) = = = 1.29 × 10−5
𝑛 𝑚𝑜𝑙 +55.5 𝑚𝑜𝑙 55.5

(n in denominator is neglected as it is << 55.5)

Thus n = 1.29× 10−5 × 55.5 𝑚𝑜𝑙 = 7.16 × 10−4 𝑚𝑜𝑙
7.16×10 −4 𝑚𝑜𝑙 ×1000 𝑚𝑜𝑙
= = 0.716 𝑚𝑚𝑜𝑙
1 𝑚𝑜𝑙

Henry’s law finds several applications in industry and explains some biological phenomena.
Notable among these are:
 To increase the solubility of CO2 in soft drinks and soda water. The bottle is seale
udder high pressure.
 That is why when the cold drink bottle is opened then the gas filled under high pressure in the
bottle over the liquid escapes in the atmosphere, so that the partial pressure of the gas above
the surface of liquid decreases , the solubility of the gas in liquid decreases and the dissolved
gas starts getting undissolved and the GAS FIZZES OUT.
 Scuba divers must cope with high concentrations of dissolved gases while breathing
of dissolved gases while breathing air at high pressure underwater. Increased pres-
sure increase the solubility of atmospheric gases in blood. When the divers come to-
wards surface, the pressures gradually decrease. This released the dissolved gase and
leads to the formation of bubbles of nitrogen in the blood. This blocks capillaries and

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crates a medical condition known as bends, are painful and dangerous to life. To
avoid bends, as well as the toxic effects of high concentrations of nitrogen in the
blood, the tank used by scuba divers are filled with air diluted with helium
(11.7% helium. 56.2% nitrogen and 32.1% oxygen):
 At high altitudes the pressure of oxygen is less than that at the ground level. This
leads to low concentrations of oxygen in the blood and tissues of people living at
high altitudes or climbers. Low blood oxygen caused climbers to become weak and
unable to think clearly, symptoms of a condition known as anoxia.
 Units/ Dimensions of KH = Units/ dimensions of pressure = bar / atm. / Pa / torr / etc.
 Q. Two gases A and B have their KH as 5 bar and 10 bar respectively , which gas is more
soluble in water ? and why ?
Ans: As under same conditions of pressure and temperature : KH α 1/ Xgas , hence gas A is
more soluble.
Intext Questions
6. H2S. a toxic gas with rotten egg like smell, is used for the qualitative analysis. If the solubility of
H2S is water at STP is 0.195 m calculate henry’s law constant.
7. Henry’s law constant for CO2 in water is 1.67×108 pa at 298 K. calculate the quantity of CO2 in
500 mL of soda water when packed under 2.5 atm CO 2 pressue at 298 K.
Solubility of a solid in a Liquid :
 sodium chloride an sugar dissolve readily in water, naphthalene and anthracites do not.
 On the other hand. Naphthalene and anthracites dissolve readily in benzene but sodium chlo-
ride and sugar do not.
 It is observed that polar solutes dissolve in polar solvents and non polar solutes in non po-
lar solvents. In general a solute dissolves in a solvent if the intermolecular interactions are
similar in the two or we may say like dissolves like.
 When a solid solute is added to add to the solvent, some solute dissolves and it concen-
tration increase in solution. this process is known as dissolution. Some solute particles in
solution collide with the solid solute particles and get separated out of solution. this
process is known as crystallisations. A stage is reached when the two processes occur at the
same rate. Under such conditions. Number of solute particles going into solution will be equal
to the solute particles separating out and a state of dynamic equilibrium is reached.
Solute + Solvent ⇋ Solution
 Such a solution in which no more solute can be dissolved at the same temperature and pres-
sure is called a saturated solution.
 An unsaturated solution is one in which more solute can be dissolved at same temperature.
 The solution which is in dynamic equilibrium with undisssolved solute in the saturated solu-
tion and contains the maximum amount of solute dissolved in a given amount of solvent then
the concentration of solute in such a solution is its solubility.
Effect of temperature :
Solute + Solvent ⇋ Solution ± heat
Being dynamic equilibrium. According to Le Chatelier’s principle, If in a nearly saturated solu-
tion, the dissolution process is endothermic ( ∆𝑠𝑜𝑙 𝐻 > 𝑂). 𝑡𝑕𝑒𝑛 𝑠𝑜𝑙𝑢𝑡𝑖𝑙𝑖𝑡𝑦 𝑠𝑕𝑜𝑢𝑙𝑑 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒
with rise in temperature and if it is exothermic (∆𝑠𝑜𝑙 𝐻˂ 𝑂) the solubility should decrease.
 The solubility of NaNO3, KNO3, NaCl etc. Increases on heating as the dissolution of these
salts in water is an endothermic process and according to Le Chatelier’s principle the for-
ward reaction is favoured on increase in temperature.
Solute + Solvent + HEAT ⇋ Solution or Solute + Solvent ⇋ Solution - HEAT

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 The solubility of Li2CO3, Na2CO3.H2O etc. Decreases on heating as the dissolution of these
salts in water is an exothermic process and according to Le Chatelier’s principle the back-
ward reaction is favoured on increase in temperature.
Solute + Solvent - HEAT ⇋ Solution or Solute + Solvent ⇋ Solution + HEAT

Effect of pressure :
Pressure does not have any significant effect on solubility of solid in liquids. It is so because solids
and liquid are liquid are highly incompressible and practically remain unaffected by changes in
pressure.
 Vapour pressure:
The pressure exerted by the vapour particles of a liquid present on the surface of the liquid
against the external pressure (atmospheric pressure in open container and against the walls of
the container in closed container), at constant temperature.
 Boiling Point:
The point of temperature at which the vapour pressure of a liquid becomes exactly equal to exter-
nal pressure.
 V.P α 1/B.P.
 Higher the vapour pressure of a liquid lower is the B.P.
 Acetone (Nail polish remover), alcohol, petrol etc. have lower B.P. as their V.P. is higher
than that of water.
Vapour pressure of Liquid Solutions
(i) liquids in liquids and (ii) solids in liquids.
(i) Vapours Pressure of Liquid Solutions(Liquid in Liquid / Both Volatile Components)
Raoult’s law: which states that for a solution of volatile liquids.
The partial vapour pressure of each component in the solution is directly proportional to its
mole fraction.
Thus for component 1
p 1 α 𝑥1
And p 1 = 𝑝10 𝑥1
Where 𝑝10 is the vapour pressure of pure component 1 at the same temperature.
Similarly: for component 2
p 2 α 𝑥2
p 1 = 𝑝20 𝑥2
where 𝑝20 represents the vapour pressure of the pure component 2.
According to Dalton’s law of partial pressure.the total pressure (𝑃𝑡𝑜𝑡𝑎𝑙 𝑜𝑣er the solution phase in
the container will be the sum of the partial pressure of the components of the solution and is given
as:
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1 + 𝑃2
𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑡𝑒𝑕 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑃1 𝑎𝑛𝑑 𝑃2 we get
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑥1 𝑝10 + 𝑥2 𝑝20
= 1 − 𝑥2 𝑝10 + 𝑥2 𝑝20
= 𝑝10 + (𝑝20 − 𝑝10 )𝑥2

