Solutions 1

Unit –1 Solutions

 Homogenous Mixture of two or more pure substances is called a solution.

 Solute – Component in lesser amount Solvent - Component in larger amount or components having
phase similar to solution is called solvent.
 For ex. – (i) Solution of salt in water (ii) Solution of gas in water (iii) Solution of ethanol in water
 Aqueous Solution – Binary Solution having water as solvent.
 Non aqueous Solution – Solution having solvent other than water like Ether, ethanol, benzene etc.
 For ex. –1 ppm of Fluoride ions in water prevents tooth decay but 1.5 ppm Fluoride ions in water become
harmful and cause tooth to become colorless. And at even higher concentration, it become poisonous. for ex.
NaF (Sodium Fluoride) act as a rat poison.
 Types of Solutions – (I) Based on No. of Components in Solution
Binary Solution Ternary Solution Quaternary Solution
Contain two components Contain three components Contain four components

(II) Based on Phases of Components in Solution

Solute Solvent Type of solution Examples
Solid Solid Solid Solution Alloys (Brass, Bronze, German Silver)
Liquid Solid Solid Solution Amalgum (Hg + Metal), Hydrated Salts
Gas Solid Solid Solution H2 gas in Pt, Ni, Adsorption of Gas on metal surfaces
Solid Liquid Liquid Solution Salt or Sugar dissolved in water
Liquid Liquid Liquid Solution Ethanol in Water, Benzene in Toluene,
Gas Liquid Liquid Solution Soda Water (CO2 in Water), O2 gas in Water
Solid Gas Gaseous Solution I2 vapors in air, Camphor in N2 gas.
Liquid Gas Gaseous Solution Humdity in air, CHCl3 in N2 gas.
Gas Gas Gaseous Solution Air (O2, CO2, N2)
Brass = Cu + Zn , Bronze = Cu + Sn , German Silver = Cu + Zn + Ni
Various Concentration Terms
I. Mass Fraction - Ratio of mass of one component to sum of mass of all components in solution.
If m1 and m2 mass of components A & B are mixed then
Mass Fraction of A = Mass Fraction of B =

Mass % = Mass Fraction x 100

II. Volume Fraction - Ratio of vol. of one component to sum of vol. of all components in solution.
If V1 and V2 mass of components A & B are mixed then
Volume Fraction of A = Volume Fraction of B =

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III. Percentage Concentration –

It is mass of solute dissolved in 100 gram of
A. Solution.
% by Mass or
For ex.– 10% by mass aq. sol. of Glucose % By Mass = x 100
Mass percent
means 10 gm of Glucose in 100 gm of
Solution or 90 gm.Water
It is the volume of Liquid solute dissolved in
% by Volume 100 mL of Solution.
B. or For ex.– 8% by volume aq. sol. of ethanol % By Volume = x 100
Volume percent means 8 mL of Ethanol (C2H5OH) in 100
mL of Solution.
It is the mass of solid solute dissolved in 100
mL of Solution.
Mass by
C. For ex.– 14 % mass/volume aq. sol. of Mass/Vol. % = x 100
Volume %
Urea (NH2CONH2) means 14 gm of Urea
in 100 mL of solution.

lIl. Strength – It is the amount of solute (in gram) dissolved in 1 Liter of Solution. Unit – gram/Liter

Strength = Strength = x 1000

Strength = Molarity x Molar mass

IV. Parts Per Million (PPM) - No. of parts by mass of solute dissolved in parts by mass of solution.

Ppm = x 106 for ex. - 15 ppm aq. solution of urea means 15g of
urea in g solution.
This concentration terms is used when solute is present in very minute amount in a solution. Like
Chloroform in water, SO2 in air, Cl2 gas dissolved in water.
V. Mole Fraction [X] – It is defined as Ratio of moles of one component to sum of the moles of all the
components in solution. If & moles of substances A & B are mixed then.

Mole fraction of A [ ]= Mole fraction of B [ ]=

 Mole fraction of A [ ]= Mole fraction of A [ ]=

 Sum of mole fractions of all components (two, three or more) in solution is always unity or 1.
 For Binary solution- + = 1 For ternary solution - + + =1

Qu.1 – What is the sum of the mole fraction of all components in a

(i) binary solution and (ii) ternary solution?
Qu.2 – Give an example of (i) Gas in solid solution (ii) Liquid in gas solution

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VI. Molarity [M] [mol L-1] : It is defined as No. of moles of solute dissolved in 1 Liter of solution.

M = M = M =
= Given mass of solute, = Molar mass of solute
V = Volume of solution in Liter
IMPORTANT POINTS ABOUT MOLARITY – (i) Molarity Equations -
If a solution is diluted (i.e. more solvent added), then
Dilution Formula =
Molarity (M2) of final solution is calculated as -
If V1 and V2 mL of two solutions of same solute
Molarity of Mixture having Molarities M1 & M2 are mixed then Molarity + = )
of resultant solution [M3] can be calculated as -

(ii) Molarity change on changing Temperature, because it depends upon volume of solutions which
change on changing temperature So molarity is not preferred to express concentration of solution.
i.e. V ∝ T & M ∝ so M ∝
(iii)
Molar solution M = 1.0 1 mol solute in 1 Ltr solution
Semi molar solution M = 0.5 0.5 mol solute in 1 Ltr solution
Deci molar solution M = 0.1 0.1 mol solute in 1 Ltr solution
Centi molar solution M = 0.01 0.01 mol solute in 1 Ltr solution
Milli molar solution M = 0.001 0.001 mol solute in 1 Ltr solution

VII. Formality [F] – This is concentration term is used for ionic compounds only. It is defined as –
No. of gram formula mass of ionic compound dissolved in 1 Liter of the solution.
Sum of the atomic mass of all atoms in
F = the formula of that ionic compound

Ionic compound exists as ions which make a bunch in aq. solution so formality is used in place of molarity.
Vlll. Molality [m] [mol Kg-1] - No. of moles of solute dissolved in 1 kg (or1000 g) of solvent.

m = m = m=

= Given mass of solute, = Molar mass of solute, = Mass of Solvent

IMPORTANT POINTS ABOUT MOLALITY –
 One Molal Solution means - 1 mole of solute dissolved in 1 kg (or 1000 g) of solvent.
 0.2m aq. solution of glucose means - 0.2 mole of Glucose in 1 kg (or 1000 g) of Water.
 Mass of Solvent = Mass of Solution – Mass of Solute
 To convert Volume of solution into mass - Mass of Solution = Density x volume of solution
 Molality is not affected by Temperature because it depends upon mass which does not change on
changing the temperature hence molality is preferred over Molarity.

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Relation between Molarity

m = = -
(M) and Molality (m)

Relation between Molarity

M = M =
(M) and Mass % (x)

Q.3 – Why is molality preferred over molarity while expressing concentration of solution?
Q.4 – What is the effect of Temperature on Molarity of solution?
Q.5 - Calculate Molality and Mole fraction of 2.5 g of ethanoic acid (CH3COOH) 75 g benzene?
Sol – Mass of solute i.e. Ethanoic acid ( ) = 2.5g , Mass of solvent ( ) = 75g ,
Molar mass of solute (Ethanoic acid) ( ) = (12 x 2) + (1 x 4) + (16 x 2) = 60 gmol-1
Molar mass of solvent (Benzene) ( ) = (12 x 6) + (1 x 6) = 78 gmol-1

Calculation of molality - m= = = 0.556 mol/kg

Calculation of mole fraction -
Moles of Ethanoic acid (n1) = = 0.0417 ; Moles of Benzene (n2) = = 0.961

Mole fraction of Ethanoic Acid [ ] = = = 0.0416

Q.6 – Cal. Mole fraction of Ethylene glycol (C2H6O2) and water in solution of 20% of glycol by mass.
Sol – 20% by mass means 20g of glycol in 100 g of solution or 80g of water.
Mass of solute i.e. glycol ( ) = 20g , Mass of solvent ( ) = 80g ,
Molar mass of solute glycol ( ) = (12 x 2) + (1 x 6) + (16 x 2) = 62 gmol-1
Moles of glycol (n1) = = 0.322 ; Moles of Water (n2) = = 4.444

Mole fraction of glycol [ ] = = = 0.068

Mole fraction of Water [ ] = 1 - = 1 - 0.068 = 0.932
Q.7 - Calculate the Mole fraction of solute in 2.5m aqueous solution ?
Sol – 2.5m aqueous solution means 2.5 moles of solute in 1000g of water so
Moles of water = = 55.55

Mole fraction of solute [ ] = = = 0.043

Q.8 - How many gram of Na2CO3 is required to dissolve in 250g of water to prepare 0.1m solution?
Sol – 0.1m aqueous solution means 0.1 moles of solute in 1000g of water s
1000g is dissolving = 0.1 mole
m=
250g is dissolving = = 0.025 mole
0.1 = = 2.65
Mass of Na2CO3 = 0.025 x 106 = 2.65 g
g
Q.9 - Calculate the mass % of benzene and CCl4 if 22g of benzene is dissolve in 122g CCl4 ?

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Sol – Mass of solution = 22g + 122g = 144g [NCERT-INTEXT 2.1]

Mass % of benzene = = = 15.28 %

Mass % of CCl4 = 100 - 15.28 % = 84.72 %

Q.10 -Calculate the Mole fraction of benzene in solution containing 30% by mass in CCl4 ?
Sol – 30% by mass in CCl4 means 30g of benzene in 100 g of solution or 70g of CCl4. [NCERT-INTEXT 2.2]
Mass of solute benzene i.e. ( ) = 30g , Mass of CCl4 ( ) = 70g ,
Molar mass of benzene ( ) = (12x6)+(1x6) = 78 gmol-1 ; Molar mass of CCl4=12+(35.5x4) = 154 gmol-1
Moles of benzene (n1) = = 0.385 ; Moles of CCl4 (n2) = = 0.455

Mole fraction of benzene [ ] = = = 0.458

Mole fraction of CCl4 [ ] = 1 - = 1 - 0.458 = 0.542
Q.11 - Calculate the Molarity of each of the following solution – (a) 30g of Co(NO3)2.6H2O in 4.3Lof
solution (b) 30 mL of 0.5M H2SO4 diluted to 500mL [Co = 58.7] [NCERT-INTEXT 2.3]
Sol - (a) Molar mass of Co(NO3)2.6H2O = 58.7 + 2 + 14 + 48 + (6x18) = 310.7 g/mol

Molarity = = = 0.022 M
(b) = 0.5 , = 30 mL , = ? , = 500 mL
= 0.5 x 30/1000 = x 500/1000 = 0.03
Q.12 - Calculate the mass of urea (NH2CONH2) required for making 2.5 kg of 0.25 molal aqueous
solution. [NCERT-INTEXT 2.4]
Sol - 2.5 molal aqueous solution means 2.5 moles of urea in 1000g of water
Molar mass of urea = (14x2) + (1x4) + 12 + 16 = 60 gmol-1
Mass of urea = moles x molar mass = 2.5 x 60 = 15 g
Total Mass of solution = 1000 + 15 = 1015 g = 1.015 kg
1.015 kg solution contain = 15g of urea
2.5 kg solution will contain = = 37g
Q.13 - Calculate the (a) Molality (b) Molarity (c) Mole fraction of KI if the density of 20%
(mass/mass) aqueous solution is 1.202 g/mL. [NCERT-INTXT 2.5]
Sol - 20% by mass KI in aqueous solution means 20g of KI in 100 g of solution or 80g of water
Mass of KI = 20g, Mass of water i.e. solvent = 80g, Molar Mass of KI = 39 + 127 = 166 g/mol
(a) Calculation of Molality - m = = = 1.5 mol/kg

