CHAPTER

1 Solutions

Topicwise Weightage of JEE Main 6 Years Paper (124 Sets)

Solubility and Vapour Pressure Expressing Concentrations

of Liquid Solutions of Solutions
31%
17%

Ideal and Non-Ideal Solutions 2%

50%

Colligative Properties and

Abnormal Molar Mass

“How’s the Josh?” for these Topics: Mark your confidence level in the blank space around the topic (Low-L, Medium-M, High-H)

INTRODUCTION other is called solute. Example, alcohol in water, benzene

A solution may be defined as a homogeneous mixture of a single in toluene etc.
phase containing two or more of the chemical species dispersed Types of Solution
on a molecular scale. The characteristics of any one section of
the homogeneous solution will be completely identical to those S.No. Solvent Solute Examples
of any other section of the solution. Depending upon the number 1. Gas Gas Mixture of gases, air.
of total constituents present in the solution, it is called binary 2. Gas Liquid Water vapour in air, mist.
solution (two constituents), ternary solution (three constituents), Sublimation of a solid into a gas,
quaternary solution (four constituents) and so on. 3. Gas Solid
smoke storms.
(i) Solvent: The liquid or medium of dissolution which allows CO2 gas dissolve in water (aerated
the solute to dissolve in it so as to form a solution is called 4. Liquid Gas
drink), soda water.
a solvent.
Mixture of miscible liquids e.g.
(ii) Solute: The substance which dissolves or disappears in the 5. Liquid Liquid
alcohol in water.
solvent to form a solution is called solute.
6. Liquid Solid Salt in water, sugar in water.
Solute + Solvent = Solution.
Adsorption of gases over metals,
(iii) The component which has the same physical state in pure 7. Solid Gas
hydrogen over palladium.
form as the solution is called solvent and the other is called
Mercury in zinc, mercury in gold
solute. Example, in case of solution of sugar and water, 8. Solid Liquid
i.e. all amalgams.
sugar is the solute and water is solvent.
Homogeneous mixture of two
(iv) If both the components have same state as the solution, the
9. Solid Solid or more metals (i.e. alloys) e.g.
one component which is in excess is called solvent and the
copper In gold. zinc In copper.

1 JEE (XII) Module-1 CHEMISTRY PW

CONCENTRATION TERMS ™ Formality (F):
Before proceeding further, it is worth reviewing the units in which  It may be defined as the number of gram formula masses of the

the concentration of the solution may be expressed. ionic solutes dissolved per litre of the solution. Mathematically
Mass of the ionic solute (in gram)
Concentration Terms Formality (F) =
Formula mass of the solute ´ Volume of solution(L)
™ % Concentration
Commonly, the term formality is used to express the

weight of solute (g) concentration of the ionic solids which do not exist as
(i) % w/w = × 100
weight of solution (g) molecule but as network of ions.
Example: 10% w/w urea solution = 10 gm of urea is present ™ Mole Fraction
in 100 gm of solution. For binary mixture
(ii) % wt/vol. (w/v)
moles of solute n
% w/v = wt. of solute/100 mL of solution Xsolute = =
total moles in solution n+N
weight of solute (g)
% w/v = ´ 100 moles of solvent N
volume of solution (mL) XSolvent = =
Example: 10% (w/v) urea solution. = 10 gm of urea is present Total moles in solution n+N
in 100 mL of solution. Xsolute + XSolvent = 1
volume of solute [Here n ⇒ moles of solute and N ⇒ moles of solvent]
(iii) % v/v = × 100
volume of solution ™ ppm (Parts Per Million)

Example: 10% v/v ethanol aqueous solution → 10 mL of wt.of solute (in g)