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(i) Total vapour pressure over the solution can be related to the mole fraction of any one
component.
(ii) Total vapour pressure over the solution varies linearly with the mole fraction of compo-
nent 2.
(iii) Depending on the vapour pressures of the pure components 1 and 2 total vapour pressure
over the solution decrease or increase with the increase if the mole fraction of compo-
nent 1.
assuming that component 1 is less volatile than component 2, i.e.,𝒑𝟎𝟏 < 𝒑𝟎𝟐
the composition of vapour phase in equilibrium with the solution is determined by
the partial presseu of the components. If y1 and y2 are the mole fractions of the
components 1 and 2 respectively in the vapour phase then, using Dalton’s law of par-
tial pressure:
𝑃1 = 𝑦1 𝑃𝑡𝑜𝑡𝑎𝑙
𝑃2 = 𝑦2 𝑃𝑡𝑜𝑡𝑎𝑙

𝐼𝐼𝐼 𝑝02
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑃1 +𝑃2
𝐼𝐼
𝑣𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑠𝑢𝑒
𝑝01 𝑃2

𝑃1
𝐼

𝑥1 = 1 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑥1 = 1
𝑥2 = 0 𝑥2
𝑥2 = 0

Examples Vapour pressures of chloroform (CHCl3) and dichloromethane (CH2Cl2) at 298 K are 200
mm Hg 415 mm Hg respectively. (i) Calculate the vapour pressure of the solution prepared
by mixing 25.5g of CHCl3 and 40g of CH2Cl2, at 298 K and, (ii) mole fractions of each com-
ponent in vapour phase.
Solution (i) molar mass of CH2Cl2 = 12×1+1×2+35.5×2 = 85 g mol-1
Molar mass of CHCl3 = 12×1+1×1+35.5×3 = 119.5 g mol-1
40𝑔
Moles of CH2Cl2 = = 0.213 𝑚𝑜𝑙
85𝑔 𝑚𝑜𝑙 −1

Total number of moles = 0.47 + 0.213 = 0.683 mol

0.47 𝑚𝑜𝑙
𝑥𝐶𝐻2 𝐶𝑙2 = = 0.688
0.683 𝑚𝑜𝑙

𝑥𝐶𝐻𝐶𝑙3 = 1.00 − 0.688 = 0.312

Using equation (2.16).
𝑃𝑡𝑜𝑡𝑎𝑙 = 𝑝10 + (𝑝20 − 𝑝10 )𝑥2 = 200+ (415 – 200) ×0.688
= 200 + 147.9 = 347.9 𝑚𝑚 𝐻𝑔
(ii) 𝑦1 = 𝑃1 /𝑃𝑡𝑜𝑡𝑎𝑙
𝑝𝐶𝐻2 𝐶𝑙2 = 0.668 × 415 𝑚𝑚 𝐻𝑔 = 285.5 𝑚𝑚 𝐻𝑔

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𝑝𝐶𝐻𝐶𝑙3 = 0.312 × 200 𝑚𝑚 𝐻𝑔 = 62.4 𝑚𝑚 𝐻𝑔

𝑦𝐶𝐻2 𝐶𝑙2 = 285.5 𝑚𝑚 𝐻𝑔/347.9 𝑚𝑚 𝐻𝑔 = 0.82
𝑦𝐶𝐻𝐶𝑙3 = 62.4 𝑚𝑚 𝐻𝑔𝐻𝑔/347.9 𝑚𝑚 𝐻𝑔 = 0.18
Note since, CH2Cl2 is a more volatile components than CHCl3.
0 0
[𝑝𝐶𝐻 2 𝐶𝑙 2
= 415 𝑚𝑚 𝐻𝑔 𝑎𝑛𝑑 𝑝 𝐶𝐻𝐶𝑙 3 = 200 mm Hg] and the vapour is also richer in CH 2Cl2 /
𝑦𝐶𝐻2 𝐶𝑙2 = 0.82 and 𝑦𝐶𝐻𝐶𝑙3 = 0.18]
 It may thus be concluded that at equilibrium, vapour phase will be always rich in the compo-
nent which is more volatile.
 Raoult’s Law as a Special case of Henry’s Law:
According to Raoult’s the vapour pressure of a volatile component in a give solution is given by p i
= X1𝑝10 in the solution of a gas in a liquid. One of the components is so volatile that it exists as a
gas and we have already seen that its solubility is given by Henry’s law which states that
𝑃 = 𝐾𝐻 𝑥.
𝑖𝑓 𝑤𝑒 𝑐𝑜𝑚𝑝𝑎𝑟𝑒 𝑡𝑕𝑒 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛𝑠 𝑓𝑜𝑟 𝑅𝑎𝑜𝑢𝑙𝑡 ′ 𝑠 law and Henry’s law ,it can be seen that the partial
pressure of the volatile component or gas is directly proportional to its mole fraction in solution,
only the proportionality constant KH differs from 𝑝10 thus Raoult’s law becomes a special case of
Henry’s law in which KH becomes equal to 𝑝10
 In a very dilute solution of liquids, the solvent obeys Raoul’s Law whereas the solute obeys
Henry Law, but opposite is not true.

 Ideal and Non ideal Solution:

1. Ideal Solutions:
 The solutions (liquid-liquid mixtures) in which each component obeys Raoult’s law over the en-
tire range of concentration at a given temperature are known as ideal solutions.
 The ideal solutions have two other important properties. The enthalpy of mixing of the pure compo-
nents to form the solution is zero and the volume of mixing is also zero i.e.
∆𝑚𝑖𝑥 𝐻 = 𝑂 ∆𝑚𝑖𝑥 𝑉 = 𝑂
 It means that no heat is absorbed or evolved when the components are mixed.
 Also, the volume of solution would be equal to the sum of volumes of the two components.
 At molecular level, ideal behaviour or the solutions can be explained by considering two components
A and B in pure components. The intermolecular attractive interactions will be of types A – A and B
– B, whereas in the binary solutions in addition to the intermolecular attractive force between the A –
A and B- B are equal to those between A- B. This leads to the formation of ideal solution.
 A perfectly ideal solution is rare.(are hypothetical)

1L 2L
1L

A A + A B
B B
A B

∆Vmix = 0
∆Hmix = 0
As:
A A
= A B
B B

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 Characteristics of an ideal solution:

(a) It obeys Raoults law at all concentrations and temperatures.
(b) Δsol V= 0, i.e., there is no change in volume when an ideal solution is formed.
(c) Δsol H= 0.,i.e., heat is neither evolved not absorbed during the formation of an ideal solution.