(b) Calculation of Molarity - Volume of solution = = = 83.2 mL

M = = = 1.44 mol/L
(c) Calculation of Mole Fraction

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Moles of KI (n1) = = 0.12 ; Moles of water (n2) = = 4.44

Mole fraction of KI [ ] = = = 0.0263

Q.14 - Concentrated Nitric Acid used in the lab is 68% by mass in aqueous solution. What should be
the molarity of such a sample of the acid if the density is 1.504 g/mL? [NCERT-EX. 2.4]
Sol - 68 % by mass aqueous HNO3 solution means 68g of HNO3 in 100 g of solution or 80g of water
Mass of HNO3 = 68g, Mass of water = 80g, Molar Mass of HNO3 = 1 +14 + (16 x 3) = 63 g/mol
Volume of solution = = = 66.5 mL

M = = = 16.23 mol/L
Q.15 – A sample of glucose in water is 10%w/w. What would be molality and mole fraction of each
component in solution? If the density is 1.2 g/ml, then what is molarity of the solution? [NCERT-EX. 2.5]
Sol - 10 % (w/w) aqueous glucose solution means 10g of glucose in 100 g of solution or 80g of water
Molar mass of Glucose = (12x6) + (1x12) + (16x6) = 180 gmol-1

Moles of glucose (n1) = = 0.0556 ; Moles of water (n2) = =5

(a) Calculation of Molality - m = = = 0.617 mol/kg

(b) Calculation of Mole Fraction -

Mole fraction of glucose [ ]= = = 0.01 , [ ]= 1 - = 1 - 0.617 = 0.493

(c) Calculation of Molarity - Volume of solution = = = 83.3 mL

M = = = 0.67 mol/L
Q.16 – A solution obtained by mixing 300g of 25% and 400g of 40% solution by mass. Calculate the
mass percentage of the resulting solution? [NCERT-EX. 2.7]
Sol - 25 % means 100g solution contain 25g solute so 300g will have 75 g of solute
40 % means 100g solution contain 40g solute so 400g will have 160 g of solute
Total mass of solute = 75 + 160 = 235g ; Total mass of solution = 300g + 400g = 700g
Mass percentage of solute in the solution = = 33.5%
Q.17 – An antifreeze solution is prepared from 222.6 g of ethylene glycol (C2H6O2) and 200 g water.
Calculate the molality of solution. If density of solution is 1.072 g/cc, Find its molarity? [NCERT-EX. 2.8]
Sol - (i) Molality(m) = = = 17.95 mol/kg

(ii) Mass of solution = 222.6g + 200g = 422.6g

Volume of solution = = = 394.21 mL

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Molarity (M) = = = 9.1076 mol/L

Q.18 – A sample of drinking water is severely contaminated with chloroform CHCl3 supposed to be
carcinogenic. The level of contamination is 15 ppm (by mass). [NCERT-EX. 2.9]
(a) Express this in percentage by mass (b) Determine the molality of chloroform in the sample ?
Sol - 15 ppm (by mass) means 15 parts (g) CHCl3 in 1 million 106 parts (g) of solution
(a) Percentage by mass = = 15 x

(b) Since the mass of solute is very-2 less then solution so mass of solvent is ≈ 106
Molar mass of CHCl3 = 12 +1 + (35.5 x 3) = 119.5 g/mol
m = = = 1.25 x m

Q.19 - Which among 1 molar (1M) & 1molal (1m) solution has higher concentration and why ?
Ans. - In Aqueous solution, 1M has higher conc. then 1m solution. It is because 1m solution is 1 mol
solute in 1000g solvent or 1000cc. of solvent (d = 1 g/cc) But 1 M solution is 1 mol solute in 1000cc. of
solution which contain less than 1000cc of solvent because solute is also present in this solution. Hence,
1000cc of the solvent will contain more than 1 mole of solute.
In Non-Aqueous solution, 1M can be more, lesser or equal to 1m depending upon the density of solution.
Q.20 - Under what condition molality = Molarity . Explain?
Sol. - If solution is very-2 dilute & density is 1g/cc. So 1000mL solution ≈ 1000 g solution ≈ 1000 g solvent
and molarity = molality
Q.21 - What is mole fraction of a solute in 2.5m aq. Solution ?
Sol - 2.5 m aq. Solution means 2.5mol solute in 1000g water.
Moles of water (n2) = = 55.5 , Moles of solute (n1) = 2.5

Mole fraction of solute = = 0.0431

Q.22 - Calculate moles of methanol in 5 Litres of its 2m if density of solution = 0.981 kg/L. Molar
mass = 32g/mol ?
Sol - Mass of 5L solution = d x V = 0.981kg/L x 5L = 4.905 kg = 4905gm
2m solution means 2 moles of methanol (CH3OH) in 1000g of solvent
Mass of methanol = moles x molar mass = 2 x 32 = 64g
Mass of 2m solution = Mass of (solvent + solute) = 1000g + 64 = 1064g
1064g solution contain = 2 mol methanol
4905g solution contain = = 9.219 mol

Solubility of Solid into Liquid - Maximum amount of solute dissolved in a fixed amount of solvent to from
a saturated solution at constant temperature is solubility of solid in liquid .
Factors affecting Solubility of Solid in Liquid –
(i) Nature of Solute & Solvent - Polar solute dissolve easily in polar solvent but not in non-polar solvent
while Nonpolar solute dissolve easily in non-polar solvent and not in polar solvent.

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 Actually when solute particle are added to the solvent, solvent particles surrounds solute particle from all
side (Solvation), Now if solute-solvent attraction are greater than solute-solute attractions, dissolution take
place otherwise not.
(ii) Temperature - Generally increase in temperature weaken attraction between atoms in solute particle so
its solubility in solvent become faster. For Ex- KCl, NaCl, KBr, NaNO3.
For salts like Na2CO3, Na2SO4.10H2O, CaO, solubility increase on decreasing temperature as energy is
released during the dissolution of these salts. i.e. their dissolution is endothermic.
 The Solubility of Glauber’s salt (Na2SO4.10H2O) initially increases upto 32.4oC as it remain hydrated or
solvated in aq. solution. But beyond 32.4oC, the solubility decreases as it change to anhydrous form or salt so
its dissolution become endothermic as a result its solubility decreases.
Solution of Gases in Liquid
 Most of gases are soluble in water to less or more amount. For ex - Aquatic animal are alive in lake
because O2 gas is soluble in water. Some gases are soluble in Ethanol, benzene etc.
 “Volume of gas (mL or cc) which can be dissolved in 1 ml (cc) of liquid to form Saturated solution at
constant Temp. and Pressure is called solubility of gas in liquid.”
 Solubility of gas in liquid at constant temp. is also expressed as Mole Fraction (Xgas) or Molarity.
Factors Affecting Solubility of Gas in solvent :-
1. Nature of gas and solvent - Permanent gases [O2, N2, H2] are nonpolar and have very low critical
Temp (Tc) so lesser soluble in water but more soluble in nonpolar solvent like Ethanol, Benzene, CS2.
 Gases like (CO2, NH3,) are highly soluble in water because these gases react with water and make H2CO3,
NH4OH respectively. Gas HCl undergo ionization in water ( ) so become soluble.
 Generally, Easily liquefiable gases (High Critical Temp) are more soluble in water than in nonpolar
solvent. For eg. NH3 , CO2 , CH4
2. Effect of Temperature - [ T ∝ ] Solubility of gases in liquid decrease with increase in
temperature as dissolution of gas is an exothermic process.
Gas + Solvent Gas/Liquid solution + Heat
Q.23 – Why do gases always tend to be less soluble in liquid as temp. is raised? [NCERT-EX. 2.11]
 Dissolution of gas in water is a reversible process and exothermic in nature i.e. energy is released. So if
temperature is raised (increased), according to Le-Chatelier principle, backward reaction is favoured/
increased i.e. gas escape/come out of solution and hence solubility or conc. of gas in solution decreased.
 Actually as Temp. is raised, attractions between gas particles and liquid molecules decreases so, solubility
or conc. of gas in solution decreases.
Thermal Pollution – During summers, temperature of water in lakes increases as a result, solubility of O2
gas in water decreases. It is called Thermal Pollution. It is very harmful for aquatic animals as they feel
suffocation and ultimately dies.
 The solubility of gases like H2, He, Ne in alcohol & acetone increase slightly as T is increased.
3. Effect of Pressure - [ P ∝ Solubility of gas] On increasing partial pressure, gas compresses so no. of
particles per unit volume increases as a result, rate of collision of gas particles on solution surface increases
thus concentration or solubility of gas in solution increases.
Henry’s Law – It explain the effect of pressure on solubility of gas in a liquids.

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1. Old Law - The solubility (mass) of gas dissolved in a given volume of liquid at constant temp is
directly proportional to pressure of gas over the solution.
Mathematically m ∝ p or m = p ………………(i)
m = mass of gas dissolved in liquid, p = partial pressure of gas over liquid
= Henry constant
The Value of depends upon nature of Gas, nature of Solvent and Temperature
 If solubility of gas at is then solubility of same gas at pressure can be calculated as -

= ………………..(ii)

2. New Law [Dalton-Henry Law]- If mole fraction of gas in solution represent solubility of gas then,
“Partial pressure of gas at given temp. is directly proportional to mole fractions of gas in solution.
Mathematically ∝
or
= . =

= Henry Constant. Its value change on changing Gas, Solvent, Temperature as well as Pressure
= Partial pressure of gas ; = Mole Fraction of gas dissolved in solution
Characteristic of - 1. The value of is different for different gases.
2. The value of for a gas is different in different solvents also it increase with increase in temperature.
3. Determination of the Solubility of Gas - We know that = so ∝ ……..(1)

Significance of – so Higher the value, lesser is the solubility of gas in liquid (Solution)or vice versa.
4. Unit of – It is similar to the unit of pressure - atm, bar, k bar or Pa
5. Effect of Temperature ( ∝ T ) - The value of increase on increasing temperature and
solubility of gas decreases at same pressure. So hot water in summer season contain lesser amount of oxygen
gas which is not suitable for aquatic animals.
Q.24 – Why do aquatic animals feel more comfortable in lakes during winter than in summer?
Ans - Aquatic animal are more comfortable in cold water than in hot water because at low temp. more
oxygen gas is dissolved (available) in cold water so it suits fishes and other animals.
Q.25 - Among gases He and H2, the for He is more than H2. Which gas is more soluble?
Ans - H2 gas , because KH is inversely proportional of Mole fraction of the gas
Limitation of Henry Law - Henry law is applicable – (i) At Low pressure (ii) At High temp. (Gas
behave ideally) (iii) If gas does not react with water & does not dissociates or associates so Henry law fails
in HCl & NH3 gas as both react with water.
Application of Henry Law - 1. In the functioning of Lungs during gases exchange.
2. Soda water, Cold water, Hard drinks bottles are sealed at high pressure to keep gas(CO2) dissolved in it.
3. When scuba divers go deep in sea, solubility of atmospheric gases increases in blood. When drivers come
up, solubility of gases in blood decreases so gases release out of blood and forms bubbles of nitrogen in our
blood capillaries. These bubbles get stuck in joints and cause pain which is called Bends. To avoid bends,
cylinder filled with mixture of 11.7% He + 56.2% N2 + 32.1% oxygen gas are used.
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4. At High Altitude, partial pressure of oxygen gas is low. It leads to low concentration of oxygen in blood
of people living there which causes Anoxia. It means unable to act & think properly.
 Dissolution of Gas in sugar solution is less than in pure water.
 Dissolution of Gas in aq. Electrolytic solutions is lesser than in pure water.
Q.26 – H2S is a toxic gas with rotten egg like smell is used for qualitative analysis. If the solubility of
gas in water at STP is 0.195m, calculate Henry Law constant. [NCERT-intext.2.6]
Sol. - 0.195m means 0.195 moles H2S gas in 1000g of water ; At STP, Pa = 1 bar
Moles of water = = 55.5 ; Now Mole fraction of Gas = = 3.5 x

