02

Solutions
Solution is a homogeneous mixture of two or more substances. A solution of IN THIS CHAPTER ....
two substances is called a binary solution. The substances forming the
solution are called components of the solutions. As a generalisation, the Types of Solutions
component present in smaller amount is called solute and the other present Solubility
in larger amount is called solvent. Concentration of Solution
Vapour Pressure of Solutions and
Types of Solutions Raoult's Law
In case of binary solutions, each component may be solid, liquid or in gaseous
Ideal Solutions
state and on this basis different types of solutions are possible as
summarised, in the following table. Non-Ideal or Real Solutions

Different Types of Solutions Colligative Properties

Types of solution Solute Solvent Common example Osmosis

Abnormal Colligative Properties :
Gas Gas Mixture of oxygen and nitrogen gases
van't Hoff Factor
Gaseous solutions 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

Remember A solution in which water is the solvent is called an aqueous

solution. The solutions in which solid is present in larger proportion are called
solid solutions. Amalgam is a solution of liquid in solid. Alloys are solution of
a solid is another solid.

Solubility
The maximum amount of a solute that can be dissolved in a given amount of
solvent (generally 100 g) at a given temperature is termed as solubility at
that temperature.
628 JEE Main Chemistry

Values of Henry’s law Constant (K H )

Solubility of Gas in Liquid for Some Selected Gases in Water
All gases are soluble in water as well as in other liquids
Temp. KH Temp. KH
to a greater or lesser extent. The solubility of a gas in Gas Gas
(K) (k bar) (K) (kbar)
liquids depends upon the following factors
He 293 144.97 Argon 298 40.3
1. Nature of the Gas H2 293 69.16 CO2 298 1.67
The gases which can be easily liquified, are more soluble N2 293 76.48 HCHO 298 1.83 ´ 10 -5
in common solvents, e.g. CO2 is more soluble than H 2 and N2 303 88.84 CH4 298 0.413
O2 in water. Different gases dissolve to a different extent O2 293 34.86 Vinyl chloride 298 0.611
in the same solvent and same gas has different O2 303 46.82 (CH2 == CH— Cl)
solubilities in different solvents.
e.g. non-polar gases like O2 , N 2 etc., are very less soluble It is obvious from Eq. (i) that higher the value of K H at a
in water whereas polar gases like HCl, SO2 , NH3 , CO2 given pressure, the lower is the solubility of the gas in
etc., are highly soluble in water. the liquid. It can be seen from Table that the K H value
for both N 2 and O2 increases with increase of temperature
2. Nature of the Solvent indicating that the solubility of gases decreases with
The gases which are capable of forming ions in aqueous increase of temperature. It is due to this reason that
solutions are much more soluble in water than in other aquatic species are more comfortable in cold water rather
solvents. e.g. gases like HCl and NH3 are highly soluble than in warm water.
in water but not in organic solvents in which these do not
100
ionise.

Partial pressure
of HCl in torr
3. Temperature 500
The solubility of most gases in liquids decreases with
increase of temperature. When a solution of a gas is
heated, the gas is usually expelled.
However, some gases are more soluble at higher 0.01 0.02
temperature than at lower. e.g. H 2 and inert gases are c B (HCl in cyclohexane)
slightly more soluble in non-aqueous slovents with
Plot of solubility of HCl gas in
increase in temperature.
cyclohexane at 293 K.

4. Pressure Limitations of Henry’s Law

The solubility of a gas in liquid is also influenced by • At high pressures, the law becomes less accurate and
pressure. The relation between the solubility and the proportionality constant shows considerable
pressure is given by Henry’s law. According to this law, deviations.
p µ c ; p = K H c, m µ p or m = K H p …(i) • Also Henry’s law will hold true if temperature is not
too low.
where, m = mass of the gas dissolved per unit volume of a
solvent • Henry’s law is only applicable when gas is not highly
soluble (i.e. not under high pressure) and also when
c = mole fraction of gas in liquid
gas neither react chemically with the solvent nor
p = pressure of the gas at equilibrium with the dissociate or associate with the solvent.
solution
Applications of Henry’s Law
K H = Henry’s constant
• Production of carbonated beverages Soft drinks,
Thus, Henry’s law can also be stated as, the pressure of a soda water and other carbonated beverages contains
gas over a solution in which the gas is dissolved is equal dissolved carbon dioxide. In the preparation of these
to the amount fraction of the dissolved gas multiplied by beverages, CO2 is passed at high pressure to increase
Henry’s constant. Also in other words Henry’s law states its solubility.
that mass of a gas dissolved per unit volume of the
• Functioning of lungs In lungs, oxygen present in
solvent at constant temperature is directly proportional
the inhaled air dissolves in blood because of its high
to the pressure of gas.
partial pressure and combines with haemoglobin to
Different gases have different K H values at the same form oxyhaemoglobin. In tissues, where partial
temperature. This suggests that K H is a function of the pressure of oxygen is low, oxyhaemoglobin releases
nature of the gas. Table gives K H values of some common oxygen for its utilisation in cellular activities.
gases at specified temperature.
Solutions 629

• Anoxia in climbers At higher altitudes, the partial Example 2. Which one of the following statements
pressure of oxygen is less than that at the ground regarding Henry’s law is not correct? (JEE Main 2019)
level. This leads to low concentration of oxygen in (a) Different gases have different KH (Henry’s law constant)
blood and other tissues of the people living at higher values at the same temperature
altitudes or those of mountain climbers. The low (b) Higher the value of KH at a given pressure, higher is the
content of blood oxygen causes the climbers to become solubility of the gas in the liquids
weak and reduces their thinking ability which are (c) The value of KH increases with increase of temperature and
symptoms of conditions called anoxia. KH is function of the nature of the gas
• Deep sea diving Scuba divers (deep sea divers (d) The partial pressure of the gas in vapour phase is
carrying breathing kit containing compressed air) proportional to the mole fraction of the gas in the solution
suffer from the painful effects called bends when they
Sol. (b) At constant temperature, solubility of a gas ( S) varies
come towards the surface.
inversely with Henry’s law constant (KH)
• These painful effects arise due to decompression of
Pressure p
gases dissolved in their blood while breathing air at KH = =
high pressure under water. Solubility of a gas in a liquid S
Thus, higher the value of KH at a given pressure, the lower is the
These bends are minimised by using compressed air
solubility of the gas in the liquid.
that has been diluted with less soluble helium in the
breathing apparatus. In general, a compresed gaseous
mixture of 11.7% He, 56.2% N 2 and 32.1% O2 is used Solubility of Liquid in Liquid
in breathing kit (called scuba). A liquid may or may not be soluble in another liquid.
Depending upon the relative solubility of a liquid in
Example 1. H2S, a toxic gas with rotten egg like smell, is another, the following three cases are possible
used for the qualitative analysis. If the solubility of H2S in water
(i) Miscible When two substances dissolve in each
at STP is 0.195 m , calculate Henry’s law constant. (NCERT)
other, these are said to be completely miscible, e.g.
(a) 152 bar (b) 100 bar (c) 200 bar (d) 282 bar water and alcohol, benzene and toluene.
Sol. (d) Since, molality is given and molality is the moles present in (ii) Immiscible Two chemically different liquids such as
1000 g of water so first we find the moles of H2 S. water and oil, water and mercury, do not dissolve in
Using the formula, each other and are said to be completely immiscible.
n H2S (iii) Partially miscible Certain liquids like water and
c H2S =
n H2S + n H2O phenol, water and ether, which dissolve only to a
limited extent are known as partially miscible.
calculate Henry’s law constant.
Calculation of mole fraction of H 2S 0.195 m means that 0.195 mole Solubility of Solid in Liquid
of H2S are dissolved in 1000 g of water.
Solubility of solid solutes increases or decreases with
Number of moles of water in1000 g, (nH2O) increase in temperature depending on the nature of
(1000 g) solute. The effect of pressure on the solubility of solids in
= = 55.55 mol
(18 g mol-1) liquids is generally very small.
n H2S On the basis of solubility of solid (solute) in a liquid
Mole fraction H2S ( c H2S) =
n H2S + nH2O (solvent), solution may be of the following types
(0.195 mol) (i) Unsaturated solution A solution in which more
= solute can be dissolved without raising temperature
(0.195 + 55.55) mol
is called an unsaturated solution.
(0.195 mol)
= = 0.0035 (ii) Saturated solution A solution in which no solute
(55.745 mol) can be dissolved further at a given temperature is
Calculation of Henry’s law constant called a saturated solution.
According to Henry’s law, (iii) Supersaturated solution When the solution
partial pressure of H2S contains more solute than would be necessary to
c H2S = at STP saturate it, then it is termed as supersaturated
KH for H2S
solution. Supersaturated solutions are not in
partial pressure of H2S equilibrium with the solid substance.
KH for H2S =
c H2S Thus, if a small crystal of solute (say sodium
(0.987 bar) thiosulphate) is added to its supersaturated solution,
= = 282 bar
(0.0035) the excess immediately crystallises out.
630 JEE Main Chemistry

Mole fraction of A in vapour phase

Concentration of Solution pA p° c 0.5 × 400
The concentration of a solution is defined as the YA = = A A = = 0.4
ptotal ptotal 500
relative amount of a solute present in the solution . It is
generally expressed as the amount of solute present in a mole of B in vapour phase,
unit volume of solution. Solutions with relatively low YA + YB = 1
concentration are called dilute solutions, while those YB = 1 - 0.4 = 0.6
with relatively high concentration are called
concentrated solutions. Parts Per Million (ppm)
Various expression for the concentrations of solutions can When the amount of solute (in g) is present in one million
be summarised as (1 million = 106) per mL of solution, the concentration of
the solution is expressed in ppm.
Mass Percentage mass of solute (in g)
It is the amount of solute present in 100 g of the solution. ppm = ´ 106
total volume of solution (in mL)
mass of solute (in g)
Per cent by mass = ´ 100 In case of gases, ppm refers to volumes rather than
mass of solution (in g)
masses, i.e. 1 ppm means 1 cm3 of gaseous components is
Volume Percentage present in 1000 L.

The volume of solute (in mL) present in 100 mL of the

solution is called volume per cent.
Strength or Concentration in Gram
volume of solute (in mL) Per Litre
Per cent by volume (v/V ) = ´ 100
volume of solution (in mL) It represents the number of grams present in 1 L of
solution.
Mole Fraction (c) mass of solute (in g)
Strength of solution =
It is the ratio of the number of moles of one component volume of solution (in L)
(i.e. solute or solvent) to the total number of moles of
solute and solvent (i.e. moles of solution). Molarity (M)
moles of solute It is the number of moles of solute present in one litre of
csolute =
moles of solute + moles of solvent the solution.
moles of solvent number of moles of solute
csolvent = Molarity ( M ) =
moles of solute + moles of solvent volume of solution (in L)
c solute + c solvent = 1 =
mass of solute (in g)
mol. wt. of solute ´ volume of solution (in L)
Example 3. The vapour pressures of pure liquids A and B
Molarity varies with temperature due to accompanied
are 400 and 600 mmHg, respectively at 298 K. On mixing the
change in volume of the solution.
two liquids, the sum of their initial volumes is equal to the
volume of the final mixture. The mole fraction of liquid B is Unit of molarity = mol/L
0.5 in the mixture. The vapour pressure of the final solution, Relation between molarity and strength in g/L
the mole fractions of components A and B in vapour phase,
mass of solute (in g)
respectively are (JEE Main 2019) Molarity ( M ) =
(a) 450 mmHg, 0.4, 0.6 (b) 500 mmHg, 0.5, 0.5 molecular mass of solute ´ volume of
(c) 450 mmHg, 0.5,0.5 (d) 500 mmHg, 0.4,0.6 solution (in L)

Sol. (d) According to Dalton’s law of partial pressure strength in g/L

Molarity ( M ) =
ptotal = pA + pB molecular mass of solute
= pA° c A + pB° cB …(i) Relation between molarity (M) and mole fraction of
the solute (c )
Given, p°
A = 400 mm Hg, p°
B = 600 mm Hg
MM1
cB = 0.5, c A + cB = 1 c=
M ( M1 - M 2 ) + d
\ c A = 0.5
On substituting the given values in Eq. (i) we get, where, d = density of the solution
ptotal = 400 ´ 0.5 + 600 ´ 0.5 M1 = molar mass of solvent
= 500 mm Hg M 2 = molar mass of solute
M = molarity of solution
Solutions 631

Dilution Law on Basis of Molarity Molality (m)

If molarity and volume of solution are changed from M1 , It is the number of moles of the solute dissolved in 1000 g
V1 to M 2 ,V 2 then of the solvent.
number of moles of solute
M1V1 = M 2V 2 (Molarity equation) Molality ( m ) = ´ 1000
mass of solvent (in g)
If n1 moles of reactant ‘ 1’ react with n 2 moles of reactant mass of solute (in g) ´ 1000
M1V1 M 2V 2 =
‘ 2’ then = molecular weight of solute ´ mass of solvent (in g)
n1 n2
Molality is independent of temperature.
If two solutions of the same solute are mixed then
Unit of molality = g moles/kg of solvent.
molarity of the resulting solution,
Relation between molality and weight percentage
M1V1 + M 2V 2
M= of solute (x)
V1 + V 2 1000 ´ weight % of solute ( x )
m=
Example 4. Calculate the molarity of KI if the density of 20% (100 – x ) ´ molecular weight of solute
(mass/mass) aqueous KI is 1.202 g mL-1. (NCERT) Relation between molality (m) and mole fraction of
(a) 0.04 M the solute (c )
(b) 1.25 M mM1
c=
(c) 0.25 M 1 + mM1
(d) 1.45 M where, M1 = molecular mass of the solvent
Sol. (d) Since density is given, so first we calculate volume and Relation between molality (m) and molarity (M)
then molarity. M
Weight of the solution = 100 g Molality (m) = (If d in kg/L and M2 in kg/mol)
d - MM2
Density of the solution = 1.202 g mL-1
M
weight of solution Molality (m) = ´ 1000
Volume of the solution = 1000d - MM2
density (If d in g/L and M2 in g/mol)
(100 g) m´d
= Molarity (M ) =
(1.202 g mL-1) 1+
m ´ M2
= 83.19 mL = 0.083 L 1000

number of gram moles of KI where, M2 = molar mass of the solute

Molarity of the solution (M) = d = density of the solution.
volume of solution in litres
(20 g) /(166 g mol-1) Example 6. A solution of glucose in water is labelled as
= 10% w / w. What should be the molality of the solution, if the
(0.083 L)
density of solution is 1.2 g mL-1?
= 1.45 mol L-1 = 1.45 M (NCERT)

Alternate Method (a) 0.45 (b) 0.62 (c) 0.82 (d) 0.19
% by mass ´ density ´ 10 Sol. (b) 10% means
Molarity =
molar mass of KI WB = Mass of glucose = 10 g
20 ´ 1.202 ´ 10 Mass of solution = 100 g
= = 1.45 M
166 WA = Mass of water (solvent)
Example 5. 10.30 mg of O 2 is dissolved into a litre of sea = 100 - 10 = 90 g = 0.09 kg
water of density 1.03 g/mL. The concentration of O 2 in ppm is MB = Molar mass of glucose (C6H12O6)
(JEE Main 2020)
= (12 ´ 6) + (1 ´ 12) + (16 ´ 6)
Sol. (10.00)
= 72 + 12 + 96 = 180 g mol-1
Mass of O2 = 10.30 mg (Given)
WB /MB (10 g)/(180 g mol-1)
Mass of sea water solution = volume ´ density Molality of solution (m) = =
WA (0.09 kg)
= 1L ´ 1.03 g /mL
= 1000 mL ´ 1.03 g mL-1 = 1030 g (10 g)
=
(180 g mol-1) ´ (0.09 kg)
mass of O2
ppm = ´ 10 6
mass of solution = 0.617 mol kg -1 or 0.617 m
= 10 ppm
632 JEE Main Chemistry

Example 7. An ‘m’ molal solution of a compound in Þ normality ´ equivalent weight = molarity

benzene has mole fraction of solute equal to 0.2. The value of ´ molecular weight
‘m’ is molecular weight
For an acid, = basicity
(a) 0.018 (b) 0.14 (c) 0.040 (d) 0.0032 equivalent weight
Sol. (d) Mole fraction of solute is given by \ Normality of an acid = molarity ´ basicity
mM1 molecular weight
c= For a base, = acidity
1 + mM1 equivalent weight
where, M1 = molecular mass of the solvent, i.e. benzene = 78 \ Normality of a base = molarity ´ acidity
m ´ 78 Relation between normality and percentage of solute
0.2 =
1 + m ´ 78 x ´ d ´ 10
N =
0.2 + 0.2 ´ 78 m = 78 m E
where, x = % of the solute by mass
or (78 - 15.6) m = 0.2
d = density of solution in g/mL
or 62.4 m = 0.2
E = equivalent mass of solute
0.2
or, m= = 0.0032
62.4 Dilution Law on Basis of Normality
If normality and volume of solution are changed from N 1 ,
Normality (N) V1 to N 2 ,V 2 then
Normality is the number of gram equivalents of
N 1V1 = N 2V 2 (Normality equation)
substance dissolved per litre of the solution.
number of gram - equivalent of solute If n1 moles of reactant ‘ 1’ react with n 2 moles of reactant
Normality ( N ) = ‘ 2’ , then
volume of solution (in L)
N 1V1 N 2V 2
mass of solute (in g) =
= n1 n2
equivalent weight ´ volume (in L)
mass of solute ( w) (in g) If two solutions of the same solute are mixed then
N = ´ 1000 normality of the resulting solution,
equivalent weight ( E ) ´ volume (V ) (in mL)
N 1V1 + N 2V 2
w ´ 1000 NEV N =
or N = Þ w= V1 + V 2
E´V 1000
Volume of water added to get a solution of normality N 2
Again, Normality ( N ) from V1 mL of normality N 1 is
percent of solute
= ´ 10 æN - N2ö
equivalent weight of the solute V 2 - V1 = ç 1 ÷ V1
è N2 ø
weight percent of solute ´ sp. gravity of the solution ´10
= Normality changes with temperature since it involves
equivalent weight of the solute
volume. When a solution is diluted x times, its normality
Relation between normality and strength in g/L also decreased by x times.
mass of solute (in g) Unit of normality = gram equivalents per litre.
Normality ( N ) =
equivalent weight ´ volume (in L)
Example 8. What will be the normality of a solution
strength in g/L
= obtained by mixing 0.45 N and 0.60 N NaOH in the ratio 2 : 1
equivalent weight by volume ?
Relation between normality and molarity (a) 0.15 N (b) 0.8 N
number of g - equivalents of solute (c) 0.5 N (d) 0.45 N
Normality =
volume of solution (in L) Sol. (c) g-equivalents = 0.45 ´ 2V + 0.60 ´ V
number of moles of solute
and, Molarity = Total volume =2 V + V = 3V
volume of solution (in L)
Þ g-equivalents of NaOH solution obtained = N ´ 3V
Normality number of g - equivalent of solute \ N ´ 3V = 0.45 ´ 2V + 0.6V
\ =
Molarity number of moles of solute 3NV = 0.9V + 0.6V
molecular weight 1.5V 1
= N= = = 0.5
equivalent weight 3V 2
Solutions 633