2. NEARLY Ideal Solutions: Those solutions(liquid - liquid mixture) which follow the Roult’s Law
of ideal solutions at a wide range of concentrations are called Nearly Ideal Solutions solution.
These are the mixtures of similar types of compounds , having similar interactions with each other
as they have individually among their particles.
e.g. Solution of (i) n – hexane and n -heptane
(ii) Bromoethane and chloroethane,
(iii) benzene and toluene.
3. Non – ideal Solutions:
 When a solution does not obey Raoult’s law over the entire range of concentration. Then it is called
non – ideal solution.
 The vapour pressure of such a solution is either higher or lower than predicted by Raoult’s law.
 If it is higher, the solution exhibits positive deviation and if it is lower it exhibit negative deviation
form Raoult’s law.
3.1. Non – ideal Solutions Showing POSITIVE DEVIATION from ROULT’S LAW:

1L 1L 2.15 L
(i)

A A B B A B
A B

(ii) ∆Vmix = +ve ∆Hmix = +ve ( endothermic) Solution becomes cold

(iii)
A A
B B > A B

 In case of positive deviation from Rault’s law. A-B interactions (solute – solvent molecules) are
weaker than those between the solute – solute and solvent- solvent molecules. This means that in
such solutions molecules of A (or B) will find it easier to escape than in pure state. this will in-
crease the vapour.
 Mixture of ethanol and acetone behave in this manner. In pure ethanol. Molecules are hydrogen
bonded on adding acetone. Its molecules get in between them. Due to weakening of interactions. The
solution shown positive deviation from Raoult’s law.
 Solution formed by adding carbon disulphide and Acetone the interactions are weaker than the respec-
tive interactions among the solute - solute molecules and solvent -solvent molecules. This solution also
shows positive deviation.
 Solution of Ethyl Alcohol + Water.

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Vapour pressure of
solution

Vapour pressure
P1
P2

X1 = 1 Mole fraction X1 = 0
X2 = 0 X2 X2 = 1
 X1

3.2. Non – ideal Solutions Showing NEGATIVE DEVIATION from ROULT’S LAW:

1L 1L 1.95 L
(i)
A A B B A B
A B

(ii) ∆Vmix = - ve ∆Hmix = - ve ( exothermic) Solution becomes hot/warm

(iii)
A A
B B ˂ A B

 In case of negative deviations from Raoult’s law the intermolecular attractive forces between A –
A and B – B are weaker than those between A – B
 This leads to decrease in vapour pressure resulting in negative deviations.
 An example of these types is mixture of phenol and aniline. In this case the intermolecular hydrogen
bonding between phenolic proton and lone pair on nitrogen atom of aniline is stronger than the respec-
tive similarly.
 A mixture chloroform and acetone forms a solution with negative deviation from Raoult’s law. This is
because chloroform molecule is able to form hydrogen bond what acetone molecules as shown.

H3C Cl
C = O ----------------------H – C Cl
CH3 Cl

 This decrease the escaping tendency of molecules for each component and consequently the vapour
pressure decrease resulting in negative deviation from Raoult’s law

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P01
P02
Vapour pressue P1
P2

X1 = 1 Mole fraction X1 = 0
X2 = 0 X2 X2 = 1
 X1

 AZEOTROPIC MIXTURES: or CONSTANT BOILING MIXTURES :

Some liquid binary mixtures having the same composition in liquids and vapour phase and
boil at a constant temperature.
 Properties : (i) In such case it is not possible to separate the components by fractional distillation.
(ii) The liquid mixture behaves like a true liquid, having its unique vapour pressure and
boiling point.
 Types :There are two types of azeortropes :
(i) Minimum boiling azeortropes:
 The solution which show a large positive deviation from Raoult’s form minimum boiling azeortropes
at a specific composition.
 For examples ethanol water mixture (obtained by fermentation of sugars) on fractional distillation
gives a solution containing approximately 95% by volume of ethanol. Once this composition, known
as azeortropes composition, has been achieved the liquid and vapour have the same composition, and
no further separation occurs.
 In this case the B.P. of the azeotropic mixture is less than the B.P. of both the pure components e.g. in
case of ethanol(95%)(B.P.= 351.3K) and water (5%)(B.P.= 373K) .the azeotropic mixture has its B.P.=
351.15K
 That is why 100% concentrated ethanol can not be obtained by fractional distillation .
 100% ethanol can be obtained by chemical methods.
(ii) Maximum boiling azeortropes:
 The solutions the show large negative deviation from Raoult’s law forms maximum boiling azeor-
tropes at a specific composition.
 Nitric acid(B.P.= 359K) and water is an examples of this class azeortropes this azeortropes has the
approximate composition. 68% nitric acid and 32% water by mass. With a boiling point of 393.5 K.
Intext Question
8. The vapour pressure of pure liquids A and B are 450 and 700 mm Hg respectively at 350 K. Find
out the composition of the liquids mixture if total vapour pressure is 600 mm Hg. Also find the
composition if the vapour phase.

 Vapour pressure of Solutions of Solids in Liquids :

 Solids dissolved in liquid/Non Volatile solute in volatile solvent.
 for example, sodium chloride, glucose urea and cane sugar in water .
 Iodine and sulphur dissolved in carbon disulphide.

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 If a non volatile solute is added to a solvent to give a solution, the vapour pressure of the
solution is solely from the vapour pressure of the solvent alone, as the solute is non –
volatile and does not make its vapours under normal conditions.
 At this temperature the vapour pressure of the solution is found to be lower than the va-
pour pressure of the pure solvent at the same temperature.
 In the solution the surface has both solute and solvent molecules; thereby the fraction of
the surface covered by the solvent molecules gets reduced.
 Consequently the number of solvent molecules escaping from the surface is correspond-
ing reduced thus the vapour pressured is also reduced.
 The decrease in the vapour pressure of solvent depends on the quantity of non –
volatile solute present in the solution. Irrespective of its nature.
 For examples decrease in the vapour pressure of water by adding, 1.0 mol of sucrose to
one kg of water is nearly similar to that produced by adding 1.0 mol of urea to the same
quantity of water at the same temperature.
 Raoult’s law for solid in liquid:
‘For any solution the partial vapour pressure of each volatile component in the solution is
directly proportional to its mole fraction.’
 When the solute is non – volatile, the solvent(volatile) molecules are present in va-
pour phase can contribute to vapour pressure.
 let pi be the vapour pressure of the solvent, xi be its mole fraction 𝑝10 be its vapour pres-
sure in the pure state. then according to Raoult’s law
𝑝1 𝛼 𝑥1
𝑝1 = 𝑥1 𝑝10
The proportionality constant is equal to the vapour pressure of pure solvent 𝑝10 .
𝑎 plot between the vapour presseu and the mole fraction of the solvent is linear