Calculation of KH - = = = 285.6 bar

Q.27 – KH for CO2 in water is 1.67 x Pa at 298K. Calculate the quantity of CO2 in 500mL of soda
water when packed under 2.5 atm pressure at 298 K. [NCERT-intext.2.7]
Sol. - Pressure of CO2 = 2.5 atm = 2.5 x 1.013 x = 253312.5 Pa

From Henry law - = = = = 1.52 x

Calculation of Mole of CO2 - = ≈ (as nCO2 < < nH2O )

nCO2 = x nH2O = 1.52 x x ( ) = 0.0422 mol

Calculation of amount of CO2 = Moles x Molar mass = 0.0422 mol x 44 g/mol = 1.86 g
Q.28 – The partial pressure of ethane over a saturated solution containing 6.56 x g ethane is 1
Bar. If solution contain 5.00 x ethane what shall be the pressure of gas? [NCERT-EX.2.13]

Sol. - According to Henry law for two different solutions =

So = = p2 = 76.21 bar
Q.29 – Henry law constant for the molality of methane in benzene at 298K is 4.27 x mmHg.
Calculate the solubility of methane in benzene at 298K and at 760 mmHg pressure? [NCERT-EX.2.35]
Sol. - = 4.27 x g p = 760 mm Hg
= = = 1.78 x
Q.30 – The air is a mixture of a no. of gases. The major components are oxygen and nitrogenwith
aprox. Proportion of 20% and &9% by volume at 298K. The water is in equilibrium with air at a
pressure of 10atm. A 298K, if the Henry constant for O2 and N2 are 3.30 x mm Hg and 6.51 x
mm Hg respectively, Calculate the composition of these gases in water. [NCERT-EX.2.39]
Sol. – Total pressure of air = 10atm , Vol. of O2 = 20% , Vol. of N2 = 79%

Partial pressure of O2 ( ) = 10 x ( ) = 2 atm = 2 x 760 mm = 1520 mm

Partial pressure of N2 ( ) = 10 x ( ) = 7.9 atm = 7.9 x 760 mm = 6004 mm

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Mole fraction of O2 = = = 4.61 x

Mole fraction of N2 = = = 9.22 x

Q.31 – What conc. of N2 gas should be present in a glass of water at room temp.? Assume a total
pressure of 1atm, and mole fraction of N2 in air 0.78. For N2 = 8.42 x g [CBSE 2009]
Sol. – Partial pressure of N2 ( ) = 1 x 0.78 = 0.78 atm = 0.78 x 760 mm = 592.8 mm
Since the unit of KH given in g so formula of henry is applied as –
Conc. of N2 is - = = 592.8 mm x 8.42 x g = 4.99 x
Vapour Pressure of a Pure Liquid - The pressure exerted by vapour on its liquid surface at constant
temperature when liquid and gas are in equilibrium.
V.P. of any liquid is recorded only when the Rate of evaporation = Rate of condensation.
Factors affecting Vapour Pressure -
(1) Temperature (∝ Vapour Pressure) – Higher the temperature of liquid, more will be the escaping
tendency of liquid particles and higher will be the vapour pressure of the liquid.
(2) Attraction between Molecules of liquid ( ∝ ) – Weaker the intermolecular attraction
in solution, more will be the escaping tendency of liquid particles and Greater will be the vapour pressure.
Vapour Pressure of the Solution – There are following two types of Liquid solutions –
(i) Solid - Liquid Solution (ii) Liquid - Liquid Solution
(i) Vapour Pressure of Solid-Liquid Solution (having Non-Volatile, Non-Electrolyte Solute) –
or Effect of adding Non-volatile solute on Vapour Pressure of Solvent
When a non-volatile solute is added to a liquid solvent, its vapour pressure decrease i.e. the V.P. of liquid
(i.e. volatile component) in this solution ( ) become lower than V.P. of liquid in pure state ( ).
It is because some solute particle occupy positions of solvent particles on liquid surface, so fraction of
solvent particle on surface of such solution decrease thus the rate of evaporation of volatile liquid decrease so
V.P. of solution become lesser them that of pure solvent at same temperature.

R t’ L w – This law give relationship between - Vapour Pressure of volatile component ( ) in

solution and its Concentration or Mole fraction ( ) in that solution. It is stated as –
“At constant temperature, the Vapour Pressure of Volatile component ( ) in solution
is directly proportional to its mole fraction ( ) in that solution.”
i.e. ∝ or = .

The Raoult’s Law is applicable to – (i) Solid - Liquid Solution (ii) Liquid - Liquid Solution
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 Solutions 12

Case–1 Solid - Liquid Solution or R t’ L w f ti n c nt ining N n-Volatile Solute

According to this - “At constant temperature, the Vapour Pressure of Solution ( ) containing Non-
Volatile Solute is directly proportional to mole fraction ( ) of Volatile Component in that solution.”
Mathematically - ∝ or = . -------------- (1)

So Raoult’s Law for a Solid - Liquid solution can also be stated as – At constant temp. , Vapour
pressure of solution containing non-volatile solute is equal to the product of vapour pressure of volatile
component in Pure state ( ) and Mole fraction of volatile component ( ) in that solution.
In Eq. (1), = Vapour Pressure of Solution containing Non-Volatile Solute
= Vapour Pressure of Volatile Component in pure state
= Mole fraction of Volatile Component in solution
From Eq. (1), = (1 - ) = (1- )

Or
= =

Here = = Relative Lowering of Vapour Pressure ; = Mole Fraction of Solute

=
Moles of solute ; = Moles of solvent
So Raoult’s Law for a Solid - Liquid solution can also be stated as –
“At constant temperature, for a solution containing non-volatile solute, Relative Lowering
of Vapour Pressure is equal to the Mole fraction of solute in that solution.”

Case–2 Liquid-Liquid Solution or R t’ L w f Binary solution of two Volatile Liquids

When two volatile liquids are mixed to make a solution, the Vapour phase of such solution contain
Vapours of both volatile liquids. Now Raoult’s law for such solution is given as --
“At constant temp., for a solution containing two volatile liquids, the Partial Vapour Pressure
of each volatile component is directly proportional to its mole fraction ( ) in that solution.”
Suppose we mix and moles of volatile liquids A and B to make a binary solution,
Now & are the partial V.P. of Liquid A and B in this binary solution

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 Solutions 13

Now & are the V.P. of Liquid A and B in Pure State

And & are the Mole fraction of Liquid A and B in this binary solution
Now according to Raoult’s law
Partial V.P. of Liquid A in solution, ∝ = . -------------(1)
Partial V.P. of Liquid B in solution, ∝ = . -------------(2)
Now according to Dalton’s Law, Total Vapour Pressure over this solution is equal to the sum of the Partial
Vapour Pressure ( & ) of each volatile component in solution. i.e.
So Total Vapour Pressure of solution is calculated as- = + ------------(3)

= . + . & = .(1 - ) + .

Graphical Representation of Raoult’s Law for Liquid-Liquid Solutions

Conclusions of Graph for Liquid-Liquid Solutions -

(1) Minimum Total Vapour Pressure =
(2) Maximum Total Vapour Pressure =
(3) Total Vapour Pressure of solution depends upon the mole fraction of any component i.e. or
i.e. ∝ & ∝
(4) Since both the liquids are volatile, the vapour phase above the solution contain molecules of both the
liquids. However more volatile liquid have more no. (or share) of molecules in vapour phase.
(5) Liquid solutions Which obey Raoult’s law are called Ideal Solutions. Very few solution are ideal, for ex-
Benzene + Toluene , n-Hexane + n-Heptane , Chlorobenzene + Bromobenzene
Calculation of Mole Fractions of Volatile Components in Vapour Phase
Compositions of Vapour Phase of Solution – The mole fraction (or compositions) of the Volatile
Components in Vapour Phase can be calculated by using Partial pressure of both components.
Let and are the mole fractions of components in vapour phase then –

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 Solutions 14

Mole Fractions of Liquid A in Vapour Phase ( ) = =

Mole Fractions of Liquid B in Vapour Phase ( ) = =

= . = .
+ = 1 = 1–

Raoult’s Law as a special case of Henry Law –

According to Raoult’s Law, the vapour pressure of volatile component is directly proportional to its mole
fraction as - ∝ = .
While in a solution of gas in Liquid, the gas is taken as volatile component & its solubility is goverened by
Henry Law as - ∝ = .
On comparing the two equation, we conclude the same fact that,
“The pressure of volatile component is directly proportional to its mole fraction in solution.”
And only difference is their proportionality constant which is in Raoult’s Law and Henry’s law.
Now if = , Both Law become identical and Raoult’s law become a special case of Henry Law i.e. Henry
constant become equal to Vapour Pressure of volatile component in pure state.
Q.32– Cutting onion taken from the fridge is more comfortable than at room temperature? Explain.
Ans. – At lower temp. in fridge, the vapour pressure is quite low so lesser vapours of tear producing
chemicals are released and hence cutting onion taken from fridge are more comfortable.
Q.33 – Why is the liquid ammonia bottle first cooled in ice before opening?
Ans. – At room temperature, the Vapour pressure of NH3 is very high so its rapid vapourization cause harm.
Now on cooling, Vapour pressure of NH3 becomr low and it will not splash out and cause no harm.
Q.34 – The Vapour pressure of ethanol and methanol are 44.5 and 88.7 mm Hg respectively. An ideal
solution is formed at the same temp. by mixing 60g ethanol and 40g methanol. Calculate the total
Vapour pressure of the solution and mole fraction of methanol in Vapour phase.
Sol. – Moles of Ethanol (n1) = = 1.304 ; Moles of Methanol(n2) = = 1.25

Mole fraction of Ethanol [ ] = = = 0.51

Mole fraction of Methanol [ ] = 1 - = 1 - 0.51 = 0.49
V.P. of Pure Ethanol ( ) = 44.5 mm Hg ; V. P. of Pure Methanol ( ) = 88.7 mm Hg
V.P. of Ethanol in Solution - = . = 44.5 mmHg x 0.51 = 22.69 mmHg
V.P. of Methanol in Solution - = . = 88.7 mmHg x 0.49 = 43.46 mmHg

Total Vapour Pressure of the solution = + = 22.69 + 43.46 = 66.15 mmHg

(ii) Calculation of Mole fraction of Methanol in vapour phase -
Mole fraction of Methanol in Vapour phase ( ) = = = 0.657 mmHg

Mole fraction of Ethanol in Vapour phase ( ) = = = 0.343 mmHg

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 Solutions 15

Q.35 – The Vapour pressure of Pure Liquid A and B are 450mm Hg and 700mm Hg at 350K. Find the
composition of liquid mixture and also in Vapour if total vapour Pressure is 600mm Hg?
Sol. – = 600mm Hg , = 450mm Hg = 700mm Hg [NCERT-intext.2.8 ]
Let mole fraction of Liquid A is and mole fraction of Liquid B is
= .(1 - ) + .
600 = 450 .(1 -) + 700. 600 = 450 - + 700.
600 = 450 - 250. 250. = 600 - 450
Mole fraction of Liquid B [ ] = = 0.6
Mole fraction of Liquid A [ ] = 1 - = 1 - 0.6 = 0.4