Formality (F) The vapour pressure of liquid in solution is known as its

partial vapour pressure and is less than the vapour
This is the concentration unit for ionic compounds which pressure of the pure liquid at the same temperature.
dissolve in a polar solvent to give pair of ions. This
represents number of gram-formula weight of the If p° be the vapour pressure of pure liquid and ps be that
substance dissolved per litre of the solution. It is almost of liquid in solution then lowering of vapour pressure of
the same as molarity. It describes the solute that is the liquid = p° - ps
p° - ps
mixed in a liquid rather than the solute present in \ Relative lowering in pressure =
solution after the dissolution process. p°

Formality =
moles of substance added to solution Raoult’s Law
volume of solution (in L) Raoult’s law states, “For a solution of two miscible
If formula weight is equal to molecular weight, formality liquids, the vapour pressure of each liquid in the solution
and molarity will be same. is less than the respective vapour pressure of the pure
Formality is also dependent on temperature. liquid and at the equilibrium, partial vapour pressure of
the liquid is directly proportional to its mole fraction in
Demal (D) solution.”
It is equal to molar concentration at 0°C, i.e. 1D For a solution containing two liquids A and B, the partial
represents one mole of the solute present in one litre of vapour pressure of liquid A is
the solution at 0°C. pA µ c A or pA = kc A
nA
Remember Normality and molarity changes with where, c A = = the mole fraction of liquid A
( nA + nB )
temperature because these involve volumes while molality,
mole fraction and mass fraction do not change with The proportionality constant k is obtained by considering
temperature because they involve weights. the pure liquid when c A = 1, then k = pA° , (the vapour
pressure of pure liquid), hence,
Vapour Pressure of Solutions pA = pA° c A
Similarly, pB = pB° c B
and Raoult’s Law
The pressure exerted by the vapours of a solvent while in According to Dalton’s law of partial pressure, the
equilibrium with pure solvent, at a given temperature, is total pressure ( ptotal ) over the solution phase in the
called vapour pressure. container will be the sum of the partial pressures of the
components of the solution and is given as
ptotal = pA + pB
Factors Affecting Vapour Pressure Substituting the values of pA and pB , we get
Vapour pressure gets affected by following factors ptotal = c A p°A + c B p°B
(i) Purity of the liquid Pure liquid always has a = (1 - c B ) p°A + c B p°B
vapour pressure higher than its solution.
= p°A + ( p°B - p°A )c B
(ii) Nature of the liquid Liquids which have weak
intermolecular forces are volatile and have greater Following conclusions can be drawn from the equation
vapour pressure. • Total vapour pressure over the solution can be related
(iii) Temperature The vapour pressure of a liquid to the mole fraction of any one component.
increases with increase in temperature. This is • Total vapour pressure over the solution varies
because on increasing the temperature the kinetic
linearly with the mole fraction of component B.
energy of molecules increases that results into the
fact that more molecules of the liquid can go into • Depending on the vapour pressures of the pure
vapour phase. components A and B, total vapour pressure over the
(iv) Effect of adding non-volatile solute When a solution decreases or increases with the increase of
liquid contains a non-volatile solute, some of the the mole fraction of component.
solvent molecules are replaced by the solute particles The composition of vapour phase in equilibrium with the
on the liquid surface and therefore, the available solution is determined by the partial pressures of the
surface area for the escape of solvent molecule components. If y1 and y2 are the mole fractions of the
decreases. component 1 and 2 respectively in the vapour phase then,
Due to the less available area on the surface of liquid using Dalton’s law of partial pressures :
for escape, rate of evaporation and hence, the rate of p1 = y1 ptotal
condensation both lowers. p2 = y2 ptotal
634 JEE Main Chemistry

In general, pi = yi ptotal Mole fraction of heptane

Also in other words the vapour pressure of a solution nB (0.26 mol)
( cB) = = = 0.458
containing non-volatile solute is directly proportional to nA + nB (0.307 + 0.26) mol
the mole fraction of the solvent. Vapour pressure of pure heptane ( pB° ) = 105.2 kPa

pB pB Vapour pressure of pure octane ( p°A ) = 46.8 kPa

p = pA + pB
Vapour pressure

pA
= p B+ In the mixture of 26.0 g heptane and 35.0 g octane
pB (i) Vapour pressure of heptane ( pB) = pB° cB
pA =
pA c
A = (105.2 kPa ´ 0.458)
cA = 1 Mole fraction cA = 0 = 48.18 kPa
cB = 0 cB = 1 (ii) Vapour pressure of octane
Relationship of vapour pressure and mole fraction of an ( pA ) = p°A c A = (46.8 kPa ´ 0.541) = 25.32 kPa
ideal solution at constant (Raoult’s law is being followed). (iii) Total vapour pressure of the mixture
( p) = pA + pB
Raoult’s Law as a Special Case of = 25.32 + 48.18 = 73.5 kPa
Henry’s Law
According to Raoult’s law, the vapour pressure of a Example 10. The vapour pressure of chloroform (CHCl3)
volatile component in a given solution is given by and dichloromethane (CH2Cl2) at 298 K is 200 mm Hg and
pi = xi p°i . In the solution of a gas in a liquid, one of the 415 mm Hg, respectively. If a solution is prepared by mixing
components is so volatile that it exists as a gas and we 25.5 g of CHCl3 and 40 g of CH2Cl2 at 298 K, calculate the
have already seen that its solubility is given by Henry’s mole fractions of chloroform in vapour phase. (NCERT Exemplar)
law which states that (a) 0.18 (b) 0.82 (c) 0.34 (d) 0.48
p = KHx
Sol. (a) Molar mass of CH2Cl2 = 12 ´ 1 + 1 ´ 2 + 35.5 ´ 2
If we compare the equations for Raoult’s law and Henry’s
law, it can be seen that the partial presssure of the = 85 g mol-1
volatile component or gas is directly proportional to its Molar mass of CHCl3 = 12 ´ 1 + 1 ´ 1 + 35.5 ´ 3
mole fraction in the solution. Only the proportionality = 119.5 g mol-1
constant K H differs from p°i , 40 g
Moles of CH2Cl2 = = 0.47 mol
Thus, Raoult’s law becomes a special case of Henry’s law 85 g mol–1
in which K H becomes equal to p°i . 25.5 g
Moles of CHCl3 = = 0.213 mol
119.5 g mol-1
Example 9. Heptane and octane form an ideal solution. At
Total number of moles = 0.47 + 0.213 = 0.683 mol
373 K, the vapour pressure of the two liquid components are 0.47 mol
105.2 kPa and 46.8 kPa respectively. What will be the vapour c CH2Cl2 = = 0.688
0.683 mol
pressure of a mixture of 26.0 g of heptane and 35 g of octane?
(NCERT) c CHCl3 = 1.00 - 0.688 = 0.312
(a) 82.8 kPa (b) 73.5 kPa (c) 39.2 kPa (d) 88.2 kPa ptotal = p°CHCl3 + ( p°CH2Cl2 - p°CHCl3 ) c CH2CH2
Sol. (b) Number of moles of octane = 200 + ( 415 - 200) ´ 0.688
Mass 35 g = 347.9 mmHg
(nA ) = = = 0.307 mol
Molar mass 114 g mol-1 To calculate the mole fraction of component in vapour phase,
[Molar mass of octane cVi = pi / ptotal
-1
C8H18 = (12 ´ 8) + (1 ´ 18) = 114 g mol ] \ pCH2Cl2 = 0.688 ´ 415 mmHg = 285.5 mmHg
Number of moles of heptane pCHCl3 = 0.312 ´ 200 mmHg = 62.4 mmHg
26 g 285.5 62.4
(nB) = = 0.26 mol V
c CH2Cl2 = = 0.82 and cVCHCl3 = = 0.18
100 g mol-1 347.9 347.9
[Molar mass of heptane C7H16 = (12 ´ 7) + 16 = 100 g mol-1] Note Since, CH2Cl2 is more volatile component than CHCl3
Mole fraction of octane [p°CH2Cl2 = 415 mm Hg and p°CHCl3 = 200 mm Hg] and the vapour
nA (0.307 mol) phase is also richer in CH2Cl2 [cVCH2Cl2 = 0.82 and cVCHCl3 = 0.18], it
( cA) = = = 0.541 may be concluded that at equilibrium, vapour phase will be always
nA + nB (0.307 + 0.26) mol
rich in the component which is more volatile.
Solutions 635

Limitations of Raoult’s Law The resultant graph III (representing

p = pA ° c A + pB ° c B ) is the plot for solution and is a
• It is applicable only to very dilute solutions as in case
straight line joining pA ° and pB ° . Hence, the vapour
of non-dilute solutions there occur strong interactions pressure at various compositions of ideal solutions is
between solute and solvent molecules which causes intermediate between the values of pA ° and pB ° .
either positive or negative deviations.
• It is applicable only to solutions containing
non-volatile and non-electrolytic solutes which exist
Non-Ideal or Real Solutions
as a single molecule. Solutions, which do not obey Raoult’s law, are called
non-ideal solutions. Hence, for such solutions pA ¹ p°A c A
• It is not applicable to solutes which dissociate or
and pB ¹ p°B c B .
associate in the particular solution.
For such mixtures,

Ideal Solutions DH mixing ¹ 0

Ideal solutions are those, which obey Raoult’s law over and DV mixing ¹ 0;
the entire range of concentration at a given temperature. Non-ideal solutions show the following two types of
The total vapour pressure of an ideal solution containing deviations from ideal behaviour
components A and B is given by
p = pA + pB = p°A c A + p°B c B 1. Solution Showing Positive Deviation
In an ideal solution of two components say A and B, all The vapour pressure of each component in such a
cohesive forces ( A — A, B— B and A — B)must be identical. mixture is more than what would be expected on the
basis of Raoult’s law of components A and B alone.
• both have similar structure,
• both have similar molecular sizes,
If the attraction between A and B molecules is less than
the attractive forces between A to A and B to B, the
• both have identical intermolecular forces.
escaping tendency in solution is higher than in either of
Examples of the ideal solutions are the pure components.
Benzene-toluene, n-hexane-n-heptane; ethyliodide-ethyl For such a deviation
bromide, chlorobenzene- bromobenzene.
pA > pA ° c A , pB > pB ° c B
Characteristics of an Ideal Solution and hence, ptotal > pA ° c A + pB ° c B
The mixture of two liquids results in an ideal solution also DH mixing > 0
when
as the new bonds formed are weaker and energy is
(i) These obey Raoult’s law. absorbed.
(ii) DH mixing = 0, i.e. no energy evolved or absorbed on DV mixing > 0, i.e. there is increase in volume.
mixing.
(iii) DV mixing = 0, i.e. on mixing no expansion or ptotal
contraction occurs. p A°

Graphical Representation of Ideal pB ° pA

Solutions
The curve I (straight line) gives variations of vapour
VP

pB
pressure of liquid A and the curve II gives that of liquid B
with their respective mole fractions.
p°B 0 cA 1
(III) 1 cB 0
Vapour pressure

Graph of solution showing positive deviation from Raoult’s law

p°A (II)
e.g. Ethanol-water, ether-acetone, carbon
(I) disulphide-acetone, carbon tetrachloride-methanol,
cyclohexane-ethanol, water-methanol, carbon
Mole fraction tetrachloride-benzene, carbon tetrachloride-toluene,
Vapour pressure behaviour of ideal solutions acetone-benzene.
obeying Raoult’s law
636 JEE Main Chemistry

2. Solutions Showing Negative Deviation DVmixing < 0, i.e. there is decrease in volume.
For such solutions, the partial vapour pressure of each p A°
component is less than what would be expected on the
basis of Raoult’s law. pB° ptotal
In such a mixture, the attraction between molecules of A

VP
and B is greater than the force between A¾ A molecules pA
or B¾ B hence the escaping tendencies of both the
components are lowered.
For a mixture showing negative deviation pB
0 cA 1
pA < pA ° c A 1 cB 0
or pB < pB ° c B , Graph of solution showing negative
deviation from Raoult’s law
hence, ptotal < pA ° c A + pB ° c B
e.g. Acetic acid-methanol, acetic acid-pyridine
DH mixing < 0, i.e. heat is evolved due to the formation of acetone-aniline, acetone-chloroform, benzene-chloroform,
stronger bonds. water-hydrochloric acid, water-nitric acid etc.

Comparison between Ideal and Non-Ideal Solutions

Non-ideal solutions
Ideal solutions
Positive deviation from Raoult’s law Negative deviation from Raoult’s law
Each component obeys Raoult’s law Their components do not obey Raoult’s law. Their components do not obey Raoult’s law,
at all temperature and pressure, i.e. pA > p °A c A and pB > pA° cB i.e. pA < p°Ac A and pB < pB° cB
i.e. pA = p °Ac A and pB = p B
° cB
D mix V = 0, D mix H = 0 D mix V > 0, D mix H > 0 (endothermic) D mix V < 0, D mix H < 0 (exothermic)
Intermolecular interactions, i.e. A—B Intermolecular interactions, i.e. A—B Intermolecular interactions, i.e. A ¾ B
interactions are same as present in pure interactions are weaker than in pure interactions are stronger than in pure
components, i.e. A—A or B—B. components, i.e. between A—A or B—B components, i.e. between A ¾ A or B ¾ B.
e.g. Benzene + toluene, n-hexane + n-heptane; e.g. Ethanol + water, ether e.g. Acetic acid + methanol, acetic acid +
chlorobenzene + bromobenzene; ethyl bromide + acetone, acetone + benzene, carbon pyridine, acetone + aniline, acetone +
+ ethyl iodide; n-butyl chloride + n-butyl disulphide + acetone, carbon tetrachloride + chloroform, benzene + chloroform, water +
bromide. methanol, cyclohexane + ethanol, water + hydrochloric acid,
methanol, carbon tetrachloride +benzene. water + nitric acid.

Azeotropic Mixtures of the two pure components. These are formed by

A mixture of two liquids which boils at a constant non-ideal solutions showing positive deviations.
temperature and distils over without any change in 2. Maximum boiling azeotropes These are the
composition is called azeotropic mixture. mixtures of two liquids boiling point of which is more
Azeotropic mixtures are of two types than either of the two pure components.
1. Minimum boiling azeotropes These are the mixture These are formed by non-ideal solutions showing
of two liquids boiling point of which is less than either negative deviations.

Some Azeotropic Mixtures

Components Composition Boiling point (K)
A B (mass % B) A B Azeotrope
Minimum Boiling Azeotropes
H2O2 C2H5OH 95.6 373 351.5 351
H2O n-C3H7 OH 72.0 373 370.2 361
CHCl 3 C2H5OH 6.8 334.2 351.3 223.3
Maximum Boiling Azeotropes
H2O HCl 20.2 373 188 381.6
H2O HNO3 68.0 373 359 393.5
H2O HCOOH 77.0 373 374 380.0
CHCl 3 CH3COCH3 20.0 334.2 329.1 337.7
Solutions 637

Example 11. A graph of vapour pressure and temperature for These does not depend on the chemical nature of solute.
three different liquids X, Y, and Z is shown below : These are proportional to the number of solute particles
X Y Z in the solution.
Vapour pressure

800
Factors affecting colligative properties are as follows
(mm Hg)

500
• Fraction of solute and solvent particles in solution.
400
• Nature of solvent.
200
• Extent of association and dissociation of solute
0 293 313 333 353
particles in solution.
Temp
There are four colligative properties are as follows
The following inference are made (JEE Main 2020) • Relative lowering of vapour pressure
A. X has higher intermolecular interactions compared to Y. • Elevation in boiling point
B. X has lower intermolecular interactions compared to Y.
• Depression in freezing point
C. Z has lower intermolecular interactions compared to Y.
• Osmotic pressure
The correct inference(s) is/are
(a) (C) (b) (B)
(c) (A) (d) (A) and (C) Relative Lowering of Vapour Pressure
When a non-volatile solute is added to a solvent, the
Sol. (b) From given graph it can be seen that, X has higher vapour vapour pressure is lowered. So, vapour pressure of a
pressure as compared to Y at lower temperature (or to attain same solution ( p) is always less than the vapour pressure of
vapour pressure, Y need higher temeprature than X). It means that
pure solvent ( p° ) at that temperature. Therefore, ( p° - p)
intermolecular interaction must be weaker in X as compared to Y,
is called the lowering in vapour pressure and the
which further must be weaker than Z by the same reason also.
æ p° - p ö
Hence, option (b) is correct. ratio ç ÷ is known as the relative lowering in
è p° ø
Example 12. A 4% solution of sucrose C12H22O11 is isotonic vapour pressure.
with 3% solution of an unknown organic substance. The According to Raoult’s law, “the relative lowering in
molecular mass of the unknown substance will be vapour pressure of a dilute solution is equal to the mole
(a) 2.565 g (b) 25.65 g fraction of the solute present in the solution. i.e.
(c) 256.5 g (d) 2565 g p° - p
= cB
p°
Sol. (c) Since the two solutions are isotonic, they must have same
concentrations in moles/litre.
where, c B = mole fraction of solute
Determination of Molecular Mass
For sucrose solution, we have concentration
= 4 g /100 cm3 (given)
If n moles of solute be dissolved in N moles of the solvent,
n
40 the mole fraction of the solute =
= 40 g L-1 = mol L-1 n+N
342
Then, according to Raoult’s law,
(Molecular mass of sucrose C12H22 O11 = 342) p° - ps n
\ =
For unknown substance, suppose m is the molecular mass, then p° n+N
concentration = 3 g/100 cm3 (given) w
30 p° - ps m é w Wù
= 30 g L-1 = mol L-1 = êQn = and N =
Mw p° w
+
W ë m M úû
30 40 m M
Thus, we have = For very dilute solutions,
Mw 342
30 ´ 342 n <<< N
Mw = = 256.5 p° - ps n
40 \ =
p° N
p° - ps w´M
Colligative Properties or
p°
=
m´W
The properties of a dilute solution which depends only
upon the number of particles present in a solution and This expression is used to find the molecular weight of an
their concentration are called colligative properties. unknown solute dissolved in a given solvent.
638 JEE Main Chemistry

p° - ps w /m w M
Alternate Formula for the Relative Lowering \ = = ´
p° W /M m W
of Vapour Pressure (When the solution is not
Dilute) 17.53 - 17.22 17.10 18
Þ = ´
p° - ps nB 17.53 m 100
= …(i) 17.10 ´ 18 ´ 17.53
p° nA + nB Þ m=
0.31 ´ 100
On reversing Eq. (i), we get
p° n + nB n m = 174.05
= A =1+ A
p° - ps nB nB 174 is nearest to the molecular weight of glucose (C6H12O6), thus the
p° nA substance ‘ X’ can be glucose.
Þ -1=
p° - ps nB
p° - p° + ps n A ps n Experimental Method of Calculation of
Þ = Þ = A
p° - ps nB p° - ps n B Relative Lowering in Vapour Pressure
The experimental setup for determining relative lowering
p° - ps n B
or = in vapour pressure is shown in the figure. It consists of
ps nA two sets of bulbs. The first set of three bulbs is filled with
solution, to half of their capacity and the second set of
Example 13. Calculate the mass of a non-volatile solute another three bulbs is filled with the pure solvent.
(molar mass 40 g mol-1) which should be dissolved in 114 g
Dry air
octane to reduce its vapour pressure to 80%. pS p°
(a) 20 g (b) 10 g (c) 30 g (d) 45 g Air