𝑉𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑜𝑓
𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑛𝑡
𝑉𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑜𝑙𝑣𝑒𝑛𝑡

𝑋𝑠𝑜𝑙 𝑣𝑒𝑛𝑡

 Colligative Properties:
All the properties depend on the number of solute particles irrespective of their nature relative
to the total number of particles present in the solution, such properties are called colligative
properties
1. Relative Lowering of Vapour Pressure:
Raoult established that the lowering of vapour pressure depends only on the concentration of the
solute particles and it is independent of their identity.
𝑝1 = 𝑥1 𝑝10
= 𝑝10 (1 − 𝑥2 )

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AS 𝑥1 = 1-𝑥2
𝑝1
= 1 − 𝑥2
𝑝10
𝑝1
1 − 0 = 𝑥2
𝑝1

∆𝒑𝟏 𝒑𝟎𝟏 − 𝒑𝟏
= = 𝒙𝟐
𝒑𝟎𝟏 𝒑𝟎𝟏
The expression on the left hand side of the equation as mentioned is called relative lowering
of vapour pressure and is equal the mole fraction of the solute.
The above equation can be written as.
𝑝10 − 𝑝1 𝑛2 𝑛2
0 = 𝑠𝑖𝑛𝑐𝑒 𝑥2 =
𝑝1 𝑛1 + 𝑛2 𝑛1 + 𝑛2
𝑕𝑒𝑟𝑒 𝑛1 𝑎𝑛𝑑 𝑛2 𝑎𝑟𝑒 𝑡𝑕𝑒 number of moles of solvent and solute respectively present in the solu-
tion. for dilute solutions 𝑛2 << 𝑛1 𝑕𝑒𝑛𝑐𝑒 𝑛𝑒𝑔𝑙𝑒𝑐𝑡𝑖𝑛𝑔 𝑛2 𝑡𝑕𝑒 𝑑𝑒𝑛𝑜𝑚𝑖𝑛𝑎𝑡𝑜𝑟 𝑤𝑒 𝑕𝑎𝑣𝑒
𝑝10 − 𝑝1 𝑛2
=
𝑝10 𝑛1
𝑝10 − 𝑝1 𝑤2 × 𝑀1
𝑜𝑟 =
𝑝10 𝑀2 × 𝑤1
𝑕𝑒𝑟𝑒 𝑤1 𝑎𝑛𝑑 𝑤2 are he masses and 𝑀1 and 𝑀2 are the molar masses o the solvent and solute re-
spectively.
𝑓𝑟𝑜𝑚 𝑡𝑕𝑖𝑠 𝑒𝑞𝑎𝑡𝑖𝑜𝑛, knowing all other quantities, the molar mass of solute (𝑀2 ) can be calcu-
lated.
Examples The vapour pressure of pure benzene at a certain temperature is 0.850 bar. A non – volatile
non – electrolyte solid weighing 0.5 g when added to 39.0 g benzene (molar mass 78 g
mol-1 ) vapour pressure of the solutions, then is 0.845 bar. What is the molar mass of the
solid substance?
Solution the various quantities known to us are as follows:
𝑝10 = 0.850 𝑏𝑎𝑟; 𝑝 = 0.845 𝑏𝑎𝑟; 𝑀1 = 78𝑔 mol-1 𝒘𝟐 = 𝟎. 𝟓𝒈 𝒘𝟏 = 𝟑𝟗𝒈
As w2 << w1
𝑝10 − 𝑝1 𝑤2 × 𝑀1
=
𝑝10 𝑀2 × 𝑤1

0.850 𝑏𝑎𝑟 − 0.845 𝑏𝑎𝑟 0.5𝑔 × 78 𝑔 𝑚𝑜𝑙−1

=
0.850 𝑏𝑎𝑟 𝑀2 × 39𝑔
Therefore 𝑀2 = 170𝑔 𝑚𝑜𝑙−1

2. Elevation of Boiling Point:

A liquid boils at the temperature at which vapour pressure is equal to the atmospheric pressure
.for example, water boils at 373.15 (100 0C) because at this temperature the vapour pressure of wa-
ter is 1.013 bar atmosphere). Vapour pressure of the solvent decrease in the presence of non vola-
tile solute. So the boiling point of a solution is always higher than that of the boiling point of the
pure solvent in which the solution is prepared.
Let 𝑇10 𝑏𝑒 𝑡𝑕𝑒 𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑛𝑡 𝑜𝑓 𝑝𝑢𝑟𝑒 𝑠𝑜𝑙𝑣𝑒𝑛𝑡 𝑎𝑛𝑑 𝑇𝑏 𝑏𝑒 𝑡𝑕𝑒 𝑏𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛.
the increase in he boiling point ∆𝑻𝒃 = 𝑻𝒃 − 𝑻𝟎𝟏 𝒊𝒔 𝒌𝒏𝒐𝒘𝒏 𝒂𝒔 𝒆𝒍𝒆𝒗𝒂𝒕𝒊𝒐𝒏 of boiling point.

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For a dilute solution the elevation of boiling point (∆𝑇𝑏 ) is directly proportional to the molal con-
centration of the solution in solution. thus
∆𝑇𝑏 𝛼 𝑚
𝑜𝑟 ∆𝑇𝑏 = 𝐾𝑏 m
 𝒉𝒆𝒓𝒆 𝒎 𝒎𝒐𝒍𝒂𝒍𝒊𝒕𝒚 𝒘𝒉𝒊𝒄𝒉 𝒊𝒔 𝒕𝒉𝒆 𝒏𝒖𝒎𝒃𝒆𝒓 𝒐𝒇 𝒎𝒐𝒍𝒆𝒔 𝒐𝒇 𝒔𝒐𝒍𝒖𝒕𝒆 dissolved in 1 kg of solvent
 The constant of proportionally 𝑲𝒃 is called Boiling point Elevation constant or Molal Elevation con-
stant (Ebullioscopic constant).
 The units of 𝑲𝒃 is K Kg mol-1
𝑤 2 /𝑀2 1000 ×𝑤 2
 As ; 𝑚 = =
𝑤 1 /1000 𝑀2 ×𝑤 1

𝑠𝑢𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑡𝑕𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑚𝑜𝑙𝑎𝑖𝑡𝑦 in equation, we get

𝐾𝑏 × 1000 × 𝑤2
∆𝑇𝑏 =
𝑀2 × 𝑤1
1000 × 𝑤2 × 𝐾𝑏
𝑀2 =
∆𝑇𝑏 × 𝑤1
Thus, in order to determine 𝑀2 molar mass of the solute, known mass of solute in a known mass
of the solvent is taken and ∆𝑇𝑏 is determined experimentally for a known solvent whose 𝐾𝑏 value
is known.