Mole Fractions of Liquid A in Vapour Phase ( ) = =

= = 0.3
Q.36 – The Vapour pressure of Chloroform (CHCl3) and Dichloromethane (CH2Cl2) at 298K are 200
and 415mm Hg. Calculate – [NCERT-example]
(i) Vapour pressure of solution prepared by mixing 25.5 g of CHCl3 and 40g of CH2Cl2 at 298K.
(ii) The mole fraction of each component in Vapour phase.
Sol. - (i) Calculation of Vapour pressure of solution -
Mass of CHCl3 = 25.5 g ; Mass of CH2Cl2 = 40g
Molar mass of CHCl3 = 12 + 3 + (3 x 35.5) = 119.5 g/mol
Molar mass of CH2Cl2 = 12 + 2 + (2 x 35.5) = 85 g/mol
Moles of CHCl3 (n1) = = 0.213 mol ; Moles of CH2Cl2 (n2) = = 0.470 mol

Mole fraction of Chloroform [ ] = = 0.312

Mole fraction of Liquid A [ ] = 1 - = 1 - 0.312 = 0.688
= . + . = 200 x 0.312 + 415 x 0.688 = 62.4 + 285.5 = 347.9 mm Hg
(ii) Calculation of Mole fraction of both liquid in Vapour phase -
Mole Fractions of CHCl3 in Vapour Phase ( ) = = = 0.18

Mole Fractions of CH2Cl2 in Vapour Phase ( ) = = = 0.82

Q.37 – Heptane (C7H16) and Octane (C8H18) from ideal solution. At 373K, the vapour pressure of the
two liquid components are 105.2 kPa and 46.8 kPa respectively. What will be the vapour pressure, in
bar, of a mixture of 26.0g of heptane and 35.0 g of octane? [NCERT-ex 2.16]
Sol - Molar mass of Heptane = (12 x 7) + 16 = 100 , Molar mass of Octane = (12 x 8) + 18 = 114
Moles of Heptane (n1) = = 0.26 mol ; Moles of Octane (n2) = = 0.31 mol

Mole fraction of Heptane [ ] = = 0.456

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 Solutions 16

Mole fraction of Octane [ ] = 1 - = 1 - 0.456 = 0.544

= . + . = 105.2 x 0.456 + 46.8 x 0.544 = 47.97 + 25.46 = 73.43 kPa
Q.38 - 100g of liquid A (molar mass = 140g) was dissolved in 1000g of liquid B (molar mass = 180g)
the vapour pressure of pure B was found to be 500 torr. Calculate the vapour pressure of pure A and
its vapour pressure in solution if total Vapour Pressure of solution is 475 torr. [NCERT-ex 2.36]
Sol - Moles of A (n1) = = 0.714 mol ; Moles of B (n2) = = 5.556 mol

Mole fraction of A [ ] = = 0.114

Mole fraction of B [ ] = 1 - = 1 - 0.114 = 0.886
= . + . 475 = ( x 0.114) + (500 x 0.886)
475 = ( x 0.114) + 443 = = 280.70 torr
Vapour Pressure of Pure A = 280.70 torr
Vapour Pressure of A = . = 280.70 x 0.114 = 32 torr
Q.39 - Benzene and Toluene from ideal solution over entire range of composition. The vapour pressure of pure
Benzene and Toluene at 300K are 50.71 mm Hg and 32.06 mm Hg respectively. Calculate mole fraction of
benzene in vapour phase if 80 g of benzene is mixed with 100g of Toluene. [NCERT-ex 2.38]

Ideal and Non-ideal Solutions – On the basis of Raoult’s Law, Liquid-Liquid Solution are of two types-
(i) Ideal Solutions (ii) Non-ideal Solutions
Ideal Solutions – Solutions which obey Raoult’s Law at all concentrations & temperatures are
called ideal solutions. For an Ideal solution -
(i) = . and = .
(ii) Δ = 0 ; Heat change on mixing is zero i.e. no heat is released/absorbed on mixing two Liquids
(iii) Δ = 0 ; Volume change on mixing is zero i.e. volume of solution is equal to sum of the volume
of both liquids. = +
(iv) There should not be any chemical reaction between solute and solvent i.e. both liquids. For ex. -
NH3 + H2O NH4OH CO2 + H2O H2CO3
(v) Solute should not dissociate or associate in the solution.
Cause of Ideal Behavior – If attractions between A – B (solute & solvent) particles are similar to
attractions between A–A (solute-solute) and B–B (solvent- solvent) particles in their pure state, such solution
behave ideally.
Substances having similar structure, shapes and polarity make nearly ideal solutions. Practically no
solution is ideal however very dilute solution show nearly ideal behavior.
Examples of Ideal solutions – (i) Benzene + Toluene (ii) Chloro Benzene + Bromo Benzene
(iii) n-Heptane + n-Octane (iv) CCl4 + SiCl4 (v) Chloroethane + Bromoethane
For such solution, the vapour pressure of solution at any compositions is always intermediate between the
vapour pressure of both component liquids in pure state i.e. & .
Non-Ideal Solutions – Solutions which do not obey Raoult’s Law at any concentrations &
temperatures are called Non-ideal solutions. For a non-Ideal solution -

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 Solutions 17

(i) ≠ . and ≠ .
(ii) Δ ≠ 0 ; i.e. Heat is released or absorbed on mixing two Liquids
(iii) Δ ≠ 0 ; There will be change in volume on mixing both liquids i.e. volume of solution is
either more or less then sum of the volume of both liquids. ≠ +
Cause of Non-Ideal Behavior – If attractions between A – B (solute and solvent) particles are different
(weaker or stronger) then attractions between A–A (solute-solute) and B–B (solvent-solvent) particles in
their pure state, a non-ideal solution is obtained.
Types of Non-Ideal Solutions –
(i) Non-ideal solutions showing Positive deviation from Raoult’s law
(ii) Non-ideal solutions showing Negative deviation from Raoult’s law
(i) Non-ideal Solutions showing Positive deviation from Raoult’s law –
If the partial Vapour Pressure of each component (A & B) and total Vapour Pressure of solution is more
than the ideal behavior. Such solution show positive deviation from Raoult’s Law.
Cause of Positive Deviation – If attractions between A – B (solute and solvent) particles are weaker
then attractions between A–A (solute-solute) and B–B (solvent-solvent) particles in their pure state, the
escaping tendency of particles of both A and B liquids increases. As a result, Partial V.P. of each components
and Total V.P. of solution become more than ideal behavior and positive deviation from Raoult’s Law will
be observed. For such solution –
(i) > . and > .
(ii) Δ > 0 ; i.e. Endothermic Process. It means Heat is absorbed on mixing both Liquids
(iii) Δ > 0 ; i.e. > + i.e. volume of solution is more than sum of
the volume of both liquids because particles are loosely held so occupy larger volume.
(iv) Boiling point of such solution is lower than the boiling point of both components. It is because
Vapour Pressure of solution is higher than ideal behavior so it will become equal to atmospheric Pressure
earlier than normal B.Pt.
Examples of Non-Ideal solutions showing +ve Deviation –
(i) Acetone + Benzene/Ethanol/CS2 (ii) CCl4 + Benzene/Chloroform/Toluene
(iii) Water + Methanol/ Ethanol (v) Cyclohexanone + Ethyl alcohol
 On mixing CS2 and Acetone, +ve deviation from R t’ L w i b e ved. It is because attraction
between Acetone and CS2 molecules are weaker than pure acetone and pure CS2 molecules, as a result
escaping tendency of particles of both liquids increases. so, Partial V.P. of both liquids and Total V.P. of
solution become more than ideal behavior and positive deviation from Raoult’s Law will be observed.
 Similarly Solution of Cyclohexane (or Acetone) and Ethanol show +ve deviation. There exist H-
Bonding between Ethanol molecules. When Cyclohexane (or Acetone) is added, molecules of Cyclohexane
try to adjust between Ethanol molecules. As a result H-Bonding between Ethanol molecules decreases and
hence V.P. of both Cyclohexane and Ethanol increases and +ve deviation arises.
Q.40 – What role does molecular interaction play in solution of Alcohol and Water? [NCERT-ex 2.10]
Sol – There exist H-Bonding in both Alcohol and Water. Now on mixing alcohol and water, H-Bonding
arises between the molecules of alcohol and water. But this H-Bonding between alcohol and water
molecules is weaker than H-Bonding in Pure alcohol and Pure water so partial V.P. of both alcohol and water

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 Solutions 18

and total V.P. of solution increases and hence +ve deviation is observed. This solution will have higher V.P.
and lower B. Pt. than pure liquids.
(i) Non-ideal Solutions showing Negative deviation from Raoult’s law –
If the partial Vapour Pressure of each component (A & B) and total Vapour Pressure of solution is lower
than the ideal behavior. Such solution show negative deviation from Raoult’s Law.
Cause of Negative Deviation – If attractions between A – B (solute and solvent) particles are stronger
then attractions between A–A (solute-solute) and B–B (solvent-solvent) particles in their pure state, the
escaping tendency of particles of both A and B liquids decreases. As a result, Partial V.P. of each
components and Total V.P. of solution become lower than ideal behavior and Negative deviation from
Raoult’s Law will be observed. For such solution –
(i) < . and < .
(ii) Δ < 0 ; i.e. Exothermic Process. It means Heat is released on mixing both Liquids
(iii) Δ < 0 ; i.e. < + i.e. volume of solution is lesser than sum of
the volume of both liquids because particles are tightly held so occupy smaller volume.
(iv) Boiling point of such solution is greater than the boiling point of both components. It is because
Vapour Pressure of solution is lesser than ideal behavior so it will become equal to atmospheric Pressure at
a temperature higher than normal B.Pt of pure liquid.
Examples of Non-Ideal solutions showing -ve Deviation –
(i) Water + HCl/ HNO3 (ii) Acetone (CH3COCH3) + Aniline (C6H5NH2)
(iii) Chloroform + Diethyl ether (iv) Acetone (CH3COCH3) + Chloroform(CHCl3)
(v) Chloroform(CHCl3) + Nitric Acid (HNO3)

Q.41 - How can you explain the formation of solution showing –ve deviation from Raoult‟s law if
acetone is mixed with Chloroform.
Ans – There exist weaker dipole-dipole attraction between molecules in pure chloroform and pure acetone.
On mixing Acetone and Chloroform, H-Bonding arise between Chloroform and acetone, which is stronger
than this dipole-dipole attraction in pure chloroform and pure acetone molecules. Hence escaping tendency

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of both Chloroform and acetone molecules in solution decreases so partial V.P. decrease and this solution
show –ve deviation from Raoult’s Law.
Q.42 - Two liquid A and B on mixing produce a warm solution. Which type of deviation from
Raoult‟s law does it show?
Ans - It is –ve deviation from Raoult‟s law because in this deviation, energy is released which is absorbed
by resultant solution and it become warm.
Q.43 - 10cc. of liquid A were mixed to 10cc. of liquid B and the resultant solution has volume 19.92cc.
What deviation from Raoult‟s law you expect ?
Ans - It is –ve deviation from Raoult’s Law because the volume of resultant solution is lesser than sum of
volume of both liquid (10 + 10 > 19.92 cc) i.e. ΔV = –ve . OR Volume decrease means stronger attraction
between the molecules after mixing thus –ve deviation is observed.
Q.44 – Mention some difference between solutions showing +ve and –ve deviation from Raoult’s Law?
Constant Boiling Mixture or Azeotropic Mixtures
Liquid mixture which boil at same temperature like pure liquid and have same composition both in solution
and vapour phase are called constant Boiling Mixture or Azeotopes. These are of two types
(i) Minimum Boiling Azeptropes (ii) Maximum Boiling Azeptropes
(i) Minimum Boiling Azeptropes - It is formed by the liquids pair showing +ve deviation from
Raoult‟s law. At one intermediate composition, their vapour pressure is highest and boiling point is lowest
i.e. B.pt. is lower than the B.pt. of both component liquid. At this point, compositions i.e. mole fraction of
components in solution and vapour is same and Liquid mixture boils at same temp.
For Eg - 95.5% Ethanol + 4.5% Water make minimum boiling azeotropes which boil at 351.1 K temp
which is higher than B.Pt. of Ethanol (351.3K) as well as Water (373K)
Components Mass % of B. Pt.
A B Liquid B Liquid A Liquid B Azeotropic Mix.
Water (H2O) Propan-1-ol (C3H7OH) 71.7% 373 K 370 K 350.72 K
Chloroform (CHCl3) Ethanol (C2H5OH) 67% 334 K 351.3 K 332.3 K
Aceton (CH3COCH3) Carbon di Sulphide (CS2) 6.8% 329.25 K 320 K 312.2 K