Sol. (b) According to Raoult’s law, relative lowering of

vapour pressure,
p°A - pS
= cB …(i) Solution Solvent Weighed CaCl2 tubes
p°A
Ostwald and Walker method
nB WB/MB
cB = = …(ii)
nB + nA WB + WA Each set is separately weighed accurately. Both sets are
MB MA connected to each other and then with the accurately
Given vapour pressure is reduced to 80%when non-volatile solute weighed set of guard tubes which contain anhydrous
is dissolved in octane. It means calcium chloride or some other dehydrating agents such
as P2O5 , concentrated H2 SO4 , etc. The bulbs of solution and
If pA° = 1 atm then pS = 0.8 atm; p°A - pS = 0.2 atm;
pure solvent are kept in a thermostat maintained at a
MA (C8H18) = 114 g mol-1; WA = 114 g; MB = 40 g mol-1; WB = ? constant temperature.
Applying Eq. (ii) A current of pure dry air is bubbled through the series of
0.2 WB/40 W /40 bulbs as shown in the figure. The air gets saturated with
= = B
1 WB 114 WB the vapour in each set of bulbs. The air takes up an
+ +1
40 114 40 amount of vapours proportional to the vapour pressure of
WB the solution first and then it takes up more amount of
0.2 =
WB + 40 vapour from the solvent which is proportional to the
0.2WB + 8 = WB difference in the vapour pressure of solvent and the
WB = 10
vapour pressure of solution, i.e. p° - ps . The two sets of
bulbs are weighed again. The guard tubes are also
Example 14. The vapour pressure of 100 g water reduces weighed.
from 17.53 mm to 17.22 mm when 17.10 g substance ‘X’ is Loss in mass in solvent bulbs WB / M B
=
dissolved in it. Substance X can be Gain in mass of guard tubes W A / M A + W B / M B
(a) methanol (b) glucose
The above relationship is used for the calculation of
(c) carbon dioxide (d) cannot predict
w molecular masses of non-volatile solutes.
p° - ps n m For very dilute solutions, the following relationship can
Sol. (b) = =
p° n+N w +W be applied
m M p° - ps loss in mass in solvent bulbs W B / M B
w W = =
Q <<< p° gain in mass of guard tubes W A / M A
m M
Solutions 639

Example 15 A current of dry air was bubbled through a Determination of Molecular Mass from
bulb containing 26.66 g of an organic compound in 200 g of Elevation in Boiling Point
water, then through a bulb at the same temperature, containing
We know that molality,
water and finally through a tube containing anhydrous calcium
chloride. The loss of mass in the bulb containing water was weight of solute ´ 1000
m=
0.087 g and the gain in the mass of calcium chloride tube was mol. wt. of solute ´ mass of solvent
2.036 g. Calculate the molecular mass of the organic substance. w ´ 1000
=
(a) 35.23 (b) 53.75 (c) 40.21 (d) 21.15 m¢ ´ W
p° - ps loss in the mass of solvent bulb 0.087
Sol. (b) = = On putting the value of m in expression of elevation in
p° gain in the mass of CaCl2 tube 2.036
boiling point, we get
Let the molecular mass of the organic substance be M2. k ´ w ´ 1000
or DTb = b
According to Raoult’s law, m¢ ´ W
p° - ps W2 /M2
= kb ´ w ´ 1000
p° W 2 W
+ 1
or m¢ =
M2 M1 DTb ´ W
26.66 where, kb = molal boiling point elevation constant or
0.087 M2 26.66 ebullioscopic constant of the solvent
= =
2.036 26.66 + 200 26.66 + 200 M w = weight of the solute
2
M2 18 18 W = weight of solvent
M2 = 53.75 g mol -1 m¢ = molecular weight of the solute
Sometimes the value of kb is given per 0.1 kg (100 g), in
Elevation in Boiling Point of the such case the expression becomes
Solvent (Ebullioscopy) 100 ´ kb ´ w
m=
The boiling point of a liquid may be defined as the DTb ´ W
temperature at which vapour pressure becomes equal to kb is defined as the elevation in boiling point produced
the atmospheric pressure (760 mm). As the vapour when 1 mole of the solute is dissolved in 1 kg of the
pressure of a solution is decreased due to the presence of solvent.
a non-volatile solute, the solution boils at a higher
Unit of k b = K (mol/ kg)–1
temperature as compared to the pure solvent.
The boiling point of the solution is therefore higher than = K kg mol-1
the boiling point of the pure solvent. If Tb° is the boiling Molal boiling point elevation constant ( kb ) can be
point of pure liquid and Tb is the boiling point of solution calculated from molar enthalpy of vaporisation (DH vap) of
then, the solvent using the expression,
Atmospheric
pressure MR(Tb° )2
kb =
( DH vap ´ 1000)
Vapour pressure

nt
lve where, M = molar mass of solvent,
So ion
(atm)

lut Tb° = boiling point of solvent

So
Elevation in R = gas constant .
DTb boiling point
Molal boiling point elevation constant ( kb ) can also be
calculated from latent heat of evaporation ( lv ) of pure
Temperature (K) Tb° Tb
solvent using the expression.
Elevation in boiling point 0.002(T ° )2
kb =
lv
Elevation in boiling point, DT = Tb - Tb°
The elevation in boiling point is proportional to the where, T ° = normal boiling point of the pure solvent
molality of the solution, i.e. lv = latent heat of evaporation in cal/g of pure
DTb µ m or DTb = kbm solvent
640 JEE Main Chemistry

Example 16. Calculate the boiling point of a solution where, kf = molal freezing point depression constant or
containing 0.456 g of camphor (molar mass = 152) dissolved cryoscopic constant of the solvent
in 31.4 g of acetone (= 56.30°C), if the molecular elevation t
ven
constant per 100 g of acetone is 17.2°C. id sol
u
(a) 56.46°C (b) 36.56°C Liq
ion
lut

Vapour pressure
(c) 56.14°C (d) 72.52°C So

nt
ve
l
so
Sol. (a) We know that

en
oz
Fr
100kb ´ w 100 ´ 17.2 ´ 0.456
DTb = = Freezing point
W ´ m¢ 31.4 ´ 152
DTf depression
= 0.16° C
\ Boiling point of solution (Ts ) = T° + DTb Tf°
Tf
= 56.30 + 0.16 Temperature(K)
= 56.46° C Depression in freezing point graph

Example 17 The elevation of boiling point of 0.10 m Determination of Molecular Mass from
aqueous CrCl3 ×xNH3 solution is two times that of 0.05 m Depression in Freezing Point
aqueous CaCl2 solution. The value of x is ....... . w ´ 1000
As we known, molality, m =
[Assume 100% ionisation of the complex and CaCl2, m¢ ´ W
coordination number of Cr as 6, and that all NH3 molecules On putting this value in the expression of depression in
are present inside the coordination sphere] freezing point, we get
(JEE Main 2020) kf ´ w ´ 1000 kf ´ w ´ 1000
Sol. (5.00) DT f = or m ¢ =
DTb = i ´ m ´ Kb
m¢ ´ W DT f ´ W
For CaCl2, i = 3, m(CaCl2 ) = 0.05 m where, w = weight of the solute
\ DTb = 3 ´ 0.05 ´ Kb = 015
. Kb W = weight of the solvent
Molality of CrCl3 ×xNH3 = 01
. m m¢ = molecular weight of the solute
\ DTb¢ = i ´ m ´ Kb = 01
. iKb Sometimes the value of kf is given per 0.1 kg (100 g), in
such case the expression becomes
. iKb = 2 ´ 015
Given that : 01 . ´ Kb
100 ´ kf ´ w
\ i = 3 and coordination number is 6. m¢ =
DT f ´ W
Thus, complex will be [Cr(NH3 )5 Cl]Cl2
\ x=5 kf is defined as the depression in freezing point produced
when 1 mole of the solute is dissolved in 1 kg of the solvent.
Hence, the correct answer is 5.
Unit of kf = K (mol/ kg –1 ) = K kg - mol -1
Depression in Freezing Point of the Molal depression constant, kf can be calculated from
Solvent (Cryoscopy) molar heat of fusion of the solvent using the expression
The temperature at which the liquid and solid states of a MR (T f° )2
substance have the same vapour pressure is called kf =
( DH fusion ´ 1000)
freezing point.
Since, the vapour pressure of a solvent is lowered by the where, M = molar mass of solvent,
addition of non-volatile solute, the freezing point of the T f ° = boiling point of solvent
solution (T f ) is always lower than the freezing point of R = gas constant
the pure solvent (T f° ).
Molal freezing point depression constant ( kf ) can also be
Therefore, depression in freezing point, DT f = T f° - T f calculated from latent heat of fusion ( l f ) of pure solvent
The depression in freezing point is proportional to the using the expression
molality of the solution, i.e. 0.002(T ° )2
kf =
DT f µ m lf
where, T ° = normal freezing point of the solvent
or DT f = kf m
l f = latent heat of fusion in cal/g of pure solvent
Solutions 641

Some Practical Applications of Depression Osmosis

of Freezing Point It is the spontaneous flow of the solvent molecules
(i) Antifreeze solutions Water is used in radiators of through semipermeable membrane pure to the solution
vehicles as cooling liquid. If the vehicle is to be used side or from a dilute to a concentrated solution.
at high altitudes where the temperature is sub-zero, Semipermeable membrane
water would freeze in the radiators. To avoid this
difficulty, a solution of ethylene glycol in water is used
in radiators. This solution has freezing point lower
Solvent molecules
than zero. Solvent
Freezing point can be lowered to the desired extent by Solution
changing the concentration. With proper ratio of
ethylene glycol and water, it is possible to protect the Solute molecules
automotive cooling system to temeprature up to - 48°C.
(ii) Clearing of ice from roads in the hills Salts such
as NaCl or CaCl2 are scattered on icy roads at higher Direction of movement
of solvent molecules
altitudes. This helps in melting the ice as long as the
outdoor temeprature is above the lowest freezing Semipermeable Membranes
point of salt-water mixture. NaCl can melt ice at
temperature as low as - 21°C. CaCl2 is effective in These are thin sheets, which allow the passage of only
melting the ice at a temperature as low as - 55°C. solvent molecules through them, e.g. egg membrane,
goat’s bladder, cell membrane are natural
Example 18. Calculate the mass of ascorbic acid semipermeable membranes.
(Vitamin C, C6H8O6 ) to be dissolved in 75 g of acetic acid to Artifical membranes of gelatinous inorganic substances
lower its melting point by 1.5° C . K f = 3.9 K kg mol-1. (NCERT) such as calcium phosphate, copper ferrocyanide, freshly
(a) 5 g (b) 4 g (c) 8 g (d) 9 g prepared silicates of iron, cobalt nickel etc., are also
semipermeable. Cellophane and perchment papers etc.,
Sol. (a) Mass of ascorbic acid (WA ) = 75 g = 0.075 kg
are also used for the same purpose.
Depression in melting point ( DTf ) = 1.5° C = 1.5 K
Molar mass of ascorbic acid Difference between Osmosis and Diffusion
(MB) = (12 ´ 6) + (8 ´ 1) + (16 ´ 6) = 176 g mol-1 • Diffusion is intermingling of molecules or ion etc.,
Molal depression constant (Kf ) = 3.9 K kg mol-1 resulting from the random thermal agitation
Since, lowering of melting point is given, apply the formula for thus there is no restriction to motion of any kind of
lowering of melting point, i.e. particles while in osmosis only solvent molecules flow.
DTf = Kf × m • Osmosis takes place through a semipermeable
K × WB DT × MB × WA membrane while for diffusion it is not required.
DTf = f or WB = f
MB ´ WA kf • A homogeneous mixture is obtained as a result of
(176 g mol-1) ´ (1.5 K) ´ (0.075 kg)
diffusion. On the other hand no mixing is possible in
WB = = 5.08 g osmosis.
(3.9 K kg mol-1)
• Diffusion cannot be prevented while osmosis can be
Example 19. How much amount of NaCl should be added to stopped by applying pressure to the solution.
600 g of water (r = 100
. g/mL) to decrease the freezing point of • Osmosis is possible in liquids only while diffussion
water to -0.2 ºC? …… (The freezing point depression constant for can take place in gases as well as liquids.
water = 2 K kg mol -1) (JEE Main 2020) • In osmosis there is movement from lower
i ´ Kf ´ wNaCl ´ 1000 concentration to higher concentration but in
Sol. (1.76) DTf = i ´ m ´ Kf = diffussion, the movement from higher to lower
MNaCl ´ wH2O
( = 58.5) concentration takes place.
w ´ 1000
(m = molality) = B Osmotic Pressure
MB ´ wA
The external pressure which must be applied on the
DTf = 0.2 because freezing point
solution in order to stop the flow of the solvent into the
= - 0.2°C; Kf of water =2 K kg mol-1 (Given)
solution through semipermeable membrane is termed as
i = van’t Hoff factor, for NaCl = 2 osmotic pressure.
DTf ´ MNaCl ´ wH2O
\ wNaCl = Osmotic pressure ( p ) = hdg (approximate)
i ´ Kf ´ 1000 where, h = increase in level in the tube of
0.2 ´ 58.5 ´ 600 unit cross-section
= = 1.755 g » 1.76 g
2 ´ 2 ´ 1000 d = density of solution
642 JEE Main Chemistry

Laws of Osmotic Pressure Determination of Molecular Mass from

van’t Hoff realised that an analogy exists between the Osmotic Pressure
gases and solutions provided the osmotic pressure of \ pV = nRT
solutions is used in place of ordinary gas pressure. He w
showed that for solutions of non-electrolytes the following Þ pV = RT
m¢
laws hold good wRT
(i) Boyle-van’t Hoff law which states that the osmotic or m¢ =
pV
pressure ( p ) of a solution is directly proportional to its
concentration (C), when the temperature is kept Example 20. Osmotic pressure of a urea solution at 10°C
constant.
is 500 mm. Osmotic pressure of the solution become 105.3
p µ C (Temperature, T is constant)
mm, when it is diluted and temperature is raised to 25°C. The
If V litres of solution contain n moles of solute then extent of dilution is
n 1
C= , or p µ (a) 4 times (b) 3 times
V V (c) 5 times (d) 2 times
p V = constant
Sol. (c) pV = nRT
Remember The osmotic pressure of a solution containing
500V1 nR ´ 283
1 mole of solute particles per litre (1M) at 0ºC is 22.4 atm. =
105.3V2 nR ´ 298
(ii) Charles’-van’t Hoff law (Gay-Lussac law) according
to which the osmotic pressure of a dilute solution is V1 1
=
directly proportional to its absolute temperature (T ), V2 5
when the concentration of solution is kept constant. or V2 = 5V1
p µ T (Concentration, C is constant)
p
Total Osmotic Pressure
or = constant If a number of solutions are present in the solution and
T
p1 , p 2 , p3 ,K are their individual osmotic pressure then
(iii) Avogadro-van’t Hoff law states that equal volumes
of dilute solutions of different solutes, having the total osmotic pressure, p = p1 + p 2 + p3 + K
same temperature and osmotic pressure contain
equal number of molecules, i.e. isotonic solutions at a Reverse Osmosis
given temperature have same molar concentration. When a pressure more than the osmotic pressure is applied to
p µn the solution, the solvent may pass from solution into the
solvent through the semi-permeable membrane. This type of
Here, n = number of moles of solute per litres of
osmosis is known as reverse osmosis. Reverse osmosis is used
solutions.
for the desalination of sea water.
(iv) General equation for dilute solutions is obtained Pressure > p
Semipermeable Semipermeable
by membrane membrane Position
pV = nRT or p = CRT
Fresh Salt Fresh Salt
On the basis of this analogy, van’t Hoff proposed that a water water Water water water
solute in dissolved state behave as a gas and the outlet
Water moves to Water moves to
osmotic pressure of the solution is equal to the pressure
which the solute would exert if it were a gas at the (a) Osmosis (b) Reverse osmosis
same temperature and occupying the same volume as A schematic set up for the reverse osmosis used for
that of solution. desalination of sea water
These laws fail to deal with concentrated solution due The osmotic pressure of sea water at 15ºC is 25 atm. Isotonic
to the fact that osmotic pressure is actually related to solutions have the same osmotic pressure. If two solutions have
the activity and not to the concentration of the different osmotic pressures, the one having lower pressure is
solution. Osmotic pressure is the most sensitive called hypotonic and the other with higher pressure is
colligative property and its magnitude is proportional hypertonic solution.
to the molality of the solution.
Solutions 643

Example 21. How many gram of glucose must be present in

0.5 L of solution for its osmotic pressure to be the same as that of
Abnormal Colligative
9.2 g of glucose per litre? Properties : van’t Hoff Factor
(a) 4.6 g (b) 5.8 g (c) 3.6 g (d) 8.4 g Various relations of colligative properties hold good in
Sol. (a) For isotonic solution, dilute solutions only when there is no change in
w1 w
molecular state of solute. In case the total number of
= 2 particles of solute changes in solution, the colligative
m1V1 m2V2
properties also change accordingly.
w1 9.2
= This change occur in the following two ways
180 ´ 0.5 180 ´ 1
or w = 4.60 g By Dissociation
When substance is an electrolyte, the number of particles
Applications of Osmotic Pressure increases in solution and the colligative property
Osmotic pressure measurement provided very good increases accordingly.
method of determination of molecular mass of polymers
In case of dissociation suppose 1 molecule of solute A
like proteins etc., due to the following reasons
dissociates to give n ions and a is the degree of dissociation.
• Osmotic pressure of a solution containing fewer A nB
particles is appreciable and can therefore be Initially 1 mol
º 0
measured accurately as compared to DTb or DT f After dissociation (1 - a) mol na
which are very small in these conditions. Total number of moles present in solution
• Osmotic pressure is measured at room temperature, = (1 - a ) + na = 1 + ( n - 1) a
hence the method is particularly useful for van’t Hoff factor, i = 1 + ( n - 1) a > 1 if n ³ 2
biomolecules which are generally unstable at higher ( i - 1)
temperatures. and a=
( n - 1)
Osmosis plays a vital role in biology also. Some examples
it are as follows By Association
• For normal functioning of the living systems, the fluid When substance undergoes association, the number of
concentration has to be maintained in the plant and particles decreases in solution and consequently the
animal cells. value of colligative property decreases. Association of
molecules is depicted as follows
• Movement of water from roots to the top of plants
takes place via osmosis. 2CH3 COOH º (CH COOH)3 2