Boiling point
solvent, solution
1 Atm
solvent

𝑉𝑎𝑝𝑜𝑢𝑟 𝑝𝑟𝑒𝑠𝑠𝑠𝑢𝑟𝑒 solution

∆𝑇𝑏

∆𝑇𝑏0
𝑇𝑏
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 /𝐾
 Q. Define Ebullioscopic constant ?
Ans: As; ∆𝑇𝑏 𝛼 𝑚
∆𝑇𝑏 = 𝐾𝑏 m
Let m=1
∆𝑇𝑏 = 𝐾𝑏
Hence; ‘Ebullioscopic constant is the elevation in boiling point of one molal solution of any
nonvolatile solute in its solvent.’

Examples: 18 g of glucose C6H12O6.Is dissolved in 1 kg of water in saucepan. At what temperature

will water boil at 1.013 bars? 𝐾𝑏 For water is 0.52 K Kg mol-1.
Solution moles of glucose = 18g / 180 g mol-1 = 0.1 mol
Number of kilograms of solvent= 0.1 mol
Thus molality of glucose solution = 0.1 mol kg-1
For water, change in boiling point
∆𝑇𝑏 = 𝐾𝑏 × 𝑚 = 0.52 𝑘𝑔𝑚𝑜𝑙−1 × 0.1 𝑚𝑜𝑙 𝑘𝑔−1 = 0.052 𝐾

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𝑠𝑖𝑛𝑐𝑒 𝑤𝑎𝑡𝑒𝑟 𝑏𝑜𝑖𝑙𝑠 𝑎𝑡 373.15 𝐾 𝑎𝑡 1.013 𝑏𝑎𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒. Therefore the boiling point of
solution will be 373.15 + 0.052 = 373.202 K.
Examples the boiling point of benzene is 353.23 K. when 1.80 g of a non – volatile solute was dissol-
vent in 90g of benzene. The boiling point is raised to 354.11 K. Calculate the molar mass of
the solute. Kb for benzene is 2.53 K kg mol-1
Solution The elevation (∆𝑇𝑏 ) 𝑖𝑛 the boiling point = 354.11 K – 353.23 K = 0.88K substituting these
values in expression (2.33) we get
253 𝐾 𝑘𝑔 𝑚𝑜𝑙 −1 ×1.8 𝑔 ×1000 𝑔 𝑘𝑔 −1
𝑀2 = = 58𝑔 𝑚𝑜𝑙−1
0.88 𝐾×90𝑔

Therefore, molar mass of the solute 𝑀2 = 58 𝑔 𝑚𝑜𝑙−1

3. Depression of Freezing Point:
 At the freezing point of a substance. The solid phase is in dynamic equilibrium with the liquid
phase. Thus the freezing point of a substance may be defined as ‘the temperature at which the
vapour pressure of the substance in its liquid phase is equal to its vapour pressue in the solid
phase’.
 A solution will freeze when its vapour pressure in the solid phase and liquid phase are equal.
 Let 𝑇0𝑓 be the freezing point of pure solvent and Tf be its freezing point when non – volatile
solute is dissolved in it. The decreases in freezing point.
∆𝑇𝑓 = 𝑇𝑓0 − 𝑇𝑓 is known as depression in freezing point.
Similar to elevation of boiling point, depression of freezing point (∆𝑇𝑏 ) for dilute solution
(ideal solution) is directly proportional to molality m of the solution. thus,
∆𝑇𝑓 𝛼 𝑚
∆𝑇𝑓 = 𝐾𝑓 𝑚

𝑡𝑕𝑒 𝑝𝑟𝑜𝑝𝑜𝑟𝑡𝑖𝑜𝑛𝑎𝑙𝑖𝑡𝑦 constant, 𝐾𝑓 which depends on the nature of the solvent is known as
Freezing Point Depression Constant or Molal Depression constant or Cryoscopy
constant. The unit of 𝐾𝑓 K kg mol-1..
𝑖𝑓𝑤2 gram of the solute having molar mass as 𝑀2 present in 𝑤1 𝑔𝑟𝑎𝑚 of solvent, produces the
depression in freezing point ∆𝑇𝑓 of eh solvent then molality of the solute is given by the equation

Liquid solvent
Solution
Frozen solvent
Vapour pressure

∆𝑇𝑓

𝑇𝑓 𝑇𝑓0
Temperature / K

𝑤2 /𝑀2
𝑚=
𝑤1 /1000
𝑠𝑢𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 this value or molality in equation we get:
𝐾𝑓 × 𝑤2 /𝑀2
∆𝑇𝑓 =
𝑤1 /1000

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𝐾𝑓 × 𝑤2 × 1000
∆𝑇𝑓 =
𝑀2 × 𝑤1
𝐾𝑓 × 𝑤2 × 1000
𝑀2 =
∆𝑇𝑓 × 𝑤1
𝑇𝑕𝑢𝑠 for determining the molar mass of the solute we should know the quantities 𝑤1 . 𝑤2 ∆𝑇𝑓 along
with the molar freezing point depression constant,
 𝑇𝑕𝑒 𝑣𝑎𝑢𝑒𝑠 of𝐾𝑓 and 𝐾𝑏 which depend upon the nature of eth solvent, can be ascertained from the fol-
lowing relations.
𝑅 × 𝑀1 × 𝑇𝑓2
𝐾𝑓 =
1000 × ∆𝑓𝑢𝑠 𝐻
𝑅 × 𝑀1 × 𝑇𝑏2
𝐾𝑏 =
1000 × ∆𝑣𝑎𝑝 𝐻
Here the symbols R and 𝑀1 st and the gas constant and molar mass of the solvent, respectively and
𝑇𝑓 and 𝑇𝑏 denote the freezing point and the boiling point of the pure solvent respectively in kelvin.
Further ∆𝒇𝒖𝒔 𝑯 𝒂𝒏𝒅 ∆𝒗𝒂𝒑 𝑯 represent the enthalpies for the fusion(solid to liquid) and vapori-
sations(liquid to gas) of the solvent, respectively.

Solvent b.p/k Kb/ k kg mol-1 f.p./k Kf/ k kg mol-1

Water 373.15 0.52 273.0 1.86

Examples 45g of ethylene glycol (C2H6O2) is mixed with 600g of water. Calculate (a) the freezing
point depression and (p) the freezing point of the solution.
Solution Depression point is related to the molality therefore, the molality of the solution with re-
𝑚𝑜𝑙𝑒 𝑠 𝑜𝑓 𝑒𝑡𝑕𝑦𝑙𝑒𝑛𝑒 𝑔𝑙𝑦𝑐𝑜𝑙
spect to ethylene glycol =
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑖𝑛 𝑘𝑖𝑙𝑜𝑔𝑟𝑎𝑚
45𝑔
Moles of ethylene glycol = = 0.73 𝑚𝑜𝑙
62 𝑔 𝑚𝑜 𝑙 −1
600 𝑔
Mas of water in kg = = 0.6 𝑘𝑔
1000 𝑔 𝑘𝑔 −1
0.73 𝑚𝑜 𝑙
Hence molality of ethylene glycol = = 1.2 𝑚𝑜𝑙𝑘𝑔−1
0.60 𝑘𝑔

Therefore freezing point depression,

∆𝑇𝑓 = 1.86 K kg 𝑚𝑜 𝑙 −1 × 1.2 mol 𝑘𝑔−1 = 2.2 K
Freezing point of the aqueous solution = 273.15 K – 2.2K = 270 .95 K
Examples 1.00 g of a non – electrolyte solute dissolved in 50g of benzene lowered the freezing point
of benzene by 0.40 K. the freezing point depression constant of benzene is 5.12 k kg mol -
1
. Find molar mass of the solute.
Solution substituting the values of various terms involved in equation wet get.