(ii) Maximum Boiling Azeptropes - It is formed by the liquids pair showing -ve deviation from
Raoult‟s law. At one intermediate composition, their vapour pressure is Lowest and boiling point is highest
i.e. B.pt. is higher than the B.pt. of both component liquid. At this point, compositions i.e. mole fraction of
components in solution and vapour is same and Liquid mixture boils at same temp.
For Eg – 20.3% HCl by mass make Maximum Boiling Azeotropes which boil at 383 K temp which is
Lower than B.Pt. of HCl (188 K) as well as Water (373K)
Components Mass % of B. Pt.
A B Liquid B Liquid A Liquid B Azeotropic Mix.
Water (H2O) Nitric Acid (HNO3) 68 % 373 K 359 K 393.5 K
Water (H2O) Hydrochloric Acid (HCl) 57 % 373 K 293 K 400 K

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 Azeotropic Mixture cannot be separated into their component liquids by the fractional distillation method
because they make constant boiling mixture i.e. both liquids boils at same temperature and their vapours
contain molecules of both liquids hence separation is not possible.
Q.45 - Components of a Binary mixture of two liquid A and B were separated by distillation. After some
time, separation of components stopped and composition of vapour phase became same as in liquid phase. Both
the components started coming in distillate. Explain why this happens?
Ans - A and B on mixing form non-ideal solution. Now at this particular composition, the Azeotropic
mixture is obtained so both liquid evaporate simultaneously at same temp. So composition of vapour &
liquid phase become same and separation of components stopped.
Q.46 - Why pure ethyl alcohol cannot be obtained from Rectified spirit (95.6% ethanol + 4.5% water) even by
Fractional Distillation ?
Ans - Because it is an azeotropic mixture i.e. constant boiling mixture and at this composition both alcohol
& water vaporises hence separation is not possible.
Q.47 – Explain the terms ideal and non-ideal solutions in the light of forces of interactions operating between
molecules in liquid solutions? [NCERT-Exampler]
Q.48 – Why is it not possible to obtain pure ethanol by fractional distillation? What general name is given to
binary mixture which show deviation from Raoult’s Law and whose components cannot be separated by
fractional distillation. How many types of mixtures are there? [NCERT-Exampler]
Ans - Pure ethanol cannot be obtain by fractional distillation because when the mixture attain a compositions of
95.6% ethanol + 4.5% water, it become Azeotropic mixture. In general such mixtures are called Azeotropes.
These are of two types - (i) Minimum Boiling Azeotrope (ii) Maximum Boiling Azeotrope
Q.49 – What is meant by positive deviation from Raoult’s law? Give an example. What is the sign of H for
positive deviation? [CBSE-2015]

Colligative Properties – Properties of dilute solutions which depend upon no. of solute particles and
not on its nature are called Colligative Properties or Democrative Properties. Important Colligative
Properties are: (1) Relative Lowering of V.P. (2) Elevation in Boiling Point
(3) Depression in freezing Point (4) Osmotic Pressure
Colligative Properties are important as these provide method for the determination of molecular mass of
dissolved solutes only If, (i) Solution should be very dilute
(ii) Solute should not be Volatile & must not dissociates or associates in solution.

1. Relative Lowering of Vapour Pressure – [ ] – For a binary solution containing non-volatile

solute, the Relative Lowering of Vapour Pressure is equal to mole fraction of solute. Mathemtically.

= =

Here = = Relative Lowering of Vapour Pressure ;

= Mole Fraction of Solute ; = Moles of solute ; = Moles of solvent
= V. P. of Volatile Component in pure state

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= V. P. of Solution containing Non-Volatile Solute = = V.P. Volatile component in solution

 R.L.V.P. is a colligative property, as it depends upon no. of moles of solute and not on its nature.

 If the Conc. of Solution is 5% or

⁄
more, R.L.V.P. is calculated by = =
⁄ ⁄
following formula -
 If the Conc. of Solution is less
⁄
than 5% (very-2 dilute), R.L.V.P. = =
⁄
is calculated by following formula -

In above formulas - = Given mass of solute, = Molar mass of solute,

= Given mass of solute, = Molar mass of solvent
 R.L.V.P. is used to calculate the molar mass of unknown solute by above formulas-
Q.50 – The Vapour pressure of 5% aq. solution of non-volatile solute at 373K is 745 mmHg.
Calculate molar mass of solute.
Sol. – 5% aq. solution means 5 g of solute in 95 g of solvent i.e. water
=5g , =? , = 95 g , = 2 + 16 = 18 g/mol
Vapour pressure of pure water ( ) = 760 mm Hg ; Vapour pressure of solution ( ) = 745 mm Hg

= =

= = = 48 g/mol
Q.51 – An aqueous solution of 2% nonvolatile solute exert a pressure of 1.004 bar at the normal
boiling point of solvent. What is the molecular mass of solute? [NCERT-Ex. 2.15]
Sol. – 2 % aq. solution means 2 g of solute in 98 g of solvent i.e. water
=2g , =? , = 98 g , = 2 + 16 = 18 g/mol
V. P. of pure water ( ) = 1.013 Bar ; V. P. of solution ( ) = 1.004 Bar
= =

= = = 41.36 g/mol
Q.52 – The Vapour pressure of water is 12.3 kPa at 300 K. Calculate the Vapour pressure of 1 molal
solution of a non-volatile solute in it? [NCERT-Ex. 2.17]
Sol. – 1 molal solution means 1 mole of solute in 1000 g of solvent i.e. water
Moles of water ( )= = 55.55

= = = 12.08 k Pa
Q.53 – Calculate mass of a non-volatile solute (molar mass = 40 g/mol) which should be dissolved in
114 g of octane to reduce its V.P. to 80%. [NCERT-Ex. 2.18]

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Sol. – Suppose = 100 ; = 80 ; Molar mass Octane (C8H18) = (12 x 8) + (1 x 18) = 114g/mol

Moles of solute ( )= ; Moles of Octane ( )= =1

⁄
= = w = 10 g
⁄
Q.54 – A solution containing 30g of a non-volatile solute exactly in 90g water has a vapour pressure of
2.8 kPa at 298 K. Further 18g water is then added to the solution, the new vapour pressure becomes
2.9 kPa at 298 K. Calculate. (i) Molar mass of the solute. (ii) vapour pressure of water at 298K
Sol. – (i) Suppose the molar mass of the solute = m [NCERT-Ex. 2.18]

Moles of solute (n ) = , Moles of solvent (n ) = = 5 moles

= = 1- =

= 1 - = =

= = 1 + --------------(1)

Now after adding 18g of water, Moles of solvent (n ) = = 6 moles

= = 1- =

= 1 - = =

= = 1 + --------------(2)

, we get = 2.9 ( ) = 2.8 ( )

2.9 + = 2.8 + = 0.1 m = 23 amu

Putting m = 23 amu in eq. (1), = 1 + = 3.53 kPa

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 Solutions 23

2. Elevation in Boiling Point – [Δ ]– Atmospheric Pressure

T1 = B.pt of pure Liquid T2 = B.pt of solution
Δ = (T2 - T1) & Δ = Elevation in B.pt.
 Temperature at which V.P. of liquid get equal to atmospheric
pressure i.e. 1atm or 1.013 bar is called Boiling point of liquid. V.P.
 At Boiling point, both Liquid and Vapour phase exist together
in equilibrium. On dissolving a non-volatile solute into solvent, ΔTb
the vapour pressure of solution become lower than its pure
solvent. Now to make this lowered V.P. equal to Atmospheric
Pressure, the solution has to be heated more at a temp. higher T T1 T2
than actual B.pt. of pure solvent. So that V.P. of solution become equal to 1 atm (1.013bar) as a result, B.pt
of solution become higher than pure solvent, and it is called Elevation in Boiling point.
Mathematically ΔTb ∝ m i.e. molality

or ΔTb = Kb . m ΔTb = Kb ( )

Here Kb = Molal Elevation Constant or Ebulioscopic Constant ; m = molality

= Given mass of solute ; = Molar mass of solute ; = Mass of solvent
 Now if molality i.e. m = 1, then ΔTb = Kb
So Molal Elevation constant is defined as Elevation in the boiling point of solution having molality one.
Or in other words Molal Elevation constant of a solvent is defined as the increase in the boiling point of
a solution containing 1 mole of non-volatile solute in 1 kg solvent.
 Unit of Kb - K/m or K.kg.mol-1 [As Kb = ΔTb /m]
 Elevation in boiling point ∝ to molal conc. of solution i.e. no. of moles or molecules of solute particles so
it is a colligative property.
 Equimolal solution of all substances in same solvent will show equal elevation in boiling point.
 Kb can be calculated by following formula -
Here R = 8.314 J/K/Mol if Kb = Kb =
R = 2 cal/deg/Mol if & in cal
Tb = Boiling Point of Pure Solvent, mA = molar mass of solvent,
= Enthalpy of Vaporization of the solvent = Latent heat of Vapourisation per gram of Solvent
 For Water, Kb = 0.52 K/m and for benzene, Kb = 2.53 K/m
Q.50 – B.pt of Benzene is 353.23K. When 1.8 g of non-volatile solute is dissolved in 90g of benzene, the
B.pt raised to 354.11K. Determine molar mass of solute. (Kb = 2.53K Kg/mol)
Sol. – T1 = 353.23K , T2 = 354.11K , Δ = (T2 - T1) = (354.11 – 353.23) = 0.88K.
= 1.8g , = 90g , Kb = 2.53 K. kg/mol

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ΔTb = Kb ( ) 0.88 K =

= 57.5g/mol
Q.51 – 18g Glucose C6H12O6 (molar mass = 180 g/mol) is dissolved in 1 kg of water in a saucepan. At
what temperature will the water boil? For water Kb = 0.52 k kg & B. Pt. = 373.15K [NCERT-intxt 2.18]
Sol. – T1 = 353.23K , T2 = ? , = 18g , = 1000 g , Kb = 0.52 K kg/mol

ΔTb = Kb ( ) = =
Δ = (T2 - T1) T2 = Δ + T1 = (353.15 + 0.052) = 353.202 K.
Q.52 – A solution of glycerol (C3H8O3) in water was prepared by dissolving some glycerol in 500g of
water. This solution has a boiling point 100.42oC while pure water boil at 100oC. What mass of glycerol
was dissolved to make the solution? (For water Kb = 0.512 K.kg/mol) [CBSE 2012]
Sol. – Δ = (T2 - T1) = (100.42 – 100) = 0.42K. =? , = 500 g ,
Molar mass = (12 x 3) + (1 x 8) + (16 x 3) = 92 g/mol
g
ΔTb = Kb ( ) 0.42K =

= = 37.73 g
Q.53 – A solution having 8g substance in 100g of Diethyl ether boils at 36.86 oC, whereas pure ether
boils at 35. 60oC. Find the molecular mass of solute. (For Ether, Kb = 2.02 K.kg/mol) [CBSE 2008]
Q.54 – On dissolving 3.24g Sulphur in 40g benzene, boiling point of solution was higher than that of
benzene by 0.81K. What is the molecular formula of the Sulphur ? (For benzene Kb = 2.53 K.kg/mol)
(Hint- First find molar mass of sulphur from ΔTb formula. Now divide molar mass by atomic mass of sulphur
& get no. of atom in that molecule)