• Flow of water to various parts of plants is due to O - - - H— O

osmosis. H3 C—C C—CH3
• Different movements of plants such as opening and O— H - - - O
closing of flowers, etc., are controlled by osmosis. H- bond
• A 0.91% solution of pure NaCl is isotonic with human Molecules of acetic acid dimerise in benzene due to
red blood red cells (RBCs). Therefore, in this solution, hydrogen bonding. It generally happens in solvents
RBCs neither swell nor undergo plasmolysis. having low dielectric constant.
• A pure NaCl solution with concentration less In case of association suppose n molecules associate to
than 0.91% is called hypotonic solution. On form one giant molecule and a is the degree of association.
placing RBCs in this solution, these will swell and nA º ( A)n
even burst. Initially 1 mol 0
a
• A pure NaCl solution with concentration more than At equilibrium (1 - a) mol
n
0.91% is called hypertonic solution. On placing Total number of moles in solution
RBCs in this solution, these shink due to plasmolysis.
a æ1 ö
• People taking a lot of salt or salty food experience
= (1 - a ) + = 1 + ç - 1÷ a
n èn ø
water osmosis. The resulting puffiness or swelling is
æ1 ö
called edema. van’t Hoff factor = 1 + ç - 1÷ a < 1 if n ³ 2
èn ø
• The use of salt and sugar as preservatives in pickels
and jams has its basis in preventing growth of fungi ( i - 1)
and a=
and bacteria by osmosis. 1
-1
n
644 JEE Main Chemistry

van’t Hoff Factor and DT f = kf mi

Normal value of colligative property µ number of DTb = kbmi
particles of solute taken and abnormal value of
colligative property µ number of particles of solute after Example 22. The freezing point depression of 0.1 molal
dissociation or association. solution of acetic acid in benzene is 0.256 K. kf for benzene is
5.12 K kg mol -1. What conclusion can you draw about the
The ratio of two values, i.e.
molecular state of acetic acid in benzene?
abnormal colligative property (a) Acetic acid is doubly associated
is termed as van’t Hoff
normal colligative property (b) Benzene is doubly associated
factor (i). (c) Both are equally associated
No. of particles after association or dissociation (d) None of the above
i=
No. of particles before association or dissociation observed colligative property 0.256 1
Sol. (a) i = = =
actual number of particles in solution calculated colligative property 0.512 2
Thus, i =
number of particles taken calculated molecular mass
Also, i=
Abnormal Molecular Weight observed molecular mass
1 Calculated molecular mass of CH3 COOH = 60
As, colligative properties µ
(molecular weight) 60
\ Observed molecular mass = = 120
Normal molecular weight 1/2
i=
Abnormal molecular weight
Hence, acetic acid exists as doubly associated.
= 1 + ( n - 1) a > 1 in case of dissociation
æ1 ö Example 23. Which one of the following aqueous
= 1 + ç - 1÷ a < 1 in case of association
èn ø solutions will exhibit highest boiling point?
(a) 0.01 M Na 2SO4
In case van’t Hoff factor is known, the various colligative
(b) 0.01 M KNO3
properties would be given by
(c) 0.015 M urea
DTf = i kf m (d) 0.015 M glucose
DTb = i kb m
Sol. (a) DT µ im (as kf is a constant)
pV = inRT
(a) DT µ 3 ´ 0.01 = 0.03 (because it gives 3 ions)
p° - p
= ixB (b) DT µ 2 ´ 0.01 = 0.02 (because it gives 2 ions)
p°
(c) DT µ 0.015 ´ 1 = 0.015 (No ions are obtained)
where, m is the molality of solution, i ´ m is sometimes (d) DT µ 0.015 ´ 1 = 0.015
referred to as effective molality or colligative
Since, DT is highest for 0.01 M Na 2SO4 so it will exhibit highest
molality ( mi ).
boiling point.
\ mi = i ´ m
 Practice Exercise
ROUND I Topically Divided Problems
Type of Solutions, Solubility and their 7. Calculate the amount of benzoic acid (C 6 H 5COOH)
Concentrations required for preparing 250 mL of 0.15 M solution
1. A beaker contains a solution of substance ‘A’. in methanol. (NCERT)
(a) 1.89 g (b) 4.57 g
Precipitation of substance ‘A’ takes place when
(c) 2.99 g (d) 3.54 g
small amount of ‘A’ is added to the solution. The
solution is (NCERT Exemplar) 8. An antifreeze solution is prepared from 222.6 g of
ethylene glycol (C 2 H 6O 2 ) and 200 g of water. If the
(a) saturated (b) supersaturated
(c) unsaturated (d) concentrated density of the solution is 1.072 g mL-1 then what
shall be the molarity of the solution? (NCERT)
2. Value of Henry’s constant K H (NCERT Exemplar)
(a) 91 M (b) 9.1 M
(a) increases with increase in temperature (c) 0.91 M (d) 0.0091 M
(b) decreases with increase in temperature
(c) remains constant 9. Increasing the temperature of an aqueous solution
(d) first increases then decreases will cause
(a) decrease in molarity
3. Low concentration of oxygen in the blood and
(b) decrease in molality
tissues of people living at high altitude is due to
(c) decrease in mole fraction
(NCERT Exemplar)
(a) low temperature (d) decrease in % w/w
(b) low atmospheric pressure 10. 19.85 mL of 0.1 N NaOH reacts with 20 mL of HCl
(c) high atmospheric pressure solution for complete neutralisation. The molarity
(d) both low temperature and high atmospheric of HCl solution is
pressure
(a) 9.9 (b) 0.99 (c) 0.099 (d) 0.0099
4. K H value for Ar ( g), CO 2 ( g), HCHO(g) and CH 4 ( g)
11. What is the molarity of H 2SO 4 solution that has a
are 40.39, 1.67, 1.83 ´ 10 -5 and 0.413 respectively.
Arrange these gases in the order of their increasing density 1.84 g/cc at 35°C and contains 98% solute
solubility. (NCERT Exemplar)
by weight?
(a) 4.18 M (b) 1.84 M (c) 8.41 M (d) 18.4 M
(a) HCHO < CH4 < CO2 < Ar
(b) HCHO < CO2 < CH4 < Ar 12. A 6.50 molal solution of KOH (aq.) has a density of
(c) Ar < CO2 < CH4 < HCHO 1.89 g cm -3. The molarity of the solution is ………
(d) Ar < CH4 < CO2 < HCHO mol dm -3. (JEE Main 2021)
5. Calculate the mass percentage of aspirin (C 9 H 8O 4 ) [Atomic masses : K : 39.0 u ; O : 16.0 u ; H: 1.0 u ]
in acetonitrile (CH 3CN) when 6.5 g of C 9 H 8O 4 is (a) 9 (b) 10 (c) 16 (d) 18
dissolved in 450 g of CH 3CN. (NCERT)
13. Calculate the molality of 1 L solution of 93% H 2SO 4
(a) 1.40 (b) 1.90 (c) 2.60 (d) 2.29 (weight/volume). The density of the solution is
6. Henry’s law constant for the molality of methane in 1.84 g/mL.
benzene at 298 K is 4.27 ´ 10 5 mmHg. Calculate (a) 11.05 (b) 12.05 (c) 13.05 (d) 10.05
the solubility of methane in benzene at 298 K 14. Which of the following solutions has the highest
under 760 mmHg. (NCERT) normality?
(a) 1.78 ´ 10-4 (b) 1.78 ´ 10-3 (a) 6 g of NaOH/100 mL (b) 0.5 M H2SO4
(c) 17.8 ´ 10-4 (d) 1.78 ´ 10-6 (c) N phosphoric acid (d) 8 g of KOH/L
646 JEE Main Chemistry

15. 100 mL of 0.3 N HCl is mixed with 200 mL of 23. A solution of two components containing n1 moles of
0.6 N H 2SO 4 . The final normality of the resulting the 1st component and n2 moles of the 2nd
solution will be component is prepared. M1 and M 2 are the molecular
(a) 0.3 N (b) 0.2 N (c) 0.5 N (d) 0.1 N weights of component 1 and 2 respectively. If d is the
16. Based on solute-solvent interactions, arrange the density of the solution in g mL -1, C2 is the molarity
following in the order of increasing solubility in and c 2 is the mole-fraction of the 2nd component,
n-octane. Cyclohexane, KCl, CH 3OH, CH 3CN. (NCERT) then C2 can be expressed as (JEE Main 2020)

(a) KCl < CH3 OH < CH3CN < Cyclohexane 1000 c 2 dc 2

(a) C 2 = (b) C 2 =
(b) CH3 OH < KCl < CH3CN < Cyclohexane M1 + c 2 (M 2 - M1 ) M 2 + c 2 (M 2 - M1 )
(c) CH3 OH < CH3CN < KCl < Cyclohexane 1000 dc 2 dc1
(c) C 2 = (d) C 2 =
(d) None of the above c
M1 + 2 (M 2 - M1 ) c
M 2 + 2 (M 2 - M1 )
17. Calculate the molarity of solution of CaCl 2 if on 24. On litre sample of hard water contains 1 mg of
chemical analysis it is found that 200 mL of CaCl 2 CaCl 2 and 1 mg of MgCl 2 . Find the total hardness
contains 3.01 ´ 10 22 Cl - ions. of water in terms of CaCO 3 per 10 6 parts of water
(a) 40 M (b) 3.01 M (c) 0.125 M (d) 0.250 M
by mass.
18. What volume of 12 N and 3 N HCl must be mixed (a) 1.753 ppm (b) 1.953 ppm
to give 1.00 L of 6.00 N HCl? (c) 1.243 ppm (d) 1.533 ppm
(a) 0.33 L, 0.66 L (b) 0.33 L, 0.33 L
25. 18 g of glucose (C 6 H12O 6 ) is added to 178.2 g water.
(c) 0.66 L, 0.66 L (d) 0.8 L, 0.2 L
The vapour pressure of water (in torr) for this
19. The volume of water to be added to 100 cm 3 of
aqueous solution is (JEE Main 2016 (Offline))
0.5 N H 2SO 4 to get decinormal concentration is
(a) 400 cm3 (b) 500 cm3 (c) 450 cm3 (d) 100 cm3 (a) 76.0 (b) 752.4 (c) 759.0 (d) 7.6
20. A dry air is passed through the solution, containing
the 10 g of solute and 90 g of water and then it is Raoult’s Law and Vapour Pressure
passed through pure water. There is the depression (Ideal and Non-Ideal Solutions)
in weight of solution by 2.5 g and in weight of pure 26. If two liquids A and B form minimum boiling
solution by 0.05 g. Calculate the molecular weight
azeotrope at some specific composition then
of solute. (NCERT Exemplar)
(a) 25 (b) 50 (c) 100 (d) 180
(a) A ¾ B interactions are stronger than those
21. Mark the correct relationship between the boiling between A ¾ A or B ¾ B
points of very dilute solutions of BaCl 2 ( t1) and KCl (b) vapour pressure of solution increases because more
( t2 ), having the same molarity. number of molecules of liquids A and B can escape
(a) t1 = t2 (b) t1 < t2 from the solution
(c) vapour pressure of solution decreases because less
(c) t2 < t1 (d) cannot be calculated
number of molecules of only one of the liquids
22. Match the following: escape from the solution
(d) A ¾ B interactions are weaker than those between
Column I Column II
A ¾ A or B ¾ B
I. Foam A. Smoke
27. Formation of a solution from two components can
II. Gel B. Cell fluid be considered as
III. Aerosol C. Jellies I. Pure solvent ® separated solvent molecules;
IV. Emulsion D. Rubber DH1
E. Froth II. Pure solute ® separated solute molecules; DH 2
F. Milk III. Separated solvent and solute molecules ®
solution, DH 3
Codes (JEE Main 2020) Solution so formed will be ideal if
(a) (I)-(D), (II)-(B), (III)-(A), (IV)-(E)
(a) DH sol = DH 1 - DH 2 - DH 3
(b) (I)-(B), (II)-(C), (III)-(E), (IV)-(D) (b) DH sol = DH 3 - DH 1 - DH 2
(c) (I)-(E), (II)-(C), (III)-(A), (IV)-(F) (c) DH sol = DH 1 + DH 2 + DH 3
(d) (I)-(D), (II)-(B), (III)-(E), (IV)-(F) (d) DH sol = DH 1 + DH 2 - DH 3
Solutions 647

28. When two liquids A and B are mixed then their yM = mole fraction of M in vapour phase;
boiling points becomes greater than both of them. yN = mole fraction of N in vapour phase
What is the nature of this solution? (JEE Main 2019)
(a) Ideal solution x y x y
(a) M > M (b) M = M
(b) Normal solution xN yN xN yN
(c) Negative deviation with non-ideal solution xM yM
(c) < (d) (xM - yM ) < (xN - yN )
(d) Positive deviation with non-ideal solution xN yN

29. For the determination of molecular weights, 35. Two open beakers one containing a solvent and the
Raoult’s law is applicable only to other containing a mixture of that solvent with a
(a) dilute solutions of electrolytes non-volatile solute are together sealed in a
(b) concentrated solutions of electrolytes container. Over time (JEE Main 2020)
(c) dilute solutions of non-electrolytes (a) the volume of the solution decreases and the volume
(d) concentrated solutions of non-electrolytes of the solvent increases
(b) the volume of the solution does not change and the
30. Vapour pressure of CCl 4 at 25°C is 143 mm of Hg
volume of the solvent decreases
and 0.5 g of a non-volatile solute (mol. wt. = 65) is
(c) the volume of the solution increases and the volume
dissolved in 100 mL CCl 4 . Find the vapour of the solvent decreases
pressure of the solution. (Density of (d) the volume of the solution and the solvent does not
CCl 4 = 1.58 g / cm 3). change
(a) 94.39 mm (b) 141.93 mm 36. At 35°C, the vapour pressure of CS2 is 512 mmHg
(c) 134.44 mm (d) 199.34 mm
and that of acetone is 344 mmHg. A solution of CS2
31. The vapour pressure of pure liquids A and B are in acetone has a total vapour pressure of 600 mmHg.
450 and 700 mmHg respectively, at 350 K. If total The false statement amongst the following is
vapour pressure is 600 mmHg, find the (JEE Main 2020)
composition of B in vapour phase. (NCERT) (a) Raoult’s law is not obeyed by this system
(a) 0.30 (b) 0.40 (c) 0.60 (d) 0.70 (b) CS 2 and acetone are less attracted to each other
than to themselves
32. 100 g of liquid A (molar mass 140 g mol -1) was (c) a mixture of 100 mL CS 2 and 100 mL acetone has a
dissolved in 1000 g of liquid B (molar mass 180 g mol volume < 200 mL
-1
). The vapour pressure of pure liquid B was (d) heat must be absorbed in order to produce the
found to be 500 torr. Calculate the vapour solution at 35°C
pressure of pure liquid A and its vapour pressure 37. The vapour pressure of two liquid P and Q are 80
in the solution if the total vapour pressure of the and 60 torr respectively. The total vapour pressure
solution is 475 torr. (NCERT) of solution obtained by mixing 3 moles of P and 2
(a) 500, 450 (b) 280, 500 moles of Q would be (AIIMS 2012)
(c) 280, 32 (d) 500, 280 (a) 140 torr (b) 20 torr
33. Liquids A and B form an ideal solution in the (c) 68 torr (d) 72 torr
entire composition range. At 350 K, the vapour 38. At a given temperature, the vapour pressure in mm
pressures of pure A and pure B are 7 ´ 10 3 Pa and of Hg of a liquid A and B is given by the equation
12 ´ 10 3 Pa, respectively. The composition of the p = 120 - 80 X B (X B = mole fraction of B)
vapour in equilibrium with a solution containing Vapour pressure of pure A and B at the same
40 mole percent of A at this temperature is temperature are respectively
(JEE Main 2019)
(a) 120, 80 (b) 120, 200
(a) c A = 0.76; cB = 0.24 (b) c A = 0.28; cB = 0.72 (c) 120, 40 (d) 80, 40
(c) c A = 0.4; cB = 0.6 (d) c A = 0.37; cB = 0.63
39. For an ideal solution with p°A > p°B , which of the
34. Liquid M and liquid N form an ideal solution. The
following is true?
vapour pressures of pure liquids M and N are 450
(a) (c A )liquid = (c A )vapour
and 700 mmHg, respectively, at the same
(b) (c A )liquid > (c A )vapour
temperature. Then correct statement is
(c) (c A )liquid < (c A )vapour
xM = mole fraction of M in solution; (d) (c A )liquid and (c A )vapour do not bear any relationship
xN = mole fraction of N in solution; with each other.
648 JEE Main Chemistry

40. Total vapour pressure of mixture of 1 mole A (b) Boiling point of pure water decreases by the
( p°A = 150 torr) and 2 moles B (p°B = 240 torr) is 200 addition of ethanol
torr. In this case (c) Boiling point of pure benzene increases by the
addition of toluene
(a) there is positive deviation from Raoult’s law
(b) there is negative deviation from Raoult’s law (d) Vapour pressure of pure benzene decreases by the
(c) there is no deviation from Raoult’s law addition of naphthalene
(d) molecular masses of A and B are also required for 48. The vapour pressure of water at 20°C is 17.54 mm.
calculating the deviation When 20 g of a non-ionic substance is dissolved in
41. A binary solution of ethanol and n-heptane example of 100 g of water, the vapour pressure is lowered by
(a) ideal solution 0.30 mm. What is the molecular mass of the
(b) non-ideal solution with + ve deviation substance?
(c) non-ideal solution with - ve deviation (a) 200.8 (b) 206.88
(d) unpredictable behaviour (c) 210.5 (d) 215.2
42. Negative deviation from Raoult’ law is observed in 49. Vapour pressure of water at 293 K is 17.535 mmHg.
which one of the following binary liquid mixtures? Calculate the vapour pressure of water at 293 K
(a) Ethanol and acetone when 25 g of glucose is dissolved in 450 g of water.
(b) Benzene and toluene (NCERT)
(c) Acetone and chloroform (a) 17.43 mmHg (b) 18.93 mmHg
(d) Chloroethane and bromoethane (c) 20.12 mmHg (d) 25.31 mmHg
(e) Acetone and carbon disulphide
50. The unit of ebullioscopic constant is (NCERT Exemplar)
43. If ethanol dissolves in water then which of the (a) K kg mol -1 or K (molality) -1
following would happen? (b) mol kg K -1 or K -1 (molality)
(a) Absorption of heat and contraction of volume. (c) kg mol -1 K -1 or K -1 (molality) -1
(b) Liberation of heat and contraction of volume.
(d) K mol kg -1 or K (molality)
(c) Absorption of heat and increase in volume.
(d) Liberation of heat and increase in volume. 51. The molar freezing point constant for water is
1.86° C mol -1. If 342 g of cane sugar (C12 H 22O11) is
44. Which one of the following binary liquid systems dissolved in 1000 g of water, the solution will freeze
shows positive deviation from Raoult’s law? at
(a) Benzene-Toluene (a) -1.86° C (b) - 2.86° C (c) +1.86°C (d) +2.86°C
(b) Carbon disulphide-acetone 52. The amount of ice that will separate out on cooling
(c) Phenol-aniline
a solute containing 50 g of ethylene glycol in 200 g
(d) Chloroform-acetone
water to –9.3°C will be ( K f = 1.86 K kg mol -1)
(e) Nitric acid-water
(a) 8.37 g (b) 161.3 g (c) 3.87 g (d) 38.7 g
45. Which will form maximum boiling azeotrope?
53. The molecular weight of NaCl determined by
(a) HNO3 + H2O solution
studying freezing point depression of its 0.5%
(b) C2H5 OH + H2O solution
aqueous solution is 30. The apparent degree of
(c) C6H6 + C6H5CH3 solution
dissociation of NaCl is
(d) None of the above (a) 0.60 (b) 0.50 (c) 0.30 (d) 0.95

Colligative Properties 54. Which of the following statements is false?