5.12𝐾 𝑘𝑔 𝑚𝑜 𝑙 −1 × 1.00𝑔 × 1000𝑔𝑘𝑔−1

𝑀2 = = 256 𝑔𝑚𝑜 𝑙 −1
0.40 × 50𝑔
𝑡𝑕𝑢𝑠, 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑡𝑕𝑒 𝑠𝑜𝑢𝑡𝑒 = 256 𝑔 𝑚𝑜 𝑙 −1
4. Osmosis and Osmotic Pressure:
 Diffusion : The movement of particles from their higher concentration to their lower
concentration.

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 Osmosis: (i) The movement of SOLVENT particles from THEIR higher concentration
to THEIR lower concentration through SPM.
(ii) The movement of solvent particles from LOWER concentrated SOLUTION (DI-
LUTE SOLUTION) towards HIGHER concentrated SOLUTION through SPM.
 Raw mangoes shrink when pickled in brine (salt water)
 Some membranes have such small pores that does not allow the solute particles to go
through it but only solvent.
 Osmotic Pressure: The flow of the solvent from its side, to solution side across a semiper-
meable membrane can be stopped if some extra pressure is applied on the solution.
 The external pressure applied on the solution which just stops the flow of solvent in the
solution when separated from its pure solvent by SPM, is called osmotic pressure of the
solution.
or
 The osmotic pressure of a solution is the excess pressure that must be applied to a solu-
tion to prevent osmosis, i.e., to stop the passage of solvent molecules through a semi
permeable membrane into the solution from its pure solvent.
 The osmotic pressure has been found to depend on the concentration of the solution.
 Osmotic pressue is a colligative prosperity as it depends on the number of solute molecules
and not on their identity.
 For dilute solutions. It has been found experimentally that osmotic pressure is proportional
to the molarity, C, of the solution at a given temperature T thus:
Π = CRT
Here π is the osmotic pressure and R is the gas constant.
Π = (n2/V) RT
Here V is volume of a solution in litres containing n2 moles of solute. If w2 grams of solute, of
molar mass M2 is present in the solution then n2 = w2 / M2 and we can write
𝑤 2 𝑅𝑇
𝛱𝑉=
𝑀2

𝑊2 𝑅𝑇
𝑜𝑟 𝑀2 =
𝛱𝑉
𝑇𝑕𝑢𝑠. 𝑘𝑛𝑜𝑛𝑤𝑖𝑛𝑔 𝑡𝑕𝑒 𝑞𝑢𝑎𝑛𝑡𝑖𝑡𝑒𝑠 𝑤2 T. Π and V we can calculate the molar mass of the solute.
 While solving the problems, we have to take proper care of units of R. If pressure is in atm, then R
should be taken as 0.0821 Lit. Atm. mol-1 K-1
 If pressure is in bar, then R should be taken as 0.0831 Lit. bar. mol-1 K-1
 This method is widely used to determine molar masses of proteins, polymers and other macromole-
cules.
 The osmotic pressure method has the advantage over other methods as pressure measurement is
around the room temperature and the molarity of the solution is used instead of molality as compared
to other colligative properties, its magnitude is large as even for very dilute solutions.
 The technique of osmotic pressure for determination of molar mass of solutes is particularly useful for
bio molecules as they are generally not stable at higher temperature and polymers have poor
solubility.
 ISOTONIC SOLUTIONS:
𝒕𝒘𝒐 Solutions having same osmotic pressure at a given temperature are called isotonic solu-
tions.
 When such solutions are separated by semi permeable membrane no osmosis occurs between them.
 Also they have same molar concentration .

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For isotonic solutions , 𝜋1= 𝜋2

Also, C1= C2
𝑛1 𝑛2 𝑊1 𝑊2
Or = =
𝑉1 𝑉2 𝑚 1 𝑉1 𝑚 2 𝑉2

 For example, Human RBC is isotonic with 0.9% (mass volume) sodium chloride solution. called
normal saline solution and it is safe to inject intravenously.
 On the other hand if we place the cells is solution containing more than 0.9% (mass volume) sodium
chloride. Water will flow out of the cells(exosmosis) and they would shrink such a solution is called
hypertonic.
 If the salt concentration is less than 0.9% (mass volume) the solution is said to be hypotonic. In this
case water will flow into the cells(endosmosis) if placed in this solution and they would swell.
 The preservation of meat by salting and of fruits by adding sugar protects against bacterial action.
Through the process of osmosis a bacterium on salted meat or candid fruit loses water, shrivels and
dies.
 EDEMA: people taking lot of salt or salty food develop swelling or puffiness of their tissues, a disease
called edema. This is due to the retention of water in the tissue cells and intercellular space on account
of osmosis.

Examples 200 cm3 of an aqueous solution of a protein contains 1.26 g of the protein. The osmotic pres-
sue of such a solution at 300 K is found to be 2.57×10-3 bar. Calculate the moles mas of the
protein.
Solution The various quantities known to us are as follow: II = 2.57×10-3 bar.
V = 200 cm3 = 0.200 litre
R = 0.083 L bar mol-1 K-1
Substituting these values in equation (2.42) we get
1.26 𝑔 ×0.083 𝐿 𝑏𝑎𝑟 𝑚𝑜𝑙 −1 𝐾 −1 𝑚𝑜𝑙 −1 ×300 𝐾
M2 = = 61,022 𝑔 𝑚𝑜𝑙 −1
2.57×10 −3 𝑏𝑎𝑟 ×0.200 𝐿

 Reverse Osmosis and Water Purification

 The direction of osmosis can be reversed of a pressure larger than the osmotic pressure is ap-
plied to the solution side.
 That is how the pure solvent flows out of the solution side, through the semi permeable
membrane.
 This phenomenon is called reverse osmosis .
 Reverse osmosis is used in desalination water.
 When pressure more than the osmotic pressure of sea water is applied the pure water is
squeezed out of the sea water through the membrane.
 The pressure required for the reverse osmosis is quite high.
 A workable porous membrane is a film of cellulose acetate placed over a suitable support.
 Cellulose acetate is permeable to water but impermeable to impurities and ions.
Intext Questions
9. Vapour pressure of pure water at 298 K is 23.8 mm Hg. 50g urea (NH 2CONH2) is dissolved in 850
of water. Calculate the vapour pressure of water for this solution and its relative lowering.
10. Boiling point of water at 750 mm Hg is 99.63 0C. How much sucrose is to be added to 500g of wa-
ter such that boils at 100 0C.