3. Depression in Freezing Point – [Δ ] –

T2 = Freezing Point of solution T1
T1 = Freezing Point of Pure Solvent
Δ = (T1 - T2) & Δ = Depression in F.pt.
 Temperature at which vapour pressure of liquid become equal
to the Vapour pressure of its solid state and both liquid and solid
state comes in equilibrium, it is called Freezing Point of Liquid.
 Decrease in the freezing point of solution than its pure solvent
is called Depression in freezing point.
 On dissolving a non-volatile solute in a solvent, the Vapour
pressure of solution become lower than its pure solvent. Now on T1 T2 T
cooling, V.P. of solution decreases and will become equal to V.P. of solid state at a temperature lower than
actual F.Pt. of pure solvent i.e. F.Pt. of solution become lower than its pure solvent.
Mathematically ΔTf ∝ m i.e. molality

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ΔTf = Kf . m ΔTf = Kf ( )

Here Kf = Molal Depression Constant or Crayoscopic Constant ; m = molality

= Given mass of solute ; = Molar mass of solute ; = Mass of solvent
 Now if molality i.e. m = 1, then ΔTf = Kf
So Molal Depression Constant is defined as Depression in the freezing point of 1 Molal solution.
or in other words Molal Depression constant of a solvent is defined as the decrease in the freezing point
of a solution containing 1 mole of non-volatile solute in 1 kg solvent.
 Unit of Kf - K/m or K.kg.mol-1 [As Kf = ΔTf /m]
 Depression in Freezing Point ∝ to molal conc. of solution i.e. no. of moles or molecules of solute particles
so it is a colligative property.
 Equimolal solution of all substances in same solvent will show equal depression in freezing point.
 Kf can be calculated by following formula -
Kf = Kf =
Here R = 8.314 J/K/Mole,
Tf = Freezing Point of Solvent, mA = molar mass of solvent,
= Enthalpy of the Fusion of the solvent, = latent heat of fusion per gram of solvent
 For Water, Kf = 1.86 K/m and for benzene, Kf = 5.12 K/m
 The method of the determination of the molar mass of solute by studying Depression in Freezing Point of
the solution is called Crayoscopic Method.
Application of the Depression in Freezing Point –
1. Anti-Freeze Solution – Substances which are added to a solvent to lower its freezing point is called
Anti-Freeze. For Eg. – Ethylene Glycol, Water. Water was used as a cooling agent earlier in Car radiator.
But in hilly area, water freezes at 0oC. To avoid this problem, Some substances are mixed in water so that
water does not freeze at 0oC, Such solution are called Anti-Freeze Solution.
The Ethylene Glycol lower the Freezing Point of water to quiet less extent.
2. To clear Ice from the roads – Common Salt (NaCl) or Calcium chloride (CaCl2) are used to clear snow
on the roads. This is because they depress the freezing point of water to such a lower extent that water cannot
freeze in to ice. Hence Ice melts off easily.
Q.55 – What is De-icing Agent ? How does it works ?
Ans. – Common Salt (NaCl) or Calcium chloride (CaCl2) are called De-icing Agent. These lower down the
F. Pt. of water such a lower extent that water cannot freeze in to ice. So used to clear snow on the roads.
Q.56 – What freeze out first when a solution of common salt is cooled?
Ans.– Water into ice.
Q.57 – Why does aq. solution of NaCl freezes at lower temp. than water but boil at higher temp. ?
Ans. – When a solute is dissolve into a solvent, the vapour pressure decreases and the solution boils at
higher temperature than the boiling point of water to make its V.P. equal to atmospheric pressure. But at the
same time, its freezing point decreases because to make its V.P. equal to the F. Pt. of its solid state, the temp.
of solution should be lowered to lower extent. Hence B. Pt. is increased while F. Pt. in decreased.

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Q.58 – Why is camphor preferred as solvent in finding molar mass of Naphthalene by rest method?
Ans. – For camphor, Kf is higher so Depression in Freezing Point is large enough for finding molar mass of
Naphthalene experimentally.
Q.59 – 45 gm Glycol (C2H6O2) is dissolved in 600g water. Calculate (i) Depression in Freezing point
(ii) Freezing point of solution. (Kf = 1.86 K Kg/mol) [NCERT-Ex.]
Sol. – = 45g, = 600g, Molar mass of Glycol = (12 x 2) + 6 + (16 x 2) = 62g/mol

(i) Cal. of ΔTf - ΔTf = Kf ( ) = = 2.25 K

(ii) Cal. of Freezing point - Δ = (T1 - T2) T2 = T1 - Δ = 273 – 2.25 = 270.75 K

Q.60 – A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the
freezing point of a 5% glucose in water if F.Pt. of pure water is 273.15K. [NCERT-Ex.2.20]
Sol. – 5% solution means 5 g of sugar in 95 g water
= 5g, = 95g, Molar mass of sugar ( ) = (12 x 12) + (1 x 22) + (16 x 11) = 342g/mol
Δ = (T1 - T2) = 273.15 – 271 = 2.15 K

(i) Cal. of Kf - ΔTf = Kf ( ) 2.15 K =

So Kf = 13.97
(ii) Cal. of ΔTf for glucose solution- = (12 x 6) + (1 x 12) + (16 x 6) = 180 g/mol

ΔTf = Kf ( ) ΔTf = = 4.08 K

(iii) Cal. of Freezing point of glucose solution -
Freezing point of glucose solution, T2 = (T1 - Δ ) = 273.15 – 4.08 = 269.07 K.
Q.61 – Two elements A & B compounds having molecular formula AB2 and AB4. When dissolved in
20g of benzene, 1g of AB2 lowers the freezing point by 2.3 K, whereas 1.0g of AB4 lower it by 1.3K. The
Molal depression constant for benzene is 5.1 K kg/mol. Calculate atomic mass of A and B.
Sol. – First we calculate molecular masses of both compounds [NCERT-Ex.2.20]

= Kf ( ) = = 110.87 g/mol

= Kf ( ) = = 196.15 g/mol
Let the atomic mass of A = a and atomic mass of B = b
So molar mass of AB2 = (a + 2b) a + 2b = 110.87
molar mass of AB4 = (a + 4b) a + 4b = 196.15
on solving the two equations, we have a = 25.58 u & b = 42.64 u
Q.62 – Calculate the mass of ascorbic acid (Vitamin C, C6H8O6) to be dissolved in 75 g of acetic acid to
lower its melting point by 1.5 oC. for Acetic acid = 3.9 K.kg/mol [NCERT-Intext.2.11].
Sol. – =?, = 75g , Molar mass of Vitamin C ( ) = (12 x 6) + (1 x 8) + (16 x 6) = 176g/mol
Δ = 1.5 K

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ΔTf = Kf ( ) 1.5 =

so = 5.08 g
OSMOSIS – “Net spontaneous flow of solvent from lower concentration (or from pure solvent)
towards higher concentration solution through SPM is called Osmosis.”
Cause of Osmosis – Movement of solvent particle take place in both direction but passing of solvent from
lower concentration pure solvent (or pure solvent) towards higher concentration solution take place in more
amount because of higher vapour pressure of dilute solution.

Semi Permeable Membrane (SPM) – It contain networks of microscopic holes or tubes filled with air.
Although solvent move continuously from both sides i.e. from lower to higher as well as from higher to
lower concentration solution, but since V.P. of the pure solvent (or dilute solution) is greater than
concentrated solution so movement (or evaporation) of solvent from higher to lower V.P. solution occur in
more amount as a result net flow take place from Lower conc. to higher conc. solution.

Natural SPM (Imperfect) Artificial SPM (Perfect)

Pig’ B dde , Gall Bladder, Copper Ferrocyanide, Cellulose Acetate, Ca3(PO4)2

Difference between Osmosis and Diffusion –

S.no. Osmosis Diffusion
It take place through Semi Permeable
1. Semi Permeable Membrane is not required.
Membrane.
It involves movement of only solvent In diffusion, both the solute and solvent
2.
particles only. particles can move.
3. In osmosis, solvent move from lower conc. In diffusion, solvent move from higher conc.
solution to higher conc. solution. solution to lower conc. solution.
4. Osmosis is limited to solution only. Diffusion occur in both Gases & in Liquids.
It can be reversed or stopped by applying
5. Diffusion cannot be reversed or reversed.
ext. pressure on higher conc. solution.

Osmotic Pressure : (π or P) The flow of solvent into the solution through SPM can be stopped by
applying pressure on the solution. The Minimum external pressure which must be applied over higher
conc. solution to just stop osmosis is called Osmotic Pressure. π = h.d.g
 It is denoted by π and measured by Berkeley & Hartley Method.
 Unit of Osmotic Pressure are atm or bar or Pascle
Reverse Osmosis - If external pressure is more than osmotic pressure is applied on solution, solvent
move from higher to lower concentration solution through SPM. It is called reverse osmosis.

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Use/Application of Reserve Osmosis - Desalination of Sea Water i.e. removal of salts from sea water.
Here sea water is separated from pure water by SPM. Now external pressure more than Osmotic pressure is
applied on to sea water so pure water flow through SPM and this water can be used for drinking. SPM used
for this purpose is Cellulose Acetate.

If External pressure (P) < Osmotic Pressure (π) Osmosis take place
If External pressure (P) = Osmotic Pressure (π) Osmosis stops
If External pressure (P) > Osmotic Pressure (π) Reverse Osmosis take place

Expression for the Osmotic Pressure – Osmotic pressure is directly proportional to the molar
concentration of solution as well as its temperature so π ∝ & π∝
So π ∝ or π= R _____________(1)

Here R = Universal Gas Constant (Solution Constant) [ R = 0.083 L.Bar/K/mol or R = 0.082 L.atm/K/mol]
C = Molarity/Concentration of solution ; T = Temperature of solution ; π = Osmotic Pressure
Since C = from Eq. (1) π = R [ ]. T or
π V= n R

No. of moles of solute, n = , So π V= [ ]. R. T ___________________(2)

Here = Mass of Solute , = Molar Mass of Solute. Eq.(2) is called Vant Hoff Equation.
 Solute in very dilute solution behave like gas and osmotic pressure of solution is equal to pressure which
solute would exert if it were a gas at same T & V.
Isotonic Solution - Two solutions having same osmotic pressure, show
no osmosis when separated by SPM. These = are called Isotonic solutions. For
Isotonic solutions.
= . R. T = . R. T

Important Points - (1) All the medicines injected directly into blood veins must be isotonic with the
body fluid otherwise RBC will either shrink or Burst.
(2) If the RBC are kept in 0.9 % (m/v) NaCl solution, the fluid inside RBC should be isotonic with this
solution so No Osmosis take place.