(NCERT Exemplar)
46. Lowering of vapour pressure is highest for (a) Units of atmospheric pressure and osmotic
(a) 0.1 M BaCl2 pressure are the same
(b) 0.1 M glucose (b) In reverse osmosis, solvent molecules move
(c) 0.1 M MgSO4 through a semipermeable membrane from a region
of lower concentration of solute to a region of
(d) Urea
higher concentration
47. Which one of the statements given below concerning (c) The value of molal depression constant depends on
properties of solutions, describes a colligative effect? nature of solvent
(a) Vapour pressure of pure water decreases by the (d) Relative lowering of vapour pressure is a
addition of nitric acid dimensionless quantity
Solutions 649

55. Consider the figure and mark the correct option. 58. The relationship between osmotic pressure at
Piston (A) Piston (B) 273 K when 10 g glucose ( p1), 10 g urea ( p2 ) and
10 g sucrose ( p3) are dissolved in 250 mL of water is
8 pm (a) p1 > p2 > p3 (b) p3 > p2 > p1
(c) p2 > p1 > p3 (d) p2 > p3 > p1
Concentrated
Fresh water sodium chloride 59. A 6% solution of urea is isotonic with
(A ) solution in
water (B)
(a) 1 M solution of glucose
(b) 0.05 M solution of glucose
(c) 6% solution of glucose
(NCERT Exemplar) (d) 25% solution of glucose
(a) Water will move from side (A) to side (B) if a
60. The osmotic pressure of a 5% (wt./vol) solution of
pressure lower than osmotic pressure is applied on
piston (B) cane sugar at 150°C is
(b) water will move from side (B) to side (A) if a (a) 3.078 atm (b) 4.078 atm
pressure greater than osmotic pressure is applied (c) 5.078 atm (d) 2.45 atm
on piston (B) 61. A 5% solution of sugar cane (mol. wt. = 342) is
(c) Water will move from side (B) to side (A) if a
isotonic with 1% solution of X under similar
pressure equal to osmotic pressure is applied on
piston (B) conditions. The molecular weight of X is
(d) Water will move from side (A) to side (B) if pressure (a) 136.2 (b) 68.4
equal to osmotic pressure is applied on piston (A) (c) 34.2 (d) 171.2

56. An unripe mango placed in a concentrated salt 62. At 300 K, 36 g of glucose present in a litre of its
solution to prepare pickle, shrivels because solution has an osmotic pressure of 4.98 bar. If the
(a) it gains water due to osmosis (NCERT Exemplar)
osmotic pressure of the solution is 1.52 bar at the
(b) it loses water due to reverse osmosis same temperature, what would be its
(c) it gains water due to reverse osmosis concentration? (NCERT)

(d) it loses water due to osmosis (a) 0.02 (b) 0.04 (c) 0.08 (d) 0.06

57. Two beakers of capacity 500 mL were taken. One 63. Which of the following units is useful in relating
of these beakers, labelled as “A”, was filled with concentration of solution with its vapour pressure?
(NCERT Exemplar)
400 mL water whereas the beaker labelled “B” was
(a) Mole fraction (b) Parts per million
filled with 400 mL of 2 M solution of NaCl. At the
(c) Mass percentage (d) Molality
same temperature both the beakers were placed in
closed containers of same material and same 64. Ethylene glycol is used as an antifreeze in a cold
capacity as shown in the figure. (NCERT Exemplar)
climate. Mass of ethylene glycol which should
be added to 4 kg of water to prevent it from
freezing at - 6°C will be
A B (K f for water = 1.86 K kg mol -1 and molar mass of
ethylene glycol = 62 g mol -1) (AIEEE 2011)
(a) 804.32 g (b) 204.30 g
(c) 400.00 g (c) 304.60 g
Water NaCl solution
65. A solution of urea in water has a boiling point of
At a given temperature, which of the following 100.128°C. Find the freezing point of the same
statement is correct about the vapour pressure of solution. Molal constants of water kf and kb are
pure water and that of NaCl solution. 1.86°C and 0.512°C respectively.
(a) Vapour pressure in container (A) is more than that (a) - 0.346°C (b) - 0.465°C
in container (B) (c) + 0.465°C (d) - 0.256°C
(b) Vapour pressure in container (A) is less than that
66. What is the freezing point of a 10% (by weight)
in container (B)
solution of CH 3OH in water?
(c) Vapour pressure is equal in both the containers
(a) 90°C (b) 10°C
(d) Vapour pressure in container (B) is twice the
(c) 6.45°C (d) – 6.45°C
vapour pressure in container (A)
650 JEE Main Chemistry

67. Two elements A and B form compounds having 75. The elevation in boiling point of a solution of 13.44
formulae AB2 and AB4 . When dissolved in 20 g g of CuCl 2 in 1 kg of water using the following
benzene, 1 g of AB2 lowers the freezing point by information will be (molecular weight of
2.3° whereas 1.0 g of AB4 lowers it by 1.3°C. K f for CuCl 2 = 134.4 and K b = 0.52 K molal -1)
benzene is 5.1 K mol -1 kg. The atomic masses of A (a) 0.16 (b) 0.05 (c) 0.1 (d) 0.2
and B are respectively 76. What is the freezing point of a solution containing
(a) 25.6, 42.6 (b) 42.6, 25.6 8.1 g HBr in 100 g water assuming the acid to be
(c) 85.3, 25.6 (d) 25.6, 85.3 90% ionised ( K f for water = 1.86 kg mol –1)?
68. The freezing point of a 0.01 M aqueous glucose (a) –0.35°C (b) –1.35°C
(c) –2.35°C (d) –3.53°C
solution at 1 atmosphere is - 0.18°C. To it, an
addition of equal volume of 0.002 M glucose 77. Determine the amount of CaCl 2 (i = 2.47) dissolved
solution will; produce a solution with freezing point in 2.5 L of water such that its osmotic pressure is
of nearly 0.75 atm at 27°C. (NCERT)
(a) - 0.036°C (b) - 0.108°C (a) 1.82 g (b) 3.42 g
(c) - 0.216°C (d) - 0.22°C (c) 2.98 g (d) 1.45 g
69. In 100 g of naphthalene, 2.423 g of S was dissolved. 78. Determine the osmotic pressure of a solution
Melting point of naphthalene = 80.1°C. prepared by dissolving 25 mg of K 2SO 4 in 2 L of
DTf = 0.661°C. L f = 35.7 cal/g of naphthalene. water at 25°C, assuming that it is completely
Molecular formula of sulphur added is dissociated. (NCERT)
(a) S 2 (b) S 4 (c) S 6 (d) S 8 (a) 2.39 ´ 10-2 atm (b) 4.29 ´ 10-3 atm
(c) 5.27 ´ 10-3 atm (d) 1.39 ´ 10-4 atm
Abnormal Colligative Properties and 79. 19.5 g of CH 2 FCOOH is dissolved in 500 g of water.
van’t Hoff Factor The depression in the freezing point of water
70. We have three aqueous solutions of NaCl labelled observed is 1.0°C. Calculate the degree of
as ‘A’, ‘B’ and ‘C’ with concentrations 0.1 M, 0.01 M dissociation and dissociation constant of
and 0.001 M, respectively. The value of van’t Hoff fluoroacetic acid.K f = 1.86 K kg mol -1 (NCERT)
factor for these solutions will be in the order
(NCERT Exemplar) (a) 0.07 and 3.07 ´ 10-3 (b) 0.04 and 3.07 ´ 10-3
(a) i A < iB < iC (b) i A > iB > iC (c) 0.082 and 4.23 ´ 10-4 (d) 0.07 and 4.23 ´ 10-4
(c) i A = iB = iC (d) i A < iB > iC
80. A 1% (w/V) KCl solution is ionised to the extent of
71. Which of the following aqueous solutions should 82%. What would be its osmotic pressure at 291 K?
have the highest boiling point? (NCERT Exemplar) ( R = 0.083 L bar K -1 mol -1)
(a) 1.0 M NaOH (b) 1.0 M Na 2SO4 (a) 1.82 bar (b) 5.9 bar
(c) 1.0 M NH4NO3 (d) 1.0 M KNO3 (c) 82 bar (d) 100 bar
72. Which has minimum osmotic pressure? 81. The osmotic pressure of a dilute solution of an ionic
(a) 200 mL of 2 M NaCl solution compound XY in water is four times that of a
(b) 200 mL of 1 M glucose solution solution of 0.01 M BaCl 2 in water. Assuming
(c) 200 mL of 2 M urea solution complete dissociation of the given ionic compounds
(d) All have same osmotic pressure in water, the concentration of XY (in mol L-1) in
73. When 20 g of naphthoic acid (C11H 8O 2 ) is dissolved solution is (JEE Main 2019)
in 50 g of benzene ( K f = 1.72 K kg mol -1), a (a) 4 ´ 10-2 (b) 16 ´ 10-4
freezing point depression of 2 K is observed. The (c) 4 ´ 10-4 (d) 6 ´ 10-2
van’t Hoff factor (i) is
(a) 0.5 (b) 1 (c) 2 (d) 13
82. Calculate osmotic pressure of a solution obtained
by mixing 100 mL of 3.4% (mass/vol.) solution of
74. The freezing point depression of 0.001 m, urea (molar mass 60) and 100 mL of 1.6 % solution
K x [Fe(CN) 6 ] is 7.10 ´ 10 -3 K. If for water, K f is of cane-sugar (molar mass 342) at 20°C.
1.86 K kg mol -1, value of x will be (a) 6.38 atm (b) 7.38 atm
(a) 4 (b) 3 (c) 2 (d) 1 (c) 4.33 atm (d) 8.38 atm
Solutions 651

83. Elevation in the boiling point for 1 molal solution of 88. 1 g of a non-volatile, non-electrolyte solute is
glucose is 2 K . The depression in the freezing point dissolved in 100 g of two different solvents A and B,
for 2 molal solution of glucose in the same solvent is whose ebullisocopic constants are in the ratio of 1 :
2 K. The relation between K b and K f is (JEE Main 2019) 5. The ratio of the elevation in their boiling points,
(a) K b = 1.5 K f (b) K b = 0.5 K f DTb ( A)
, is
(c) K b = K f (d) K b = 2K f DTb ( B) (JEE Main 2019)

84. The freezing point of benzene decreases by 0.45°C (a) 5 : 1 (b) 10 : 1

(c) 1 : 5 (d) 1 : 0.2
when 0.2 g of acetic acid is added to 20 g of
benzene. If acetic acid associates to form a dimer in 89. The freezing point of a diluted milk sample is found
benzene, percentage association of acetic acid in to be -0.2°C, while it should have been -0.5°C for
benzene will be ( K f for benzene = 5.12 K kg mol - 1) pure milk. How much water has been added to pure
(a) 64.6 % (b) 80.4 % (c) 74.6 % (d) 94.6 % milk to make the diluted sample? (JEE Main 2019)

85. A solution contain 62 g of ethylene glycol in 250 g of (a) 2 cups of water to 3 cups of pure milk
water is cooled upto –10°C. If K f for water is (b) 1 cup of water to 3 cups of pure milk
1.86 K kg mol -1, then amount of water (in g) (c) 3 cups of water to 2 cups of pure milk
separated as ice is (JEE Main 2019)
(d) 1 cup of water to 2 cups of pure milk
(a) 32 (b) 48 (c) 64 (d) 16
90. K 2 HgI 4 is 40% ionised in aqueous solution. The
86. Molal depression constant for a solvent is
value of its van’t Hoff factor (i) is (JEE Main 2019)
4.0 K kg mol -1. The depression in the freezing point
(a) 1.6 (b) 1.8
of the solvent for 0.03 mol kg -1 solution of K 2SO4 is
(c) 2.2 (d) 2.0
(Assume complete dissociation of the electrolyte) 91. Molecules of benzoic acid (C 6 H 5COOH) dimerise in
(JEE Main 2019) benzene. ‘w’ g of the acid dissolved in 30 g of
(a) 0.18 K (b) 0.36 K (c) 0.12 K (d) 0.24 K benzene shows a depression in freezing point equal
87. At room temperature, a dilute solution of urea is to 2 K. If the percentage association of the acid to
prepared by dissolving 0.60 g of urea in 360 g of form dimer in the solution is 80, then w is (Given
water. If the vapour pressure of pure water at this that K f = 5 K kg mol - 1, molar mass of benzoic acid
temperature is 35 mmHg, lowering of vapour = 122 g mol - 1) (JEE Main 2019)
pressure will be (Molar mass of urea = 60 g mol -1)
(JEE Main 2019) (a) 1.8 g (b) 1.0 g
(a) 0.027 mmHg (b) 0.031 mmHg (c) 2.4 g (d) 1.5 g
(c) 0.017 mmHg (d) 0.028 mmHg

ROUND II Mixed Bag

1. The air is a mixture of a number of gases. The 2. Henry’s law constant for CO 2 in water is
major components are oxygen and nitrogen with 1.67 ´ 10 8 Pa at 298 K. Calculate the quantity of
approximate proportion of 20% and 79% by volume CO 2 in 500 mL of soda water when packed under
at 298 K. The water is in equilibrium with air at a 2.5 atm CO 2 pressure at 298 K. (NCERT)
pressure of 10 atm. At 298 K if the Henry’s law (a) 2.82 g (b) 1.85 g
constants for oxygen and nitrogen at 298 K are (c) 9.62 g (d) 11.2 g
3.30 ´ 107 mm and 6.51 ´ 107 mm respectively, the 3. Nalorphene (C19 H 21NO 3), similar to morphine, is
composition of O 2 and N 2 gases in water used to combat withdrawal symptoms in narcotic
respectively are (NCERT)
users. Dose of nalorphene generally given is 1.5 mg.
(a) 4.6 ´ 10-5 , 9.22 ´ 10-5 Calculate the mass of 1.5 ´ 10 -3 m aqueous solution
(b) 9.22 ´ 10-5 , 4.6 ´ 10-5 required for the above dose. (NCERT)
(c) 4.6 ´ 10-5 , 4.12 ´ 10-5 (a) 3.2 ´ 10-2 kg (b) 3.2 ´ 10-4 kg
-5 -5
(d) 4.12 ´ 10 , 4.6 ´ 10 (c) 3.2 ´ 10-3 kg (d) 3.2 ´ 10-5 kg
652 JEE Main Chemistry

4. On the basis of information given below mark the 9. A 5% solution (by mass) of cane sugar in water has
correct option. Information freezing point 271 K. Calculate the freezing point of
5% glucose in water if freezing point of pure water
A. In bromoethane and chloroethane mixture
is 273.15 K. [NCERT]
intermolecular interactions of A¾ A and
B¾ B type are nearly same as A¾ B type (a) 250 K (b) 269 K
interactions. (c) 310 K (d) 275 K

B. In ethanol and acetone mixture A¾ A or B¾ B 10. Benzene and naphthalene form ideal solution over
type intermolecular interactions are stronger the entire range of composition. The vapour
than A¾ B type interactions. pressure of pure benzene and naphthalene at 300 K
C. In chloroform and acetone mixture A¾ A or B are 50.71 mmHg and 32.06 mmHg respectively.
¾ B type intermolecular interactions are Calculate the mole fraction of benzene in vapour
weaker than A¾ B type interactions. phase if 80 g of benzene is mixed with 100 g of
(NCERT Exemplar) naphthalene. (NCERT)
(a) Solution (B) and (C) will follow Raoult’s law (a) 0.67 (b) 0.32 (c) 0.85 (d) 0.42
(b) Solution (A) will follow Raoult’s law 11. A certain substance ‘ A ’ tetramerises in water to
(c) Solution (B) will show negative deviation from the extent of 80%. A solution of 2.5 g of A in 100 g of
Raoult’s law water lowers the freezing point by 0.3°C. The molar
(d) Solution (C) will show positive deviation from mass of A is
Raoult’s law (a) 31 (b) 62 (c) 122 (d) 244
12. Two solutions of glucose have osmotic pressure
5. When mercuric iodide is added to the aqueous 1.0 and 3.5 atm. If 1 L of first solution is mixed
solution of potassium iodide, the with V L of second solution, the osmotic pressure of
(a) freezing point is raised the resultant solution becomes 2.5 atm. Volume of
(b) freezing point is lowered second solution is
(c) freezing point does not change (a) 1.0 L (b) 1.5 L (c) 2.5 L (d) 3.5 L
(d) boiling point does not change 13. A solution containing 30 g of non-volatile solute
6. Which of the following aqueous solutions produce exactly in 90 g of water has a vapour pressure of
the same osmotic pressure? 2.8 kPa at 298 K. Further, 18 g of water is then
added to the solution and the new vapour pressure
(i) 0.1 M NaCl solution
becomes 2.9 kPa at 298 K. Calculate the vapour
(ii) 0.1 M glucose solution pressure of water at 298 K. (NCERT)
(iii) 0.6 g urea in 100 mL solution (a) 3.5 kPa (b) 8.2 kPa
(iv) 1.0 g of a non-electrolyte solute ( X ) in 50 mL (c) 4.2 kPa (d) 1.9 kPa
solution (molar mass of X = 200)
14. Calculate the depression in the freezing point of
(a) (i), (ii), (iii)
water when 10 g of CH 3CH 2CHClCOOH is added
(b) (ii), (iii), (iv)
to 250 g of water. K a = 1.4 ´ 10 -3;
(c) (i), (ii), (iv)
K f = 1.86 K kg mol -1. (NCERT)
(d) (i), (iii), (iv)
(a) 0.42 K (b) 0.82 K
7. A 0.025 M solution of monobasic acid had a freezing (c) 0.19 K (d) 0.65 K
point of –0.060°C. The pK a for the acid is 15. Given,
( K b = 1.86 K kg mol -1)
(a) 1.2 (b) 2 (c) 2.5 (d) 5.7 A B
1. 0.1 M KCl 0.2 M KCl
8. How many gram of sucrose (mol. wt. = 342) should
2. 0.1% (m/V) NaCl 10% (m/V) NaCl
be dissolved in 100 g water in order to produce a
3. 18 gL -1 glucose 34.2 gL -1 sucrose
solution with a 105.0°C difference between the
4. 20% (m/V) glucose 10% (m/V) glucose
freezing point and boiling temperature?
( K f = 1.860 ° C / m, K b = 0.151° C/ m) Indicate the number of solutions which is/are isotonic
(a) 34.2 g (b) 72 g (a) 1 only (b) 3 only
(c) 342 g (d) 460 g (c) 4 only (d) 2 only
Solutions 653

16. The phase diagram for the pure solvent and Codes
solution are recorded below. The quantity indicated (a) A-p, B-q, C-r, D-s
by L in the figure is (b) A-q, B-p, C-s, D-r
(c) A-q, B-r, C-p, D-s
pext (d) A-q, B-p, C-r, D-s
p*
p 23. The degree of dissociation (a ) of a weak electrolyte,
p Ax B y is related to van’t Hoff factor ( i) by the
L
expression (AIEEE 2011)
i -1 i -1
(a) a = (b) a =
(x + y - 1) x+ y+1
T Tb* Tb x+ y-1 x+ y+1
(c) a = (d) a =
(a) Dp (b) K b × m (c) K f m (d) m i -1 i -1
17. The vapour pressure of pure benzene and toluene 24. A 5% solution of cane sugar (molar mass 342) is
are 160 and 60 torr respectively. The mole fraction isotonic with 1% of a solution of an unknown
of toluene in vapour phase in contact with
solute. The molar mass of unknown solute in g/mol
equimolar solution of benzene and toluene is
(a) 0.50 (b) 0.93 (c) 0.6 (d) 0.27 is (AIEEE 2011)
(a) 136.2 (b) 171.2
18. At certain hill-station, pure water boils at
(c) 68.4 (d) 34.2
99.725°C. If K b for water is 0.513°C kg mol -1, the
boiling point of 0.69 m solution of urea will be 25. Ethylene glycol is used as an antifreeze in a cold
(a) 100.359°C (b) 103°C climate. Mass of ethylene glycol which should
(c) 100.073°C (d) unpredictable be added to 4 kg of water to prevent it from
19. The density of a solution prepared by dissolving freezing at - 6° C will be (kf for water = 1.86 K kg
120 g of urea (mol. mass = 60 u) in 1000 g of water mol -1 and molar mass of ethylene glycol = 62 g
is 1.15 g/mL. The molarity of this solution is mol -1)
(a) 0.50 M (b) 1.78 M (AIEEE 2012) (a) 804.32 g (b) 204.30 g (AIEEE 2011)
(c) 1.02 M (d) 2.05 M
(c) 400.00 g (d) 304.60 g
20. K f water is 1.86 K kg mol -1. If your automobiles
26. Match the following columns.
radiator holds 1.0 kg of water, how many grams of
ethylene glycol (C 2 H 6O 2 ) must you add to get the Column II
Column I
(Nature of solubility curve, i.e.
freezing point of the solution lowered to –2.8°C? (Salt)
solubility vs temperature)
(AIEEE 2012)
(a) 72 g (b) 93 g (c) 39 g (d) 27 g A. NH4 NO3 p. Increases continuously