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11. Calculate the mass of ascorbic acid (Vitamin C, C 6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.50C kf = 3.9 K kg mol-1
12. Calculate the osmotic pressure in rascals exerted by a solution prepared by dissolving 1.0 g poly-
mer of molars mass 185.000 in 450 mL of water at 37 0C.
 Abnormal Molar Masses:
 During the experiments of colligative properties , while the molecular masses of solutes are
found, mostly do not match their calculated values or true values according to their chemical
formulae. These incorrect or observed molecular masses are called Abnormal Molecular
Masses.
 Cause :
 It is because that most of the solutes either associate or dissociate after dissolution in their
solvents. Because of which the no. of moles of solute in the solvent differs so the collegative
property (as the colligative property is directly proportional to no. of moles of solute) and thus
the molecular mass of the solute as (MM of the solute is inversely proportional to C.P.)
 Correction:
 These abnormal molecular masses can be corrected by using van’t Hoff’s factor.
 Van’t Hoff Factor : It can be defined as ‘the corrective term which is used to rectify the
abnormalities in molecular masses observed during the experiment of colligative proper-
ties and is the ratio of experimental value of colligative to the calculated value of the col-
ligative property.’
𝑁𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
 i=
𝐴𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
𝑜𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑐𝑜𝑙𝑙𝑖𝑔 𝑕𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑡𝑦
 i=
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝐶𝑜𝑙𝑙𝑖𝑔𝑎𝑡𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑡𝑦
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙 𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛

 Case of Association:
 (i) Complete Association : Let a compound A on dissolution in its solvent undergoes
complete association making DIMER.So
2A A2
At t = 0 C 0
At t = end 0 C/2
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙 𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
So 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛

𝐶
𝑖 = = ½
𝐶 𝑥 2

𝑜𝑟 𝑖𝑛 𝑔𝑒𝑛𝑒𝑟𝑎𝑙:

nA An the van’t Hoff factor is 1/n

 (ii) Incomplete/ Partial Association: Let a compound A on dissolution in its solvent un-
dergoes incomplete association making DIMER.So
2A ⇌ A2
At t = 0 C 0
At t = eql. C-Cα Cα/2

Where the degree of association( i.e. how many out of one mole are associated) is α

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𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜 𝑐𝑖𝑎𝑡𝑖𝑜𝑛

So 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛

𝐶−𝐶𝛼 +𝐶𝛼 /2
i =
𝐶

i = 1- α/2
 Molecules of Ethanoic acid (acetic acid ) dimerise in benzene due to hydrogen bonding. This
normally happens in solvents of low dielectric constant. In this case the number of particles
is reduced due to dimerization.
 Case of Dissociation:
 (i) Complete Dissociation: Let a compound dissociate completely into its ions(or constitu-
ents) on dissolving as follows :
AB A+ + B-
At t = 0 C 0 0
At t = end 0 C C
𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛
So 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛

2𝐶
𝑖 = = 2
𝐶

𝑜𝑟 𝑖𝑛 𝑔𝑒𝑛𝑒𝑟𝑎𝑙:
AxBy XA + YB
At t = 0 C 0 0
At t = end 0 XC YC

𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙𝑒 𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛

So 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛

𝐶(𝑋+𝑌)
𝑖 = = X+Y
𝐶

 Inomplete Dissociation: Let the degree of dissociation of a weak electrolyte (i.e. how many
moles out of one mole are dissociated) is α.
AB ⇌ A+ + B-
At t = 0 C 0 0
At t = eql. C-Cα Cα Cα

𝑡𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑖𝑐𝑙𝑒𝑠 𝑎𝑓𝑡𝑒𝑟 𝑎𝑠𝑠𝑜𝑐𝑎𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜 𝑐𝑖𝑎𝑡𝑖𝑜𝑛

So 𝑖=
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 𝑏𝑒𝑓𝑜𝑟𝑒 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑖𝑜𝑛 /𝑑𝑖𝑠𝑠𝑜𝑐𝑎𝑡𝑖𝑜𝑛
𝐶−𝐶𝛼 +𝐶𝛼 +𝐶𝛼
i =
𝐶

i =1+ α
 * In case of association and dissociation α can not be more than 1.
 * if α is 1 then it is complete association or dissociation.
 * In case of association i < 1.
 * In case of dissociation i > 1.
 * i can not be negative .

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Inclusion of van’t Hoff actor modifies the equations for colligative properties as follows:
 Relative lowering of vapour pressure of solvent.
𝑝10 − 𝑝1 𝑛2
= 𝑖.
𝑝10 𝑛1
 𝐸𝑙𝑒𝑣𝑎𝑡𝑖𝑜𝑛 𝑜𝑓 𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 = ∆𝑇𝑏 = 𝑖 𝐾𝑏 𝑚
 Depression of Freezing point.∆𝑇𝑓 = i 𝐾𝑓 𝑚
Osmotic pressure of solution Π = i 𝑛2 𝑅𝑇 /𝑉
Examples 2g benzoic acid (C6H5COOH) dissolved in 25 g benzene shows a depression in freezing
point equal to 1.62 K molal depression constant for benzene is 4.9 K kg mol -1 what is the
percentage association of acid it form dimer in solution?
Solution The given quantities are : w2 = 2g; kf = 4.9 k Kg mol-1 w1 = 25g
∆𝑇𝑓 = 1.62 𝐾
𝑠𝑢𝑡𝑏𝑠𝑡𝑖𝑡𝑢𝑡𝑖𝑛𝑔 𝑡𝑕𝑒𝑠𝑒 𝑣𝑎𝑙𝑢𝑒𝑠 𝑖𝑛 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 𝑤𝑒 𝑔𝑒𝑡:
4.9 𝑘 𝐾𝑔 𝑚𝑜𝑙 −1 ×2𝑔 ×1000 𝑔𝑘𝑔 −1
M2 = = 241.98 𝑔 𝑚𝑜𝑙 −1
25𝑔 ×1.62 𝐾

Thus, experimental molar mass of benzoic acid in benzene is

= 241. 98 g 𝑚𝑜𝑙−1
Now consider the following equilibrium for the acid:
2 C6H5 COOH ⇌ (C6H5COOH)2
If x represents the degree of association of the solute then we would have (1-x) mole of
𝑥
benzoic acid left in associated form and correspondingly 𝑎𝑠 𝑎𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 moles of ben-
2
zoic acid at equilibrium therefore, total number of moles of particles at equilibrium is:
𝑥 𝑥
1 –x + = −1 −
2 2