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Hypotonic Solutions Hypotonic Solutions

A solution having concentration lesser than 0.9%
A solution having concentration more than 0.9%
(m/v) NaCl or other solution is Hypotonic
(m/v) NaCl or other solution is Hypertonic Solution
Solution.
If the RBC are kept in hypotonic Solution, RBC If the RBC are kept in hypertonic Solution, RBC
swells up and even burst due to Endo-Osmosis shrinks due to Exo-Osmosis i.e. solvent move out of
i.e. solvent passes into the RBC. the RBC.
Some Explanations Based on Osmosis –
(a) Swelling of Tissues in Peoples taking more Salts – People consuming more salts or salty food suffers
a disease called Edema i.e. swelling or puffiness of tissues (cells) due to storing or retention of water in cells
and in between cells.
(b) Absorption of Water by the Plants – It take place through the roots due to osmosis because osmotic
pressure inside the cells of roots is higher than in soil water.
(c) Shrieving of Raw Mangoes for Pickles – Raw mangoes are kept in Concentrated solution of water, so
lose water due to osmosis and finally shrivel into Pickles.
(d) Revival of Wilted Flowers and limped Carrot – If wilted flowers and Limped Carrot are kept in
fresh water, Endo-osmosis take place (inflow of water) and both get refirmed.
(e) Prevention of Meat by adding Salt –Meat is preserved from bacteria by storing in salty solution,
Bacteria on salted meat loss water through osmosis, shrivels and dies.
(f) Prevention of by adding Sugar – Fruits are preserved from bacteria by storing in sugar solution,
Bacteria on candid fruits loss water through osmosis, shrivels and dies.
 Haemolysis – Repturing or Bursting of RBC by Hypotonic solution.
 Plasmolysis – Shrinking of RBC by Hypertonic Solution.
 Turgor – Pressure develop inside the cells due to inflow of water is called Turgor.
Q.63 – What will happens if RBC are kept in (i) 1% NaCl solution (ii) 0.6% NaCl solution
Ans – (i) Exo-osmosis take place i.e. solvent come out of RBC and hence RBC shrinks.
(ii) Endo-osmosis take place i.e. solvent enter the RBC and hence RBC swells up and finally burst.
Q.64 – Why Osmotic Pressure measurement technique is good for determine molar mass of the
macromolecules like Proteins and Vitamins ?
Ans. – Osmotic Pressure measurement technique is good for determine molar mass of the macromolecules
like Proteins, Polymers and Vitamins etc. because
(i) This experiment is carried out at room temperature so molecules do not dissociates or associates.
(ii) The value of Osmotic Pressure is large enough that it can be measured easily.
Q.65 – Calculate the Osmotic pressure in Pascal exerted by a solution prepared by dissolving 1.0 g of
polymer (Molar mass = 185000 g/mol) in 450 mL of water at 37 oC ? [NCERT-intxt.2.20]
Sol. – = 1.0 g, = 185000 g, o
T = 37 C + 273 = 310 K, V = 450mL π = ?

π V= [ ]. R. T π x 450 mL = ( )

π = 3.05 x atm = 3.05 x x 1.01 x Pa = 30.8 Pa

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Q.66 – A solution prepared by dissolving 8.95 mg of a gene fragment in water to form 35mL of
solution. The osmotic pressure of the solution at 25oC is 0.335 torr. Assuming gene fragment to be
nonelectrolyte, calculate its molar mass. [CBSE-2011]
Sol. – = 8.45 x g, o
= ?, T = 25 C + 273 = 298 K, V = 35 mL
π = 0.335 torr = atm = 4.4 x atm

π V= [ ]. R. T =

= 14201.4 g/mol
Q.67 – 100 mg of a protein is dissolved in enough water to make 10 mL of a solution. If this solution
has a osmotic pressure of 13.3 mmHg at 25oC, what is the molar mass of protein? [CBSE- 2009,2011]
Q.68 – 200 cc3 of aq. solution of protein contain 1.26 g of protein. The osmotic pressure of such a
solution at 300 K is found to be 2.57 x bar. Calculate the molar mass of protein. [NCERT-exmple]
Q.69 – A solution containing 15g urea per litre of solution in water has same osmotic pressure as aq.
solution of glucose in water. Calculate the mass of glucose present in 1 litre of its solution .
Sol. – For solution having same osmotic pressure = C1 = C2

or = = w2 = 45 g
w2 = 45 g
Q.70 – A 5% solution of Cane Sugar (molar mass = 342g/mol) is isotonic with 0.877% solution of urea.
Find the molecular mass of urea. [CBSE- 2015]
Sol. – 5% solution of Cane Sugar means 5 g sugar in 1 Ltr water
=5g , = 342 g/mol , V = 1 L
0.877% solution of urea means 0.877 g urea in 1 Ltr water
= 0.877 g , = ? , V=1L
For solution having same osmotic pressure = C1 = C2

Or = = = 59.9 g/mol

Abnormal Molecular Mass - If molecular or molar mass of solute determined by colligative property is
different from that of its theoretical value, it is called Abnormal Molar Mass.
 If Solute is Non-Electrolyte, it does not undergo dissociation or association in solution so
Molecular mass of solute determined by colligative property is equal to its actual or theoretical value.
For e.g. Glucose, Sugar, Urea.
 If Solute is Electrolyte, it undergo Dissociation or Association in solution, now Molecular mass
of so formed particle in solution (determined by colligative property) become different (either less or more)
than its actual or theoretical value. For e.g. Salts, Acid, Base, Complex salts.
Van’t Hoff’s Factor (i) - It is the ratio of Normal (actual) molar mass to its Abnormal value of the
molar mass.
i =

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 It can also be defined as the Ratio of abnormal value of colligative property to Normal value of colligative
property.
i =
 “i” is used to determine the extent of dissociation or association of solute is solution.
If i = 1 If i > 1 If i < 1
No Dissociation or Association Dissociation of solute occur. Association of solute occur.

 In Association, two or more molecules of solute combines to form a single entity (Dimer, Trimer etc.) as a
result, Molar mass of such entity will be more than the actual molar mass of one molecule hence i < 1
 In Dissociation, electrolytic solutes (Acids, Bases, Salts) break into two or more ions in aq. solution, so
molar mass of each ion will be smaller than the molar mass of actual molecule & hence i > 1
 If solute is a strong electrolyte, it undergo 100% dissociation or association, Van’t Hoff factor can be
calculated by following formula -

i =

For e.g. – Strong Acids [HCl, H2SO4, HNO3], Strong Bases [NaOH, KOH, Ba(OH)2],
Salts like NaCl, KCl, K2SO4, Na2SO4, CaCl2 etc.
 If solute is a weak electrolyte, it undergo dissociation or association to some extent only.
For e.g. – Carboxylic Acids [CH3COOH, CH3CH2CH2COOH, C6H5COOH], Phenol [C6H5OH] etc.
In such cases, i can be obtained by the degree of dissociation or association of electrolytes.
 For dissociation of Weak Electrolytes,
Degree of Dissociation is given by – ∝ =
n = no. of ions formed after dissociation
For e.g. – (i) CH3COOH + ; n = 2
(ii) K4[Fe(CN)6] 4 + [Fe(CN)6]4- ; n = 5
 For Association of Weak Electrolytes,
Degree of Association is given by - ∝ =

n = no. of particles undergoing association

For the formation of Dimer, 2 CH3COOH [CH3COOH]2 ; n = 2
For the formation of Trimer, 3A [ A ]3

Formula of Colligative Property in terms of Van’t Hoff’s Factor -

(i) Relative Lowering of Vapour Pressure - = i.

(ii) Elevation in Boiling Point - ΔTb = i . Kb . m ΔTb = i . Kb [ ]

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(iii) Depression in Freezing Point ΔTf = i . Kf . m ΔTf = i . Kf [ ]

(iv) Osmotic Pressure - π = i . R.C.T

Calculation of Dissociation Constant (Ka) ∝

here C = Molarity of solution =
∝

 i = 1 ; For Non electrolyte solutes like Glucose, Sugar, (sucrose), Maltose, Urea etc. Previous formulas
of colligative properties will be used.

Q.71 – Find value of Van’t Hoff’s factor (i) for (a) NaCl (b) K2SO4 (c) (Al)2(SO4)3
Sol. – (a) NaCl + : n = 2

NaCl is strong electrolyte so i = = = 2

(b) K2SO4 2 + : n = 2 + 1 = 3

K2SO4 is strong electrolyte so i = = = 3

Q.72 – Find the value of Van’T Hoff’s factor (i) for K4[Fe(CN)6] which undergo 50% dissociation?
Sol. – K4[Fe(CN)6] 4 + [Fe(CN)6]4- ; n = 5

∝ = = 0.5 ; Now ∝ = 0.5 =

i - 1 = 0.5 x 4 i = 2 + 1 = 3
Q.73 – 2 g of Benzoic Acid [C6H5COOH ] is dissolved in 25 g benzene and depression in freezing point
is 1.62 K. Find Van’t Hoff’s factor and degree of dissociation of weak acid if it form dimer in solution?
Sol. – = 2g, = 25g , Δ = 1.62 K
Molar mass C6H5COOH ( ) = (12 x 7) + (1 x 6) + (16 x 2) = 122 g/mol
Calculation of Van’t Hoff’s factor

ΔTf = i . Kf ( ) 1.62 K =

i = i = 0.504
Calculation of degree of dissociation - 2 C6H5COOH [C6H5COOH]2 ; n = 2

∝ = ∝ = = = 0.992

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Q.74 – Aq. solution containing 1.248g of BaCl2 (molar mass = 208.34 g/mol) in 100 g water boils at
100.0832oC. Calculate the Van’T Hoff’s factor & degree of dissociation of BaCl2. [Kb = 0.52 K.kg/mol]
Sol. – = 1.248g , = 100g , Δ = (T2 - T1) = 100.0832 – 100 = 0.0832
Molar mass BaCl2 ( ) = 208.34 g/mol
Calculation of Molality - m = = = 0.059 mol/kg
Calculation of Van’t Hoff’s factor
ΔTb = i . Kb.m i = = = 2.711
Calculation of Degree of Dissociation - BaCl2 B +2 ; n = 3

∝ = = = = 0.855

∝
Calculation of Dissociation Constant [K] K = = = 0.297
∝
Q.75 – 0.6ml of acetic acid having density 1.06g/ml is dissolved in 1 Ltr of water. The depression in
freezing point observed for this strength of acid was 0.0205oC. Calculate Van’T Hoff factor and
dissociation constant of acid. [ for water Kf = 1.86 K.kg/mol ] (NCERT)
Sol. – Mass of acetic acid ( ) = Volume x Density = 0.6 mL x 1.06 g/ml = 0.636 g
Mass of Solvent ( ) = Volume x Density = 1000 x 1g/mL = 1000g, Δ = 0.0205oC

Calculation of Molality - m = = = 0.0106 mol/kg

Calculation of Van’t Hoff’s factor

ΔTf = i . Kf.m i = = = 1.039 ≈ 1.04

Calculation of Degree of Dissociation - CH3COOH +2 ; n = 2

∝ = = = 0.04
∝
Calculation of Dissociation Constant [K] K = = = 0.000017 = 1.7 x 10-5
∝

Q.76 – Calculate the depression in freezing point of water when 10 g of CH 3CH2-CH(Cl)COOH is

added to 250g of water. Given Ka = 1.4 x 10-3 , Kf = 1.86K.kg/mol [NCERT-Ex.2.32]
Sol. – Molar Mass of Solute = (12 x 4) + (1 x 7) + (16 x 2) + 35.5 = 122.5g/mol

Calculation of Molality - m = = = 0.326 mol/kg

CH3CH2CH(Cl)COOH + , n=2
Calculation of ∝ (Degree of Dissociation)

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Ka = ∝ .C ∝ = √ = ∝ = 0.065

Calculation of Van’t Hoff’s factor -

∝ = 0.065 = i = 1.065
Calculation of Depression in Freezing point -
ΔTf = i . Kf.m ΔTf = 1.065 x 1.86K.kg/mol x 0.326 mol/kg =

Q.77 – 19.5g CH2FCOOH is dissolved in 500g water. The depression in F. Pt observed is 1.00C.
Calculate Van’T Hoff Factor and Dissociation Constt. of Fluoro Acetic Acid. Kf= 1.86 K.kg/mol
Sol. – Molar Mass of Solute = (12 x 2) + (1 x 3) + (16 x 2) + 19 = 78 g/mol [NCERT-Ex.2.33]
o
= 19.5 g , = 500 g , ΔTf = 1.0 C