21. A 5.2 molal aqueous solution of methyl alcohol, B. Li 2CO3 q. First increases and then
decreases
CH 3OH, is supplied. What is the mole fraction of
methyl alcohol in the solution ? [AIEEE 2011] C. Na 2SO4 × 10H2O r. Increases but not
continuously.
(a) 0.100 (b) 0.190 (c) 0.086 (d) 0.050
D. KCl s. Decreases continuously.
22. Match the following columns.
Codes
Column I Column II
(a) A-r, B-q, C-s, D-p
A. 10.6 g Na 2CO3 dissolved in p. 0.1 M (b) A-p, B-s, C-q, D-r
100 mL solution (density (c) A-s, B-r, C-q, D-p
= 1.06 g mL- 1 ) (d) A-r, B-s, C-q, D-p
B. 34.2 g L- 1 sucrose solution q. 1M
(density = 1.0342 g mL- 1 )
Numeric Value Questions
C. 9.8% H2SO4 solution (density r. 1.25 M
1.25 g mL- 1
27. Compound PdCl 4 .6H 2O is a hydrated complex; 1 m
aqueous solution of it has freezing point. 269.28 K.
D. 20% aqueous ethanol solution s. 3.0 M
by volume (density Assuming 100% ionisation of complex, the number
= 0.938 g mL- 1 ) of ions furnished by complex in the solution ……… .
654 JEE Main Chemistry

28. The osmotic pressure of urea solution at 10ºC is 32. The osmotic pressure of a solution of NaCl is
200 mm becomes 105.3 mm when it is diluted and 0.10 atm and that of a glucose solution is 0.20 atm.
temperature raised to 25°C. The extent of dilution is The osmotic pressure of a solution formed by
……… . mixing 1 L of the sodium chloride solution with 2 L
29. The osmotic pressure of a solution containing 40 g of the glucose solution is x ´ 10 -3 atm. x is ………
of solute (molecular mass 246) per litre at 27°C is (nearest integer). (JEE Main 2020)

( R = 0.0822 atm L mol -1) ……… . 33. 10.0 mL of Na 2CO 3 solution is titrated against 0.2
30. 12.2 g of benzoic acid ( Mw = 122) in 100 g water M HCl solution. The following titre values were
had elevation in boiling point of 0.27. obtained in 5 readings.
K b = 0.54 K kg mol - 1. If there is 100% 4.8 mL, 4.9 mL, 5.0 mL, 5.0 mL and 5.0 mL.
polymerisation, the number of molecules of benzoic
Based on these readings, and convention of
acid in associated state is ……… .
titrimetric estimation of concentration of Na 2CO 3
31. The hardness of a water sample containing 10 -3 M solution is ……… mM. (JEE Main 2021)
MgSO 4 expressed as CaCO 3 equivalents (in ppm)
is ……

Answers
Round I
1. (b) 2. (a) 3. (b) 4. (c) 5. (a) 6. (b) 7. (b) 8. (b) 9. (a) 10. (c)
11. (d) 12. (a) 13. (d) 14. (a) 15. (c) 16. (a) 17. (c) 18. (a) 19. (a) 20. (c)
21. (c) 22. (c) 23. (c) 24. (b) 25. (b) 26. (d) 27. (c) 28. (c) 29. (c) 30. (b)
31. (d) 32. (c) 33. (b) 34. (a) 35. (c) 36. (c) 37. (d) 38. (c) 39. (c) 40. (b)
41. (b) 42. (c) 43. (c) 44. (b) 45. (a) 46. (a) 47. (a) 48. (c) 49. (a) 50. (a)
51. (a) 52. (d) 53. (d) 54. (b) 55. (a) 56. (d) 57. (a) 58. (c) 59. (a) 60. (c)
61. (b) 62. (d) 63. (a) 64. (a) 65. (b) 66. (d) 67. (a) 68. (b) 69. (d) 70. (c)
71. (b) 72. (b) 73. (a) 74. (b) 75. (a) 76. (d) 77. (b) 78. (c) 79. (a) 80. (b)
81. (d) 82. (b) 83. (d) 84. (d) 85. (c) 86. (b) 87. (c) 88. (c) 89. (c) 90. (b)
91. (c)

Round II
1. (a) 2. (b) 3. (c) 4. (b) 5. (b) 6. (b) 7. (c) 8. (b) 9. (b) 10. (a)
11. (b) 12. (b) 13. (a) 14. (d) 15. (b) 16. (b) 17. (d) 18. (c) 19. (d) 20. (b)
21. (c) 22. (a) 23. (a) 24. (c) 25. (a) 26. (d) 27. (2) 28. (2) 29. (4) 30. (2)
31. (100) 32. (167) 33. (50)
 Solutions
Round I 10. Molarity of base =
normality 0.1
= = 0.1
1. Precipitation occurs when the solution is acidity 1
supersaturated. M1V1 = M 2V 2
3. At high altitudes, atmospheric pressure is low and 0.1 ´ 19.85 = M 2 ´ 20
solubility of gases varies directly with pressure thus, M 2 = 0.09925 » 0.099
decreases at high altitudes.
11. Molarity
This is the reason for low concentration of oxygen in weight % of solute ´ density of the solution ´ 10
=
blood and tissues of people living at high altitude. molecular weight of the solution
4. The order of increasing solubility are 98 ´ 1.84 ´ 10
= = 18.4
Ar < CO2 < CH4 < HCHO 98

(As solubility increases as the values of K H decreases) 12. 6.5 molal KOH = 1000 g solvent has 6.5 moles KOH
5. Mass of aspirin = 6.5 g so, wt. of solute = 6.5 ´ 56 = 364 g
Mass of acetonitrile = 450 g wt. of solution = 1000 + 364 = 1364
1364
Mass of solution = (6.5 + 450) g = 456.5 g Volume of solution = mL
1.89
(6.5 g)
Mass % = ´ 100 = 1.424% Mole of solution 6.5 ´ 1.89 ´ 1000
(456.5 g) Molarity = = = 9.00
Vsolution in Litre 1364
6. K H = 4.27 ´ 105 mmHg (at 298 K), p = 760 mm 14. (a) 6 g of NaOH/100 mL
Applying Henry’s law, 6 ´ 1000
N = = 1.5 N
p = K H c (c = Mole fraction or solubility of methane) 40 ´ 100
p (760 mm) (b) 0.5 M H2SO4
x= = = 178 ´ 10-5 = 1.78 ´ 10-3
K H (4.27 ´ 105 mm) N = M ´ basicity = 0.5 ´ 2 = 1.0
7. Molarity = 0.15 M or 0.15 mol L-1 (c) N phosphoric acid, normality = 1
Volume of solution = 250 mL = 0.25 L (d) 8 g of KOH/L
strength in g / L 8
Molar mass of solute Normality = = = 0.14 N
= (12 ´ 6) + (1 ´ 5) + (12) + (16 ´ 2) + (1) equivalent weight 56
= 122 g mol-1 15. N 1V1 + N 2V 2 = N 3V3
mass 1
Molarity = ´ ; 0.3 ´ 100 + 0.6 ´ 200 = N 3 ´ 300
molar mass volume (L)
0.3 +1.2 = 3N3
W 1
(0.15 mol L-1 ) = ´ N 3 = 0.5
(122 g mol-1 ) (0.25 L)
16. (i) Cyclohexane and n-octane both are non-polar.
Mass of solute = (0.15 ´ 122 ´ 0.25) g = 4.575 g
(Benzoic acid) So, they mix completely in all proportions.
(ii) KCl is an ionic compound, but n-octane is non-polar.
8. Density of the solution = 1.072 g mL-1
So, KCl does not dissolve in n-octane.
Mass of solution = Mass of solute + Mass of solution (iii) CH3 OH and CH3CN both are polar but CH3CN is
= 222.6 g + 200 g = 422.6 g less polar than CH3 OH. As the solvent is
mass 422.6 g non-polar, CH3CN will dissolve more than CH3 OH
Volume = = = 394.2 m L
density 1.072 g mL-1 in n-octane.
= 0.3942 L Order of solubility is
mass of ethylene glycol / molar mass KCl < C H3 OH < CH3CN < cyclohexane.
Molarity (M ) =
volume in litres 17. CaCl2 ¾® Ca 2+ + 2Cl–
-1 1 mol 2 ´ 6.023 ´ 10 23 ions
(222.6 g) / (62 g mol )
=
0.3942 L 2 ´ 6.023 ´ 1023 Cl- ions are present in = 1 mole of CaCl2
-1
= 9.10 mol L = 9.10 M 1 ´ 3.01 ´ 1022
3.01 ´ 1022 Cl- ions are present in
9. An increases in temperature increase the volume of 2 ´ 6.02 ´ 1023
the solution and thus, decreases its molarity. = 0.025 mole of CaCl2
656 JEE Main Chemistry

number of moles n2(1 - c 2)

M= \ n1 = …(ii)
volume of solution (in L) c2
0.025 Place the value of n1 in eq. (i)
= ´ 1000 = 0.125 M
200 n2(1 - c 2)M1
\ + n2M 2
18. L-equivalents of solution c2
n2
æ 6.00 eq. ö Þ (M 2c 2 - M1c 2 + M1 )
= 1 L´ç ÷ = 6.00 eq c2
è L ø
Volume of solution,
Let x = volume of concentrated solution. Then n (M c - M1c 2 + M1 )
= 2 2 2 L
1.00 - x = volume of dilute solution 1000 ´ d ´ c 2
æ 12.0 eq ö æ 3.00 eq ö 1000 ´ n2 ´ dc 2
(x) ç ÷ + (1.00 - x) ç ÷ = 6.00 eq C2 =
è L ø è L ø n2(M 2c 2 - M1c 2 + M1 )
On solving, x = 0.333 1000d c 2
\ C2 =
\ Volume of concentrated solution = 0.33 L M1 + c 2(M 2 - M1 )
and, Volume of dilute solution = 1 - 0.33 = 0.67 L Hence, the correct option is (c).
19. Let the total volume of solution = x 24. m M of MgCl 2
NV 0.5 ´ 100 1 ´ 10-3 ´ 103 1 æ mass ö
\ V2 = 1 1 = = 500 cm3 = = çmilli mole = ´ 1000÷
N2 0.1 95 95 è M. mass ø
\ The volume of water added = 500 -100 cm3 = 400 cm3 1 ´ 10-3 ´ 103 1
m M CaCl 2 = =
20. Q Lowering in weight of solution µ solution pressure ( ps ) 111 111
\m M of CaCl 2, if MgCl 2 and CaCl 2 are taken in form
and lowering in weight of solvent µ p° - ps
of CaCO3 .
(Q p° = vapour pressure of pure solvent) 1 1 206
= + =
p° - ps lowering in weight of solvent 0.05 95 111 111 ´ 95
Thus, = =
ps lowering in weight of solution 2.5 (Q Ca, Mg both are bivalent, \mole ratio is 1 : 1)
But according to Raoult’s law, 206 ´ 100
1000 mL water has CaCO3 =
p° - ps w M 111 ´ 95 ´ 1000
= ´
ps m W \ 106 mL water has CaCO3
206 ´ 100 ´ 106
0.05 10 ´ 18 10 ´18 ´ 2.5 = = 1.953
\ = Þ m= = 100 g mol -1 111 ´ 95 ´ 1000 ´ 1000
2.5 90 ´ m 90 ´ 0.05
\ Hardness = 1.953 ppm.
21. BaCl2 furnishes more ions than KCl and thus, shows
25. Vapour pressure of water ( p° ) = 760 torr
higher boiling point, i.e. t1 > t2. mass ( g )
Number of moles of glucose =
22. Correct match is (I) ® E, (II) ® C, (III) ® A, (IV) ® F molecular mass ( g mol-1 )
(I) Foam – Froth 18 g
= = 0.1 mol
Foam forms gas particles trapped in solid or liquid. 180 g mol-1
(II) Gel – Jellies Molar mass of water = 18 g/mol
Gel is a colloid, where dispersed phase is liquid Mass of water (given) = 178.2 g
and dispersion medium is solid. Number of moles of water
(III) Aerosol – Smoke mass of water 178. 2g
= = = 9.9 mol
Aerosol is a colloid, where solid/liquid particles molar mass of water 18 g /mol
dispersed in gas. Total number of moles = (0.1 + 9.9) mol = 10 mol
(IV) Emulsion– Milk Now, mole fraction of glucose in solution = Change in
Emulsion is formed by mixing two liquids. (Milk is pressure with respect to initial pressure
combination of 2 liquid) Dp 0.1
i.e. =
p° 10
23. In first component, or Dp = 0.01 p° = 0.01 ´ 760 = 7.6 torr
Mass = number of moles ´ molecular weight = n1M1 \Vapour pressure of solution = (760 - 7.6) = 752.4 torr
In second component, Mass = n2M 2
26. If two liquids A and B form minimum boiling
Mass of solution = n1M1 + n2M 2 …(i) azeotrope at some specific composition then A ¾ B
n2 interactions are weaker than those between A¾ A or
Mole-fraction (c 2) =
n1 + n2 B ¾B.
Solutions 657

28. The one whose boiling point is more than that of either Vapour pressure of pure liquid B ( pB° ) = 500 torr
of the two pure components is known as azeotropic Total vapour pressure of solution ( p) = 475 torr
mixture with maximum boiling point. This is formed According to the Raoult’s law
by non-ideal solutions showing negative deviation.
p = p°A c A + pB° cB
30. Relative lowering in vapour pressure,
475 torr = p°A ´ (0.1139) + 500 torr ´ (0.8861)
p° - ps w ´ M
= 475 torr = p°A ´ (0.1139) + 443.05 torr
p° m ´W
(475 - 443.05) torr 31.95
143 - ps 0.5 154 p°A = = torr = 280.5 torr
= ´ (0.1139) 0.1139
143 65 1.58 ´ 100
[Q molecular weight of CCl4 = 154 Step II Calculation of vapour pressure of A in the
and weight = density ´ volume] solution ( pA )
143 - ps = 1.07 Þ ps = 141.93 mm According to Raoult’s law,

31. Vapour pressure of pure liquid A ( p°A ) = 450 mm pA = p°A c A = (280.5 torr) ´ (0.1139) = 32.0 torr

Vapour pressure of pure liquid B ( pB° ) = 700 mm 33. For ideal solution,
Total vapour pressure of the solution ( p) = 600 mm p = c ¢A p°A + c ¢B p °B
According to Raoult’a law, Q c ¢A = 0.4, c ¢B = 0.6
p = p°Ac A + p°A cB = p°Ac A + pB° (1 - c A ) p °A = 7 ´ 103 Pa, p °B = 12 ´ 103 Pa
On substituting the given values in Eq. (i), we get
(600 mm) = 450 mm ´ c A + 700 mm (1 - c A )
p = 0.4 ´ 7 ´ 103 + 0.6 ´ 12 ´ 103
= 700 mm + c A (450 - 700) mm
= 10 ´ 103 Pa = 1 ´ 104 Pa
= 700 - c A (250 mm)
In vapour phase,
(600 - 700) p c ¢ p° 0.4 ´ 7 ´ 103
cA = = 0.40 cA = A = A A = = 0.28
- (250 mm) p p 1 ´ 104
Mole fraction of A (c A ) = 0.40 \ c = 1 - 0.28 = 0.72 [Q cA + cB = 1]
B

Mole fraction of B (cB ) = 1 - 0.40 = 0.60 34. For a solution of volatile liquids the partial vapour
pA = p°Ac A = (450 mm) ´ 0.40 = 180 mm pressure of each component of the solution is directly
proportional to its mole fraction present in solution.
pB = pB° cB = (700 mm) ´ 0.60 = 420 mm
This is known as Raoult’s law. Liquid M and N form
Mole fraction of A in vapour phase an ideal solution. Vapour pressures of pure liquids M
pA (180) mm and N are 450 and 700 mm Hg respectively.
= = = 0.30
pA + pB (180 + 420) mm \ pº N > pº M
Mole fraction of B in vapour phase So, by using Raoult’s law
pB (420) mm yN > xN …(i)
= = = 0.70
pA + pB (180 + 420) mm and xM > yM …(ii)
Multiplying (i) and (ii) we get
32. Step I Calculation of vapour pressure of pure
yN xM > yM xN
liquid A ( p°A )
xM y
Number of moles of liquid A \ > M
xN yN
W (100 g)
(nA ) = A = = 0.7143 mol Thus, correct relation is (a).
M A (140 g mol-1 )
35.
Number of moles of liquid B Liquid Vapour
W (1000 g)
(nB ) = B = = 5.5556 mol
MB (180 g mol-1 )
Mole fraction of A
nA (0.7143 mol)
(c A ) = =
nA + nB (0.7143 + 5.5556) mol
0.7143
= = 0.1139
6.2699 Only solvent-It has Solvent+non-
Mole fraction of B (cB ) = 1 - 0.1139 = 0.8861 more vapour volatile solute-It has
pressure less vapour pressure
658 JEE Main Chemistry