Thus total number of moels of particles at equilibrium equals van’t Hoff factor i.
𝑁𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
But i =
𝐴𝑏𝑛𝑜𝑟𝑚𝑎𝑙 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠
122 𝑔𝑚𝑜𝑙 −1
=
241 .98 𝑔 𝑚𝑜𝑙 −1
𝑥 122
Or =1− = −1 − 0.504 = 0.496
2 241 .98

Or x = 2×0.496 = 0.992 = 99.2%

Examples 0.6 mL of acetic acid (CH3COOH). Having density 1.06g mL-1 is dissolved in 1 litre of
water. The depression in freezing point observed for this strength or acid was 0.0205 0c.
Calculate the van’t Hoff factor and the dissociation constant of acid.
0.6 𝑚𝐿 ×1.06 𝑔𝑚𝑜𝑙 −1
Solution Number of moles of acetic acid = = 0.0106 𝑚𝑜𝑙 = 𝑛
60𝑔 𝑚𝑜𝑙 −1
0.0106 𝑚𝑜𝑙
Molality = = 0.0106𝑚𝑜𝑙 𝑘𝑔−1
1000 𝑚𝐿 ×1𝑔𝑚𝐿 −1

Using equation
∆𝑇𝑓 = 1.86 𝑘 𝐾𝑔𝑚𝑜𝑙−1 = 0.0197 𝐾
𝑂𝑏𝑠𝑒𝑟𝑣𝑒𝑑 𝑓𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 0.0205𝐾
𝑉𝑎𝑛′ 𝑡𝐻𝑜𝑓𝑓 𝐹𝑐𝑡𝑜𝑟 𝑖 = = = 1.041
𝐶𝑎𝑙𝑐𝑢𝑙𝑎𝑡𝑒𝑑 𝐹𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 0.0197 𝐾
Acetic acid is a weak electrolyte and will dissociate into two ions acetate and hydrogen
ion per molecules of acetic acid. if x is the degree of dissociation of acetic acid than we
would have n (1-x) moles of undissociated acetic acid. nix moles of CH3COO- and moels of
H+ ions

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CH3COOH ⇌ H+ + CH3COO-
C mol o o
C(1-x) Cx mol Cx mol
Thus total moles of particles are: C (1-x+x+x) (1+x)
𝐶 1+𝑥
i = = 1 + 𝑥 = 1.041
𝐶

Thus degree of dissociation of acetic acid = x= 1.041 – 1.000 = 0.041

The [CH3COOH] = C(1-x) 0.0106 (1-0.041)
[CH3COO-] =Cx = 0.0106 ×0.041 [H+] = Cx = 0.0106 × 0.041
𝐶𝐻3 𝐶𝑂𝑂 − [𝐻 + ] 0.0106×0.041×0.0106 ×0.041
Ka = = = 1.86 × 10−5
[𝐶𝐻3 𝐶𝑂𝑂𝐻 ] 0.0106 (1.00−0.041 )

Practice Questions
1. Will the elevation in boiling point be same if 0.1 mole of sodium chloride or 0.1 mole of sugar is
dissolved in 1 L water?
2. 0.01 M solution of KCl and BaCl2 are prepared in water. The freezing point KCl is found to be
20C what freezing point will you expect for BaCl2 solution assuring both KCl and BaCl2 to be
completely ionized.
3. Give below is the sketch of a plant of carrying out a process:
a) Name the process occurring in the above plant?
b) To which container does the net flow of solvent takes place?
c) Give principle behind the plant.
Pure water

Saline Water A B

SPM

4. Benzoic acid completely dime rises in benzene. What be the vapour pressure of a solution con-
taining 61g of benzoic acid per 500 g of benzene when the vapour of pure benzene at the tempera-
ture of the experiment is 66.6 torr?
5. The osmotic pressure of a urea solution is 500 mm of Hg at 100 C. The solution is diluted and its
temperature rose to 250 C it is found that the osmotic pressure of the solution is reduced to 105.3
mm of Hg. Determine the extent of dilution of the solution.
6. Why is great care taken in intravenous injections to have comparable concentration of solution to
be injected to that of blood plasma?
7. Calculate the resulting molarity ofthe solution that is obtained by adding 5g of NaOH to 250 Ml of
M/4 NaOH solution. (Density = 1.05 g/ cm3). The density of the resulting solution is 1.08 g/cm3.
8. A motor vehicle radiator was filled with 8L of water to which 2L of methyl alcohol (density 0.8g/
ml) were added. What is the lowest temperature which the vehicle can be parked outdoors without
a danger the water in the radiator will freezer? Kfof water= 1.86 km -1

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ANSWERS
1. Elevation in boiling point is a colligative property which depends upon the number of solute par
tickles.
∆𝑇𝑓 (𝐾𝐶𝑙 ) 2
2. I for KCl = 2 I for BaCl 2 = 3 =
∆𝑇𝑓 (𝐵𝑎𝐶𝑙 2 ) 3

3. (a)The gives sketch is that if a desalination plant. (b) from A to B (c) REVERSE OSMOSIS
4. 2 CH3COOH → (C6H5COOH)2
i=½
𝑃𝑂−𝑃𝑠 𝑛2
=𝑖
𝑝𝑜 𝑛1+ 𝑛2

P0 = 66.6 torr (given)

5. ΠV = n RT
500 𝑛
at 100C = × 𝑅 × 283
760 𝑉
105 .3 𝑛
at 250C = × 𝑅 × 298 divide both equation to get the value of x
760 𝑥𝑉

6. If solution is less or more concentrated than 0.9% NaCl (aq) Solution then osmosis will occur and
RBC may swell up and burst or shrink and die respectively.
7.
a) Calculate the grams of NaOH in 250 Ml of M/4/ NaOH, then calculate the mass of 250 Ml of
NaOH solution
b) After adding solute (5g NaOH), calculate the volume of the newsolution and finally the mo-
larity.

8. First calculate the depression caused by addition of methyl alcohol

1000𝐾𝑓 𝑤2
∆𝑇𝑓 =
𝑤1 × 𝑀2
𝐹𝑟𝑒𝑒𝑧𝑖𝑛𝑔 𝑝𝑜𝑖𝑛𝑡 𝑇𝑓 = 0 − ∆𝑇𝑓
𝑣𝑒𝑕𝑖𝑐𝑙𝑒𝑠 𝑐𝑎𝑛 𝑏𝑒 𝑝𝑎𝑟𝑘𝑒𝑑 𝑜𝑢𝑡𝑑𝑜𝑜𝑟𝑠 𝑛𝑜𝑡 𝑏𝑒𝑙𝑜𝑤 𝑡𝑕𝑒 𝑎𝑏𝑜𝑣𝑒 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑇𝑓

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