Calculation of Molality - m = = = 0.5 mol/kg

Calculation of Van’t Hoff’s Factor
ΔTf = i . Kf.m i = = = 1.075
Cal. of Degree of Dissociation - CH2 (F)COOH + ; n = 2

∝ = = = 0.075

Calculation of Dissociation Constant [K]

∝
K = = = 0.00304 = 3.04 x
∝
Q.78 – Determine the amount of CaCl2 (i = 2.47) dissolved in 2.5 Litre of water such that Osmotic
pressure is 0.75 atm at 27oC. [ R = 0.082 Latm/K/mol] [NCERT-Ex.2.40]
Sol. – Molar Mass (CaCl2) = (40) + (35.5 x 2) = 111 g/mol, = ?, V = 2.5 L,
π = 0.75atm , i = 2.47 , T = 27 + 273 = 300 K

π .V = i . R .( ).T 0.75atm x 2.5L = ( )

= = 3.42 g

Q.79 – Determine Osmotic pressure of a solution prepared by dissolving 25 mg of K2SO4 in 2 Litre of

water at 25oC assuring that it is completely dissociated.
Sol. – Molar Mass (K2SO4) = (39 x 2) + 32 + (16 x 4) = 174 g/mol, = 25 mg = 25 x ,
V = 2.0 L, π= ? , T = 25 + 273 = 298 K

K2SO4 2 + ; i = = 3

π V = i . R .( ).T π x 2.0 L =

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π = 5.27 x atm
Comparison between Boiling and Freezing Point of two or more Solutions -
 If two solutions having same Molarity (or molality) are given and their Boiling or Freezing Point are to be
compared then first calculate their Van’T Hoff Factor. Now Solution having higher value of i will have
higher Boiling Point and same solution will have lower Freezing point.
 Elevation in Boiling Point Δ b ∝ i ∝ Boiling Point of solution
 Depression in Freezing Point Δ f ∝ i ∝
Q.80 – Among 0.1M NaCl and 0.1M urea, identify one with higher Boiling point & one with higher
freezing point.
Sol. – NaCl + , i=2
For urea NH2CONH2 , No dissociation or association take place so i = 1
 NaCl has higher Van’T Hoff factor than Urea so value of both Δ b & Δ f will be higher for 0.1 M NaCl
solution and hence this solution has higher Boiling Pt. and Lower Freezing Point.
 Urea has lower Van’T Hoff factor so there will be lesser decrease in its Δ f value so 0.1 M urea has higher
Freezing Point than 0.1 M NaCl solution.

COMPETITION FOCUS
Equivalent Mass : That mass of element which combines or displaces 1.008 parts by mass of hydrogen or 8
parts by mass of Oxygen or 35.5 parts by mass of Chlorine. So Eq. mass of Element =
 Equivalent mass of substance may change with change in valency. For ex. In CuO & in Cu2O, the valency
of Cu are 2 &1 so Eq. masses of Cu are 31.75 and 63.5 respectively. The Eq. mass is a pure no. and when
Eq. mass of a substance is expressed in gram it is called Gram Equivalent Mass. for ex. Eq. mass of Na is
23u & G.E.Q. is 23g.
Eq. Mass of Acid = Eq. Mass of Base =

Eq. Mass of Salt = Eq. Mass of ion =

Eq. mass of Oxidizing or Reducing Agent =

Normality : [N] It is defined as no. of gram equivalent of Solute dissolve in 1 litre (dm3) of solution.

N = N = N =

= given mass of solute, = Eq. mass of solute, = Volume of solution

Relation Between Normality & Molarity Normality = Molarity x n-factor :

Normality of Acid = Molarity x Basicity Normality of Base = Molarity x Acidity

 n –factor = = No. of replaceable H+ or OH- or total positive charge

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 for ex. - Normality of H2SO4 = 2 x Molarity of H2SO4

Normality of HCl = 1 x Molarity of H2SO4
 Like Molarity, Normality also depends upon volume so change on changing the temperature.
 Normality Equations : = + = )

Q. 1 – 1 litre of N/2 HCl solution is heated in a beaker. It was observed that volume of solution reduced
to 600 mL & 3.25 g of HCl is lost. Calculate normality of new solution.
Sol. – 1 L of N/2 HCl solution means 1/2 or 0.5 g eq. of HCl in 1 Litre of solution.
Mass of HCl in above solution = 0.5 x 36.5 = 18.25 g
Mass of HCl left in new solution = 18.25 - 3.25 g = 15 g
Volume of new solution = 600 mL
Normality = = = 0.685 g eq./L
Demal unit : [D] One Demal represents one mole of solute present in 1 Litre of the solution at 0oC.
 Normality, Demal also depends upon Volume so change on changing the Temperature.
Solid in Solid Solutions : Solution in which both solute & solvent are solid. like alloys, Tungsten Carbide.
1. Substitutional Solids : If atoms, ions or molecules of one solid lattice are replaced by atoms, ions or
molecules of different similar solid a substitutional solid is obtained. for ex. – Alloys like Brass (Cu + Zn),
Bronze (Cu + Sn), Gun Metal (Cu + Sn + Zn), Monel (Ni + Cu + Fe), Solder (Pb + Sn)
2. Interstitial Solids : If in the lattice of a solid, some small size atoms occupy interstitial sites or voids, a
interstitial solid is formed. for ex. – Tungsten Carbide [WC]. In this Tungsten atoms form f.c.c. lattice while
Carbon atoms adjust in octahedral voids. Another example is Steel [Fe + C]
Relation between Osmotic Pressure & Vapour Pressure :
= Vapour pressure of pure solvent, = Vapour pressure of solution
= = Osmotic pressure of solution, d = density of pure solvent
M = Molar mass of pure solvent, T = Temperature of solution
R = Gas constant in atm.mL/Degree/mol i.e. 82.1
Re ti n between tic P e e π B i ing P int E ev ti n Δ ) and Freezing point Depression :

π = Δ π = Δ

= Molal Elevation Constant of solvent = Molal Depression Constant of solvent

 The colligative properties [C.P.] of solutions depend on the total no. of particles present in the solution.
Since electrolytes undergo ionization and give more than one particles per formula unit so colligative effect
of electrolytic solution is always greater than non-electrolytic solution of same concentration.
 For solutions having same concentration but different electrolyte solute, the C.P. is high for the solution
having more no. of particles on ionization.
 For solutions having same conc. but different non-electrolyte solute, the C.P. have same value for all.
 For different molar conc. of same solute, the C.P. is high for more conc. solution.
 For solution of different solute having same % strength, the C.P. is high for solute of lower Mol. Mass.

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 For ex. – Amongst 0.1 M solution of Urea [i = 1], NaCl [i = 2], BaCl2 [i = 3], Na3PO4 [i = 4], & Al2 (SO4)3
[i = 5], the V. P. & freezing point will be lowest while Boiling Point will be highest for Al2 (SO4)3.
 Amongst 0.1% solution of Urea, Sucrose and Glucose [i = 1], the V. P. & freezing point will be lowest
while Boiling Point will be highest for urea.
 Osmotic pressure is best technique to determine molecular mass of a non-volatile solute.
 Substance having high V.P. [ e.g. - Petrol] evaporate more quickly than substance of lower V.P.
 When water outflow from a cell, it is Exo-osmosis & if water inflows it is Endo-osmosis.
 Gelatinous Cu2[Fe(CN)6] & gelatinous Ca3 (PO4)2 are artificial S.P.M. Cu2[Fe(CN)6] does not work in
non-aqueous solution as it dissolve in these solvents.
 Difference between Iso-osmotic and Isotonic solution – Common S.P.M. are permeable to certain solute
only. in fact, there is no perfect S.P.M. two solutions are said to be isotonic if these have same osmotic
pressure w.r.to a particular S.P.M. and such solutions are also iso-osmotic i.e. only for a particular S.P.M.,
the isotonic solution are iso-osmotic.
 Use of Camphor as solvent for depression in F. Pt – Camphor is used as solvent for determining the
molecular mass of solute as its Kf is quiet lower as compare to water i.e. aprox. 20 times more than water so
the depression is 20 times more in case of camphor than water. So solutes with high molecular mass give
measurable freezing point depression.

Q. 2 – 1.4 g of acetone dissolved in 100 g of benzene gave a solution which freeze at 277.12 K. Pure
benzene freeze at 278.4 K. 2.8 g of solid A dissolved in 100 g of benzene gave a solution which freeze at
277.76 K. Calculate the molecular mass of A. [IIT]
Sol. – We know that, ΔTf = Kf .( ) & ΔTf = ( - )

Case I - (278.4 - 277.12) = Kf .( ) 1.28 = Kf .( ) ---------(i)

Case I - (278.4 - 277.76) = Kf .( ) 0.64 = Kf .( ) ---------(ii)

Eq.(i) / Eq.(ii) we have M = 232

Q. 3 – To 500 cc of water, 3.0 x kg of acetic acid is added. If 23% of acid is dissociated, what will
be the depression in freezing point? Kf = 1.86 K.kg/mol & density of water = 0.997 g/cc. [IIT]
Sol. – Mass of the solute = 3.0 x kg = 3.0 g , Molecular mass of solute = 60 g/mol
Mass of the solvent = 500 cc x 0.997 g/cc = 498.5 g

Degree of Dissociation [ ∝ ] = 0.23 = i = 1.23 K

Δ = i. .( ) Δ = 1.23. .[ ] = 0.229K
Q. 4 – 1.22 g of benzoic acid is added to two solvents and data of Δ and are given below –
(a) in 100 g of acetone ; Δ = 0.17 K and = 1.7 K.kg/mol
(b) in 100 g of benzene ; Δ = 0.13 K and = 2.6 K.kg/mol? Find out the molecular mass
of C6H5COOH in both cases and interpret the result. [IIT 2004]

Sol. – Δ = .( ) 0.17 = 1.7.[ ] = 122

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Δ = .( ) 0.13 = 2.6.[ ] = 244

Molecular mass of benzoic acid become double in benzene it shows its Association in Benzene.
Q. 5 – (a) 10 g of a non-volatile solute were dissolved in 100g of water at 20oC. The V.P. is lowered
from 17.3555 to 17.2350 mm, calculate the m.wt. of solute.
(b) The V. P. of pure water at 25oC is 23.62 mm. what will be the V.P. of a solution of 1.5g urea in
50g of water? [IIT 2001]

Sol. – (a) = find =?

(b) = . = . find =?
Q. 6 – How much C2H5OH should be added to 1 litre water so that it will not freeze at -20oC.Kf = 1.86
Sol. – Mass of 1 litre water [ ] = 1000 g, for solute [ ] = ?, [ ] = 46, = 20 Do yourself
Q. 7 – Depression in F. Pt. of 0.1 molal solution of HF is -0.201oC. Calculate percentage degree of
dissociation of HF. Kf = 1.86 K.Kg/mole. [AIPMT2007]
Sol. – First find Van’T Hoff factor by - Δ = .m
Than Degree of Dissociation by [ ∝ ] = then find percentage dissociation.
Q. 8 – There is KI and sucrose solution with 0.1 M conc., if the osmotic pressure of KI & sucrose
solutions are 0.465 & 0.245 atm respectively. Then find the Van’T Hoff factor of KI and its degree of
dissociation. [AIPMT2008]
Sol. – For KI, π = i . R.C.T 0.465 = i x 0.1 x R.T -------(i)
For sucrose, π = i . R.C.T 0.245 = 0.1 x R.T ----------(ii)

Eq.(i)/ Eq. (ii) = i = 1.897

Degree of Dissociation [ ∝ ] = = = 0.897

Percentage Dissociation = ∝ x 100 = 0.897 x 100 = 89.7

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