If a non-volatile solute is added to a solvent to form a As B is less volatile, ptotal < p°A
solution, the vapour pressure gets decreased. (c A )vapour
\According to Raoult’s law, if vapour pressure of pure \ or (c A )vapour > (c A )liquid
(c A )liquid
solvent is p°, vapour pressure of solvent in solution ( p)
is = p°×xA. 40. ptotal (expected from Raoult’s law) = c A p°A + cB pB°
\ p < p° 1 2
= ´ 150 + ´ 240 = 50 + 160 = 210 torr which is
Since, vapour pressure of solution is less, there will be 3 3
net backward reaction [i.e. vapour ¾® liquid] in that greater than the experimental value of 200 torr. As
beaker. Thus, its volume increases. observed vapour pressure is less that expected from
Raoult’s law, it shows - ve deviation from Raoult’s law.
In another beaker containing only net reaction is
forward, 41. There is H-bonding in ethyl alcohol which is cut off on
adding n-heptane. Hence, it shows positive deviations.
Thus, volume decreases.
36. The incorrect statement among the given statements 42. On mixing acetone and chloroform, dipole-dipole
is (c) and the explanation of all the statements is as interactions take place. Hence, negative deviation
follows from Raoult’s law is observed.
According to Raoult’s law, vapour pressure of the 43. Ethanol + water form a non-ideal solution showing
solution pideal (ideal vapour pressure) + ve deviation from Raoult’s law. Hence, DH = + ve,
= p° + ( pB° - p°A ) cB i.e. there is absorption of heat and DV = + ve, i.e. there
A
is increase in volume.
(A = solvent : acetone, B = solute : CS 2)
44. In CS 2-acetone, A ¾ B interactions are weaker than
Given; p°A = 344 mmHg, pB° = 512 mmHg. A ¾ A, B ¾ B interactions.
\ pideal = 3.44 + (512 - 344)cB 45. HNO3 + H2O solution shows negative deviation from
or pideal = 344 + 168 cB and so, 0 < cB < 1. ideal behaviour and hence it forms azeotropic with
maximum boiling point.
Also, total vapour pressure ( p) = 600 mmHg
p° - ps
\ For any value of cB , p > pideal . 46. = molality ´ (1 - a + xa + ya )
p°
Since p ¹ pideal , so, option (a) is correct.
The value of p° - ps is maximum for BaCl2.
Option (b) is also correct. Since p > pideal ,
(i.e. positive deviation) therefore attractive force 47. Due to addition of nitric acid in water, the vapour
between CS 2 and acetone is weaker than CS 2 ¾ CS 2 or pressure of pure water decreases.
acetone-acetone attraction. 48. Relative lowering in vapour pressure,
Option (c) is incorrect as for positive deviation, DV > 0 p° - ps w M
because final volume of solution must be greater than = ´
p° m W
the sum of volumes of components taken. 0.30 mm 20 18
Option (d) is correct. Since, in such solution, D mix H is = ´
17.54 mm m 100
positive because energy is required to break A ¾ A and 20 ´ 18 ´ 17.54
B ¾ B bonds. Þ m= = 210.48
0.30 ´ 100
3 3
37. Mole fraction of P, (cP ) = =
3+2 5 49. wB (solute) = 25 g ; MB = 180 g mol-1; pAo = 17.535 mm
2 2 wA (water) = 450 g; M A = 18 g mol ; ps = ?
Mole fraction of Q. (cQ ) = = pA° - ps nB
3+2 5 = cB =
pA° nB + nA
Ptotal = cP 5 cP0 + cQ ´ cQ0
w 25
3 2 nB = B = = 0.1389
= ´ 80 + ´ 60 = 48 + 24 = 72 torr MB 180
5 5
w 450
38. When XB = 0, we have pure A nA = A = = 25
MA 18
\ p°A = 120 - 80 ´ 0 = 120 mm 17.535 - ps 0.1389
=
The given expression can be rewritten as 17.535 0.1389 + 25
p = 120 - 80(1 - X A ) 17.535 - ps
= 0.00552
When X A = 0, we have pure B 17.535
ps = 17.535 - 0.097
\ pB° = 120 - 80(1 - 0) = 120 - 80 = 40 mm ps = 17.438 mmHg
pA (c A )liquid p°A (c A )vapour p°A 50. The unit of ebullioscopic constant is K kg mol-1 or K
39. (cA )vapour = = or =
ptotal ptotal (c A )liquid ptotal (molality) -1.
Solutions 659

342 WB 1.52
51. DTf = 1.86 ´ = 1.86° C = = 0.0610 mol L-1
342 MB 4.98 ´ 5
\Tf = T - DTf = 0 - 1.86 = - 1.86° C
64. DTf = Freezing point of H2O - Freezing point of
52. From depression in freezing point expression, ethylene glycol solution
1000 ´ K f ´ w = 0 - (- 6° ) = 6°
M=
DT ´ W K f = 1.66° K kg mol-1
1000 ´ 1.86 ´ 50 w1 = mass of ethylene glycol in grams
62 =
9.3 ´ W w2 = mass of sovent (H2O) in grams = 4000 g
W = 161.3 g m1 = molar mass of ethylene glycol = 62 g mol-1
Total water = 200 g 1000 K f w1 1000 ´ 1.86 ´ w1
DTf = Þ 6=
Hence, ice separated = (200 - 161.3) g = 38.7 g m1 w2 62 ´ 4000
53. i =1 + a w1 = 800 g
cal. mol. weight 58.5 65. Q DTb = K b ´ m
= = = 1.95 DTb 0.128
exp. mol. wt 30 m= = = 0.25
K b 0.512
\ 1 + a = 1.95
Now, K f = 1.86° C,m = 0.25
a = 0.95
\ DTf = K f ´ m
55. In the figure water will move from side (B) to side (A)
if a pressure greater than osmotic pressure is applied \ DTf = 1.86 ´ 0.25 = 0.465° C
on piston (B). Thus, (b) is the correct option. \ Freezing point of the solution (Tb ) = T ° - DTf
56. An unripe mango placed in a concentrated salt = 0 - 0.465 = - 0.465° C
solution to prepare pickle, shivels because it loses
66. 1.00 kg contains 0.100 kg CH3 OH (and 0.900 kg H2O)
water due to osmosis.
w 1 æ 1 mol ö 3.12 mol
58. p = RT , since, wRT/V are constant thus, p µ (100 g CH3 OH) ç ÷ = 3.12 mol = = 3.47 m
mV m è 32.0 g ø 0.900 kg
\ p2 > p1 > p3 DTf = K f ´ m = (1.86° C/m)(3.47 m) = 6.45° C
6 Freezing point of the solution (Tb ) = T ° - DTf = 0 - 6.45
59. Molarity of urea = 60 =1M
100 = -6.45° C
1000 100 K f w2
67. D f =
Hence, 1 M solution of glucose is isotonic with 6% urea w1 M 2
solution. 1000 ´ 5.1 ´ 1
For AB2, 2.3 = or M AB2 = 110.87
5 1 50 20 ´ M AB2
60. C = ´ ´ 1000 = mol/L
342 100 342 1000 ´ 5.1 ´ 1
50 For AB4 ,1.3 = or M AB 4 = 196.15
p= ´ 0.082 ´ 423 = 5.07 atm 20 ´ M AB2
342
Suppose atomic mass of A = a and that of B = b. Then
61. For isotonic solution
a + 2b = 110.87 and a + 42.64 • 42,6
w1 w2 5 1 342
= Þ = Þ m2 = = 68 .4 On solving, we get
m1 m2 342 m2 5
a = 25.59 • 25.6 and b = 42.64 = 196.15
WB ´ R ´ T
62. p = CRT = 68. All other factors remaining the same, DTf µ molar
MB ´ V
concentration
For both the solutions, R, T and V are constants. (DTf )1 C1
=
For I solution (DTf )2 C 2
(36 g) ´ R ´ T
(4.98 bar) = …(i) Molar concentration after mixing can be calculated as
(180 g mol-1 ) ´ V
M1V1 + M 2V 2 = M3 (V1 + V 2)
For II solution 0.012
WB ´ R ´ T 0.01 ´ V + 0.002 V = M3 (2 V ) or M3 = = 0.006
(1.52 bar) = … (ii) 2
MB ´ V 0.18 0.01
= or (DTf )2 = 0.108
On dividing Eq. (ii) by Eq. (i), we get (DTf )2 0.006
(1.52 bar) WB ´ R ´ T 180 ´ V
= ´ \ Tf of solution after mixting = 0 - 0.108 = - 0.108°C
(4.98 bar) MB ´ V 36 ´ R ´ T
660 JEE Main Chemistry

1000 K f w2 1000 w2 RT02 Thus, number of particles after ionisation

69. M 2 = = ´
w1 DTf w1 DTf 1000 L f = 1 - a + a + 2a = 1 + 2a
1000 ´ 2.423 2(353.1) 2 1 + 2a
= ´ = 256 g mol -1 \vant’ Hoff factor (i ) = (On 100% ionisation, a = 1)
100 ´ 0.661 1000 ´ 35.7 1
1 + 2 ´1
If S x is the formula, then molecular mass i= =3
1
= x ´ 23 = 256 or x = 8
The elevation of boiling point, DTb = 3 ´ K b ´ m
70. BaCl2 gives maximum ion hence, it shows lowest
vapour pressure. Molality of CuCl2 solution
wt. of CuCl2 in g / mol wt. of CuCl2
71. Elevation in bp = iK b × m (m) =
wt. of water in kg
If kb and m are same,
13.44
Elevation in boiling point µ i
+ = 134.4 = 0.1 m
NaOH ¾® Na
14 42 OH3–
+ 44 1
2 ions Thus, DTb = 3 ´ 0.52 ´ 0.1 = 0.156° C » 0.16° C
Na 2SO4 ¾® 2Na + + SO2–
4 + –
144244 3 76. HBr º H + Br
3 ions (1 - a) a a
NH4NO3 ¾® NH4+ + NO3– i total = (1 - a ) + a + a = (1 + a )
144244 3
2 ions i = 1 + 0.9 = 1.9
KNO3 ¾® K + + NO3–
14243 8.1 1000
2 ions
DTf = iK f m = 1.9 ´ 1.86 ´ ´
81 100
72. Osmotic pressure is a colligative property.
= 3.53° C
Osmotic pressure µ no. of particles
NaCl ¾® Na + + Cl– Tf = T - DTf = 0 - 3.53° C = - 3.53° C
Concentration of particles = 2 ´ 2M = 4M 77. According to van’t Hoff equation,
Glucose does not dissociate inB RT
Osmotic pressure (p) = i CRT =
\ Concentration of particles = 1 ´ 1 M = 1 M V
Urea does not dissociate,
i = 2.47; V = 2.5 L; R = 0.0821 L atm K -1mol-1
\ Concentration of urea = 1 ´ 2 M = 2 M
\ Glucose solution will have minimum osmotic T = 27 + 273 = 300 K; p = 0.75 atm
pressure. pV (0.75 atm) ´ (2.5 L)
nB = =
73. Actual molecular weight of naphthoic acid (C11H8O2) iRT (2.47) ´ (0.0821 L atm K -1mol-1 ) ´ (300 K)
= 172 = 0.0308 mol
1000 ´ K f ´ w Amount of CaCl2 dissolved = nB ´ MB
Molecular mass (calculated) =
W ´ DTf = (0.0308 mol) ´ (111 g mol-1 )
1000 ´ 1.72 ´ 20 = 3.42 g
= = 344
50 ´ 2
78. Amount of K 2SO4 dissolved = 25 mg = 0.025 g
actual mol. wt. 172
van’t Hoff factor (i ) = = = 0.5 Volume of solution = 2 L
calculated mol. wt. 344
T = 25° C = 25 + 273 K = 298 K
74. DTf = i ´ K f ´ m Molar mass of
7.10 ´ 10-3 = i ´ 1.86 ´ 0.001 K 2SO4 = (2 ´ 39) + (32) + (4 ´ 16) = 174 g mol-1
i = 3.817 Since, K 2SO4 dissociates completely as,
Aq
i -1 ¾® 2 K + + SO24-
K 2SO4 ¾ ¾
a=
n -1 Total ions produced after dissociation (per mol) = 3
3.817 - 1 n i ´W ´ R´T
1= Þ x = 2.817 » 3 So, i = 3, p = iCRT = i ´ RT =
(x + 1) - 1 V M ´V
\ Molecular formula of the compound is K3 [Fe(CN)6 ]. 3 ´ (0.025 g) ´ (0.0821 L atm K -1mol-1 ) ´ (298 K)
=
(174 g mol-1 ) ´ (2 L)
2+ –
75. CuCl2 º Cu +2Cl
Before ionisation 1 mol 0 0
After ionisation (1 - a) a 2a = 5.27 ´ 10-3 atm
Solutions 661

79. Step I Calculation of van’t Hoff factor of acid Putting the values of i in (i)
°
DTf = 1 C = 1 K; K f = 1 . 86 K kg mol -1 2 ´ [XY ] = 4 ´ 3 ´ [BaCl2]
DTf = i K f m 2 ´ [XY ] = 12 ´ 0.01
DTf 12 ´ 0.01
or i= …(i) [XY ] =
Kf m 2
WB (19.5 g) So, the concentration of XY = 0.06 mol L-1
m= = = 6 ´ 10-2 mol L-1
MB ´ W A (78 g mol-1 ) ´ (0.5 kg)
= 0.5 mol kg -1 … (ii) 82. Given 100 mL of urea solution is mixed with 100 mL of
cane-sugar and therefore, total volume of solution
Placing the values in Eq. (i), we find the value of van’t
becomes 200 mL in which 3.4 urea and 1.6 g sugar is
Hoff factor (i )
present
1
i= = 1.0753 \p sugar ´ (200 / 1000) = (1.6 / 342) ´ 0.821 ´ 293
(1.86 K kg mol ) ´ (0.5 mol kg -1 )
-1

\ p sugar = 0.56 atm

Step II Calculation of degree of dissociation of
the acid \p urea ´ (200 / 1000) = (3.4 / 60) ´ 0.0821 ´ 293
Suppose degree of dissociation at the given \p urea = 6.82 atm
concentration is a. Total p = p sugar + p urea
aq = 0.56 + 6.82 = 7.38 atm
CH2FCOOH s CH2FCOO- + H+
Initial conc. C mol kg -1
0 0 83. Elevation in boiling point (DTb ) = K b ´ m ´ i
At equilibrium C (1 - a) Ca Ca Depression is freezing point (DTf ) = K f ´ m ´ i
Total = C (1 + a) where, m = molality
C (1 + a ) For the glucose solution (van’t Hoff factor, i = 1),
\ i= =1 + a DTb1m = DTf2m = 2K
C
a = i - 1 = 1.0753 - 1 = 0.0753 So, Kb ´ 1 ´ 1 = K f ´ 2 ´ 1
Step III Calculation of dissociation constant for Þ K b = 2K f
the acid 84. Let the degree of association of acetic acid (CH3COOH)
(Molal) C = 0.5 m (From Eq. (ii)) in benzene is a, then
- + 2
[CH2 FCOO ] [H ] Ca × Ca Ca 2CH3COOH -(CH COOH)3 2
Ka = = =
[CH2 FCOOH] C (1 - a ) (1 - a ) Initial moles 1 0
a
Moles at equilibrium 1-a
(0.5) (0.0753)2 (0.5) ´ (0.0753)2
Ka = = = 3.07 ´ 10-3 a a a2
(1 - 0.0753) (0.9247) \Total moles = 1 - a + =1 - or i = 1 -
2 2 2
80. KCl ¾® K + + Cl– Now, depression in freezing point (DTf ) is given as
DTf = i K f m K (i)
i -1 i-1
a= or 0.82 = or i = 1.82 where, K f = molal depression constant or
n -1 2- 1 cryoscopic constant.
W m = molality
pV = i B ´ RT
MB number of moles of solute 0.2 1000
100 Molality = = ´
Volume of solution = 100 mL = L weight of solvent (in kg) 60 20
1000
100 1 Putting the values in Eq. (i)
p´ = 1.82 ´ ´ 0.083 ´ 291 é aù é 0.2 1000 ù
1000 74.5 \ 0.45 = ê1 - ú (5.12) ê ´
439.58 ë 2û ë 60 20 úû
p= = 5.9 bar
74.5 a 0.45 ´ 60 ´ 20
1- =
81. Osmotic pressure is proportional to the molarity (C) 2 5.12 ´ 0.2 ´ 1000
of the solution at a given temperature, p = CRT
a
Concentration of BaCl2 = 0.01 M (Given) Þ 1- = 0.527
2
p XY = 4p BaCl 2 (Given) a
Þ = 1 - 0.527
i ´ CRT = 4 ´ i ´ CRT …(i) 2
For the calculation of i, \ a = 0.946
XY ¾® X + + Y - (Here, i = 2)
Thus, percentage of association = 94.6%
BaCl2 ¾® Ba 2+ + 2Cl- (Here, i = 3)
662 JEE Main Chemistry

85. Considering the expression of the depression in 0.60

nB 60 0.01 0.01
freezing point of a solution, = = = = = 0.0005
nA + nB 360
+
0 .60 20 + 0.01 20.01
DTf = K f ´ m ´ i
18 60
wB ´ 1000
Tf° - Tf = K f ´ ´i …(i) i = van’t Hoff factor = 1 (for urea)
MB ´ wA (in g )
Now, according to Raoult’s law, Dp = cB ´ i ´ pº
Here, Tf° = 0° C, Tf = - 10°C
On substituting the above given values, we get
wB = mass of ethylene glycol = 62 g
Dp = 0.0005 ´ 1 ´ 35 = 0.0175 mmHg
MB = molar mass of ethylene glycol
ö 88. The expression of elevation of boiling point,
æ ÷
ç CH2 — CH2 ÷
ç ÷ w2 ´ 1000
ç ½ ½ ÷ DTb = K b ´ m ´ i = kb ´ ´i
ç
OH OH ÷ M 2 ´ w1
ç ÷
ç ø
= 62 g mol -1 è where, m = molality
wA = mass of water in g as liquid solvent, i = van’t Hoff factor = 1 (for
i = van’t-Hoff factor = 1 non-electrolyte/non-associable)
(for ethylene glycol in water) w2 = mass of solute in g = 1 g (present in both of
the solutions)
K f = 1.86 K kg mol -1
M 2 = molar mass of solute in g mol -1 (same
On substituting in Eq. (i), we get solute in both of the solutions)
62 ´ 1000
0 - (- 10) = 1.86 ´ ´1 w1 = mass of solvent in g = 100 g (for both of the
62 ´ wA solvents A and B)
1.86 ´ 62 ´ 1000 K b = ebullioscopic constant
Þ wA = = 186 g
10 ´ 62
So, the expression becomes,
So, amount of water separated as ice (solid solvent) DTb µ K b
= 250 - wA = (250 - 186) g = 64 g
DTb ( A ) K b ( A ) 1 é Kb ( A) 1 ù
Þ = = ê Given, = ú
86. Depression in freezing point (D Tf ) is given by DTb (B) K b (B) 5 ë K b (B) 5 û
DTf = iK f m
89. We know that,
i = vant Hoff factor
Depression in freezing points (DTf )
K f = molal depression constant
m = molality T ° f - Tf = K f ´ m ´ i
For K 2SO4, i = 3 where, K f = molal depression constant
It can be verified by the following equation : wsolute ´ 1000
m = molality =
K 2SO4 - 2K +
+ SO2- Msolute ´ wsolvent (in g)
4
Using formula i = van’t Hoff factor
DTf = iK f ´ m = 3 ´ 4 ´ 0.03 = 0.36 K For diluted milk
87. For dilute solution, lowering of vapour pressure DTf1 = K f ´ m1 ´ i
(Dp) = p 0 - p and relative lowering of vapour pressure wmilk ´ 1000
Þ 0 - (0.2) Þ 0.2 = K f ´ ´1
Dp M milk ´ w1 (H2O)
= 0 which is a colligative property of solutions.
p For pure milk DTf2 = K f ´ m2 ´ i
Dp wmilk ´ 1000
= cB ´ i Þ 0 - (-0.5) = 0.5 = K f ´ ´1
p0 M milk ´ w2(H2O)
Þ Dp = cB ´ i ´ p0 0.2 K f wmilk ´ 1000 M ´ w2 (H2O)
So, = ´ ´ milk
where, p0 = vapour pressure of pure solvent 0.5 K f M milk ´ w1 (H2O) wmilk ´ 1000
i = van’t Hoff factor
w2(H2O)
cB = mole fraction of solute =
w1 (H2O)
Given,
w2(H2O) (in pure milk) 2
p° = vapour pressure of pure water of 25º C Þ =
w1 (H2O) (in diluted milk) 5
= 35 mmHg
i.e. 3 cups of water has to be added to 2 cups of
cB = mole fraction of solute (urea)
pure milk.
Solutions 663

90. The ionisation of K 2HgI4 in aqueous solution is as pN2 (7.9 ´ 760 mm)
cN 2 = = = 9.22 ´ 10-5
follows KH (6.51 ´ 107 mm)
K 2[HgI4 ] - 2K + + [HgI4 ]2 -
2. Step I Calculation of number of moles of CO2
van’t Hoff factor (i) for ionisation reaction is given as,
According to Henry’s law,
i = 1 + a ( n - 1)
partial pressure of CO2
where, n = number of ions, Mole fraction of CO2 (cCO2 ) =
K H for CO2
a = degree of ionisation or dissociation (1 atm)
From above equation, it is clear that n = 3 KH = 1.67 ´ 108 Pa = ´ (1.67 ´ 108 Pa)
(101325 Pa)
i = 1 + 0.4 (3 - 1) = 1.648 ´ 103 atm
[Given, % a = 40% or a = 0.4] 2.5 atm
cCO2 = = 1.52 ´ 10-3
= 1.8 (1.648 ´ 103 Pa)
91. Molecules of benzoic acid dimerise in benzene as: (500 g)
n H 2O = = 27.78 mol
2(C6H5COOH) -(C6H5COOH)2 (18 g mol-1 )
Now, we know that depression in freezing point (DTf ) nCO2 nCO2 nCO2
is given by following equation: cCO2 = = =
nCO2 + nH2O n H 2O (27.78 mol)
i ´ K f ´ wsolute ´ 1000
DTf = i ´ K f ´ m = ...(i)
Mwsolute ´ wsolvent nCO2 = cCO2 ´ (27.78 mol)
Given, wsolute (benzoic acid) = w g = (1.52 ´ 10-3 ) ´ (27.78 mol)
wsolvent (benzene) = 30 g
= 0.0422 mol
Mwsolute (benzoic acid) = 122 g mol- 1, DTf = 2 K
Note nCO2 is considered negligible due to its little
K f = 5 Kkg mol- 1, % a = 80 or a = 0.8
solubility in water.
2(C6H5COOH)
Initial 1
- (C6H5COOH)2
0
Step II Calculation of mass of dissolved CO2 in
water
Final 1- a a/ 2
= 1 - 0.8 = 0 . 2 0.8 / 2 = 0 . 4 Mass of CO2 = no × of moles of CO2 ´ molar mass of CO2
Total number of moles at equilibrium = (0.0422 mol) ´ (44 g mol-1 )
= 0.2 + 0.4 = 0.6 = 1.857 g
Number of moles at equilibrium 3. m = 1.5 ´ 10-3 m or 1.5 ´ 10-3 mol kg -1
i=
Number of moles present initially
Mass of solute = 1.5 ´ 10-3 g or 1.5 mg
0.6
i= = 0.6 Mass of solvent = ?
1
On substituting all the given values in Eq. (i), we get Molar mass of solute
0.6 ´ 5 ´ w ´ 1000 (C19H21NO3 ) = (12 ´ 19) + (1 ´ 21) + (14) + (16 ´ 3)
2= , w = 2.44 g
122 ´ 30 = 311 g mol-1
Thus, weight of acid (w) is 2.4 g. mass
Number of moles of solute =
molar mass
Round II
(1.5 ´ 10-3 g)
1. Step I Calculation of partial pressure of oxygen =
(311 g mol-1 )
and nitrogen
number of moles
Partial pressure of O2 Molality (m) =
mass of solvent in kg
20
(pO ) = (10 atm) ´ = 2 atm = 2 ´ 760 mm number of moles
2 100 Mass of solvent =
79 molality
Partial pressure of N2 ( pN ) = (10 atm) ´ = 7.9 atm
2 100 (1.5 ´ 10-3 g) 1
= -1
´ -3
= 7.9 ´ 760 mm (311 g mol ) (1.5 ´ 10 mol kg)
Step II Composition of O2 and N2 dissolved in 1
= = 0.0032 kg or 3.2 g
water 311
The amount of gases dissolved in water is calculated 5. HgI2 although insoluble in water but shows complex
in terms of their mole fractions.
formation with KI and therefore, freezing point
pO (2 ´ 760 mm)
cO = 2
= = 4.6 ´ 10-5 decreases.
2 K H (3.30 ´ 107 mm)
664 JEE Main Chemistry

6. (ii) 0.1 M glucose, p = CRT = 0.1RT Freezing point for 5% glucose solution
(iii) 0.6 g urea in 100 mL solution = (273.15 - 4.085) K = 269.07 K
n w/m 0.6 /60 ´ 1000 10. For ideal solution, Raoult’s law is pT = p°A cA + pB° cB
p= RT = RT = ´ RT = 0.1 RT
V V 100 p°A c A
and vapour pressure in vapour phase =
(iv) 1.0 g of non electrolyte solute (X) is 50 mL solution pT
1.0 / 200 Thus, the required quantities are c A , cB and pT as we
p= ´ 1000RT = 0.1 RT
50 know p°A and pB° .
Hence, option (ii), (iii), (iv) have same osmotic Molar mass of benzene (C6H6 ) = 78 g mol-1
pressure, osmotic pressure of 0.1 M NaCl is higher
Molar mass of naphthalene (C10H8 ) = 128 g mol-1
than (ii), (iii), (iv) because it dissociates to give
maximum number or particles. nC 6H6 (Number of moles of benzene)
DT -0.060 80 g
7. m = b = = 3.2 ´ 10-2 = 0.032 = = 1.026 mol
Kb -1.86 (78 g mol-1 )
i.e. 0.032 = total particles nC10H8 (Number of moles of naphthalene)
(100 g)
\ The number of H+ = (0.032 - 0.025) m = 0.007 M H+ = = 0.781 mol
(128 g mol-1 )
HA H+ + A -
+
º
-
[H ] = [ A ] = 0.007 M Mole fraction of benzene
\ HA = 0.018 (1.026 mol)
(cC 6H6 ) = = 0.568
(0.007)2 (1.026 + 0.781) mol
Ka = = 3 ´ 10-3
0.018 Mole fraction of naphthalene (cC10H8 ) = 1 - 0.568 = 0.432
-3 Applying Raoult’s law,
pK a = - log K a = - log (3 ´ 10 ) = 2.5
8. Boiling point (Tb ) = 100 + DTb = 100 + K bm Partial vapour pressure of benzene in solution ( pC 6H6 )
= pC° 6H6 ´ cC 6H6
Freezing point (Tf ) = 0 - DTf = - K f m
Tb - Tf = (100 + K bm) - (- K f m) = (50.71 mm) ´ (0.568)
105 = 100 + 0.51m + 1.86 m = 28.80 mm
5 Partial vapour pressure of naphthalene in solution
2.37m = 5 or m = = 2.11
2.37 ° H ) ´ cC H
( pC10H8 ) = p(C10 8 10 8
\ Weight of sucrose to be dissolved in 100 g water = (32.06 mm) ´ (0.432)
2.11 ´ 342 = 13.85 mm
= ´ 100 = 72 g
1000 Total vapour pressure of solution ( p)
9. For cane sugar solution = (28.80 + 13.85) mm
Wb (sugar) = 5 g; W A (water) = 100 - 5 = 95 g = 42.65 mm
MB (sugar) = 342 g mol-1; DTf = (273.15 - 271.00) K Mole fraction of benzene in vapour phase
= 2.15 K cC H ´ p°C 6H6
= 6 6
K ´ WB ptotal
DTf = f
MB ´ W A 0.568 ´ (50.71 mm)
= = 0.675
K f ´ (5 g) (42.65 mm)
(2.15 K) = ….(i)
(342 g mol-1 ) ´ (95 g) 1-i 1-i
11. Degree of association, a = Þ 0.8 =
1 1
For glucose solution 1- 1-
n 4
WB (glucose) = 5 g; W A (water) = 100 - 5 = 95 g
i = 0.4
MB (glucose) = 180 g mol-1; DTf = ?
K f ´ (5 g) Q DT = i ´ K f ´ m
DTf = …(ii) wB ´ 1000
(180 g mol-1 ) ´ (95 g) 0.3 = 0.4 ´ 1.86 ´
mB ´ wA
On dividing Eq. (ii) by Eq. (i)
2.5 ´ 1000
DTf K f ´ (5 g) (342 g mol-1 ) ´ (95 g) 0.3 = 0.4 ´ 1.86 ´
= -1
´ mB ´ 100
(2.15 K) (180 g mol ) ´ (95 g) (K f ) ´ (5 g)
342 ´ 2.15 0.4 ´ 1.86 ´ 2.5 ´ 1000
DTf = K = 4.085 K mB = = 62 g mol -1
180 0.3 ´ 100
Solutions 665

12. p 1V1 + p 2V 2 = p R (V1 + V 2) (23 g mol-1 )

2.8 kPa = p°A
(6 + 23) g mol-1
1 ´ 1 + 3.5V = 2.5 (1 + V )
2.8 ´ 29
1 + 3.5V = 2.5 + 2.5 V p°A =
23
or V = 1.5 L
81.2
13. Step I Calculation of molar mass of the solute = = 3.53 kPa
23
Case I Number of mole of solute 14. Step I Calculation of degree of dissociation
mass (30 g) 30 Mass of solute = 10 g
(nB ) = = -1
= mol
molar mass (M g mol ) M Molar mass of solute
Number of moles of water (CH3CH2CHClCOOH) = (12 ´ 4)+ (1 ´ 7) + (35.5) + (16 ´ 2)
mass (90 g)
(nA ) = = = 5 mol
molar mass (18 g mol-1 ) = 48 + 7 + 35.5 + 32
Mole fraction of water = 122.5 g mol-1
nA (5 mol) M Molal concentration of solution
(c A ) = = = mass/molar mass
nA + nB æ 30 ö (6 + M ) =
ç5 mol + mol÷
è M ø mass of solvent (kg)
(10 g)
Vapour pressure of first solution ( pA ) = 2.8 kPa =
(122.5 g mol-1 ) ´ (0.25 kg)
According to Raoult’s law, pA = p°A c A
= 0.326 m
M
(2.8 kPa) = p°A x …(i) If a is the degree of dissociation of
(6 + M ) CH3CH2CHCl COOH, then
30 - +
Case II Number of moles of solute (nB ) =
M
mol CH3CH2CHClCOOH
Initial conc. C mol -1
kg
º CH CHClCOO + H
3
0 0
Number of moles of water
mass (108 g) At equilibrium C (1 - a) Ca Ca
(nA ) = = = 6 mol
molar mass (18 g mol-1 ) Ca ´ Ca
\ Ka = = Ca 2
nA C (1 - a )
Mole fraction of water (c A ) =
nA + nB [Considering (1 - a ) = 1 for dilute solutions]
(6 mol) M K Ka
= = 2
a = a or a =
æ 30 ö (5 + M ) C C
ç6 mol + mol÷
è M ø
1.4 ´ 10-3
Vapour pressure of solution ( pA ) = 2.9 kPa So, a= = 42.9 ´ 10-4
0.326
According to Raoult’s law, pA = p°A c A = 6.55 ´ 10-2 = 0.065
M Step II Calculation of van’t Hoff factor (i)
(2.9 kPa) = p°A ´ … (ii)
(5 + M ) - +

Dividing Eq. (i) by Eq. (ii)

CH3CH2CHClCOOH º CH CH CHCl COO + H
3 2

Initial no. of moles 1 0 0

(2.8 kPa) (5 + M ) Moles at equilibrium 1 - a a a
=
(2.9 kPa) (6 + M )
Total number of moles after dissociation
(5 + M ) = (1 - a ) + (a ) + (a ) = (1 + a )
0.9655 =
(6 + M )
van’t Hoff factor
(0.9655 ´ 6) + 0.9655 M = 5 + M Total number of moles after dissocation
(i ) =
0.0345 M = 0.793 Number of moles before dissocation
0.793
M= = 23 g mol-1 i=
(1 + a )
= (1 + a ) = 1 + 0.065 = 1.065
0.0345 1
Step II Calculation of vapour pressure of water
Step III Calculation of depression in freezing
According to Raoult’s law, pA = p°A c A point (DTf )
M
or (2.8 kPa) = p°A = …(iii) DTf = i K f m
(6 + M )
= (1.065) ´ (1.86 K kg mol-1 ) ´ (0.326 mol kg -1 )
Placing the value of M in Eq. (i)
DTf = 0.65 K
666 JEE Main Chemistry

15. Isotonic solution have same molarity. 5.2

= = 0.086
60.76
18 1000
Molarity of 18 g glucose = = 0.1 10.6 1000
180 1000 22. (A) Molarity = ´ =1 M
106 100
34.2 1000
Molarity of 34.2 g sucrose = = 0.1 34.2 g L- 1
342 1000 (B) Molarity = = 0.1 M
342 g mol- 1
The concentration of 18 g L -1 glucose is same to
34.2 gL -1 sucrose. (C) 9.8% H2SO4 means 9.8 g in 100 g of solution.
Volume of solution = 100 / 1.25 = 80 mL.
16. L represents DTb = K b × m 9.8 1
Molarity = ´ ´ 1000 = 1.24 M
17. For equimolar solutions cB = cT = 0.5 98 80
(D) 20% of ethanol solution means 20 cc ethanol in
pB = cB ´ pB° = 0.5 ´ 160 = 80 mm
100 cc of solution.
pT = cT ´ pT° = 0.5 ´ 60 = 30 mm Mass of solution = 100 ´ 0.938 = 93.8 g
ptotal = 80 + 30 = 110 mm Volume of water = 80 cc
30 Mass of water = 80 g
Mole fraction of toluene in vapour phase = = 0.27
110 Mass of 20 cc ethanol = 93.8 - 80 = 13.8 g
18. DTb = K b ´ m = 0.513 ´ 0.69 = 0.354 13.8 1
Molarity = ´ ´ 100 = 3.0 M
Tb = T + DTb = 99.725 + 0.354 = 100.079° C 46 100

19. Total mass of solution = 1000 g water + 120 g urea 23. Ax By º xA y + + yBx -
After dissociation (1 - a) xa ya
= 1120 g
i = n ( Ax By ) + n ( A y + ) + n (Bx - )
Density of solution = 1.15 g/mL
mass 1120 g = 1 - a + xa + ya
Thus, volume of solution = = = 1 + a (x + y - 1)
density 1.15 g / mL
i -1
= 973.91 mL \ a=
(x + y - 1)
= 0.974 L
120 24. Two solutions are isotonic if their osmotic pressures
Moles of solute = =2 are equal.
60
Moles of solute p1 = p 2
Molarity =
Volume (L) of solution M1ST1 = M 2ST2
2 (M1 and M 2 are molarities)
= = 2.05 mol L-1
0.974 At a given temperature,
20. Coolant is glycol (C2 H6O2) and is non-electrolyte M1 = M 2
DTf = 2.8° 1000w1 1000w2
= (V1 = V 2 = 100 mL)
1000K f w1 m1V1 m2V 2
DTf =
m1w2 Cane sugar Unknown
w1 w2
1000 ´ 1.86 ´ w1 \ =
2.8 = m1 m2
62 ´ 1000
5 1
\ w1 = 93.33 g =
342 m2
moles of solute
21. Molality = 342
kg of solvent m2 = = 68.4 g mol -1
5.2 mol CH3 OH 5
=
1 kg (= 1000 g) H2O 25. DTf = freezing point of H2O - freezing point of ethylene
n1 (CH3 OH) = 5.2 glycol solution = 0 - (-6° ) = 6°
1000 K f = 1.86° kg mol -1
n2 (H2O) = = 55.56
18 w1 = Mass of ethylene glycol in gram
\ n1 + n2 = 5.20 + 55.56 = 60.76 mol w2 = Mass of solvent (H2O) in grams = 4000 g
\ cCH = Mole fraction of CH3 OH m1 = Molar mass of ethylene glycol = 62 g mol -1
3OH
n1 i = van’t Hoff factor = 1
=
n1 + n2 (ethylene glycol being non-electrolyte)
Solutions 667

1000 K f w1 (i ) 31. Hardness in ppm

DTf =
m1 w2 Mass of CaCO3 equivalent to the total number of
1000 ´ 1.86 ´ w1 ´ 1 hardness causing substances ´ 106
\ 6= moles of =
62 ´ 4000 Mass of water sample
2+ -3
w1 = 800 g Here, [Mg ] = 10 M
nMg 2+ = 10-3 per 1 L water 1000 g
26. Solubility of NH4NO3 increases with temperature but
Mass of 10-3 mole of CoCO3 + 10-3 ´ 100 g = 0.1 g
not continuously. Hence, (A) ® (r).
0.1 ´ 106
Solubility of Li2CO3 decreases continuously with ppm = = 100 ppm
temperature. Hence, (B) ® (s). 1000
Solubility of Na 2SO4 × 10H2O first increases upto 34.4ºC 32. Osmotic pressure,
and then decreases. Hence, (C) ® (q). p = i ´ C ´ RT
Solubility of KCl increases continuously with Here, i = van’t Hoff factor, T = temperature
temperature. C = concentration and R = gas constant.
Hence, (D) ® (p). For NaCl, i = 2
27. DT = iK f m So, p NaCl = i ´ C NaCl ´ RT
(273 - 269.28) = i ´ 1.86 ´ 1 0.1 = 2 ´ C NaCl ´ RT
0.05
3.72 = i ´ 1.86 C NaCl =
RT
i =2
i -1 For glucose, i = 1 because it cannot ionise
a= ; (a = 100% = 1) So, p glucose = i ´ Cglucose ´ RT
n -1
2 -1 0.2 = 1 ´ Cglucose ´ RT
1= Þn =2 0.2
n -1 Cglucose =
RT
28. Let p 1 = 200 mm; T1 = 283, p 1 = 105.3; T2 = 298 (Q nNaCl = numbers of moles NaCl)
n nNaCl in 1 L = C NaCl ´ V litre
Now, p = RT
V 0.05
n = (nglucose = number of moles of glucose)
At T1, 200 = R ´ 283 RT
V1 0.4
nglucose in 2 L = Cglucose ´ V litre =
n RT
At T2, 50 = ´ R ´ 298
V2 V total = 1 + 2 = 3L
Dividing Eq. (i) by Eq. (ii), we get 0.05
So, final conc. NaCl =
200 V 283 3RT
= 2´ 0.4
105.3 V1 298 Final conc. glucose =
3RT
Þ V 2 = 2V1
p total = p NaCl + p glucose
æ W2 ö
ç ÷ RT = [i ´ C NaCl + Cglucose ] RT
è Mw2 ø
29. p = CRT =
V æ 2 ´ 0.05 0.4 ö
=ç + ÷ ´ RT
Given, W 2 = 40 g è 3RT 3RT ø
Mw2 = 246 0.5
= atm
T = 27º C = 300 K 3
V = 1L = 0.1666 atm = 166.6 ´ 10-3 atm
Substituting all the values, we get = 167.00 ´ 10-3 atm
40 x = 167.00
p= ´ 0.082 ´ 300 = 4 atm So,
246
33. Most precise volume of HCl = 5 mL at equivalence point
30. DTb = iK bm
Meq. of Na 2CO3 = meq. of HCl.
12.2 1000
0.27 = i ´ 0.54 ´ ´ Let molarity of Na 2CO3 solution = M, then
122 100
or i = 0.5 M = 0.05 mol / L
Therefore, benzene associated as dimer, i.e. 2. = 0.05 ´ 1000 = 50 mM