(a) ppm (w/w) = × 106
ethanol in 100 mL of solution. wt.of solution (in g)
= 10 mL of ethanol in 90 mL of H2O wt.of solute (in g)
Strength of solution in g/L (b) ppm (w/v) = × 106
™ vol. of solution (in mL)
Weight of solute (in gram) per litre (1000 mL) of solution. moles of solute
(c) ppm (moles/moles) = × 106
Example: 10% (w/v) sucrose solution, then specify its moles of solution
concen­tration in g/L
Key Note
100 mL _____ 10 g
10 In general p.p.m is used for very dilute solutions.
\ 1000 mL _____ ´ 1000 = 100 g/L
100 ™ In very dilute solution, mass of solution will be
™ Molarity (M) = No. of moles of solute per litre of solution. approximately taken as equal to mass of solvent.
™ Sum of mole fractions of all components is always one.
n æwö 1000
Molarity = = ç ÷ × æWö
V (in L) è M ø V (in mL) ™ Mole fraction, ppm, molality, % ç ÷ are always
èWø
No. of moles of solute = molarity × volume ( in L)
independent of the temperature.
No. of milli moles of solute = molarity × volume (in mL)
™ Molality (m) = No. of moles of solute per kg (1000 g) of solvent. ™ Normality, molarity, % æ V ö , % æ W ö of a solution
ç ÷ ç ÷
Let w gram of solute and Molar mass = M (g/mole) is èVø èVø
dissolved in ‘W’ gram of solvent. changes with change in temperature.

æwö 1000 moles ´ 1000

Molality = ç ÷ × or molality =
èMø W(g) W(g)of solvent CONVERSION OF CONCENTRATION
™ Normality (N) = No. of equivalents per litre of solution TERMS
no.of equivalents of solute 1. Molarity and % solute by mass: Let d = density of
=
volume of solution (in L) solution in g/mL and let it contains x% (w/w) solute by
 No. of equivalents = normality × volume (in L) x × d ×10
mass. M =
(Normality = n-factor × molarity) mA
Molar mass
 Equivalent mass =
n - factor ™ Specific gravity has no units and its numerical value
Mass of the species equals density in g/mL.
 No. of equivalents of a species =
equivalent mass

2 JEE (XII) Module-1 CHEMISTRY PW

 2. Molality and mole fraction: Consider a binary solution M ×1000
consisting of two components A (Solute) and B (Solvent). 7. Molarity into Molality m =
1000d - MM 2
Let XA & XB are the mole fraction of A & B respectively. M1 and M2 are molar masses of solvent and solute.
nA nB Molarity = M mole of solute in 1000 ml of solution
XA = , XB =
nA + nB nA + nB moles of solute = M & weight of solute = MM2
weight of solution = 1000d
If molality of solution be m then:
mass of solvent = 1000d – MM2
nA nA M ´ 1000
m=
´ 1000 = ´ 1000 molality =
mass of solvent nB ´ MB 1000d - MM 2
where MB is the molecular wt. of the solvent B.
é1 M ù
mole fraction of A 1000 on simplifying d = M ê + 2 ú
X 1000 ´ ë m 1000 û
m= A ´
⇒m=
XB MB mole fraction of B M B
Dilution & Mixing of two Liquids
mole fraction of solute 1000 ™ Upon dilution no. of moles of solute remains constant. If a
m= ´
mole fraction of solvent molecular wt. of solvent particular solution having volume V1 mL and molarity M1 is
diluted upto volume V2 mL.
3. Mole fraction of solute into molarity of solution
M1V1 = M2V2
X 2 d ×1000
M= M2 : final molarity
X1 M1 + M 2 X 2
™ If a solution having volume V1 and molarity M1 is mixed
Mole fraction of solvent and solute are X1 and X2 so X1 + X2 = 1 with another solution of same solute having volume V2 &
Suppose total mole of solution is = 1 then mole of solute and molarity M2 then M1V1 + M2V2 = MR (V1 + V2)
solute and solvent are X2 & X1 respectively M V +M 2 V2
MR = Resultant molarity = 1 1
weight of solute = X2M2, weight of solvent = X1M1 V1 +V2
& total wt. of solution = X1M1 + X2M2
X1M1 + X 2 M 2 X M + X2M2 Train Your Brain
volume of solution = ml = 1 1 L
d d ´ 1000
X 2 ´ d ´ 1000 Example 1: If we have 6% w/w urea solution with density
molarity (M) =
X1M1 + X 2 M 2 1.060 g/mL, then calculate its strength in g/L.
4. Molarity into mole fraction X2 = 1000M/ [1000d– MM2] Sol. 6 g urea is present in 100 gm solution.
Molarity = M moles solute in 1000 ml of solution 100 æ mass ö
So, moles of solute = M & mass of solution = d × 1000 6 g in mL ç density = ÷
1.060 è volume ø
wt. of solute = MM2 & wt. of solvent = (1000d – MM2)
Where M2 is molar mass of solute 100
mL ® 6 gm
mole fraction of solute = 1000M / [1000d – MM2] 1.060
mM1 6
5. Molality into mole fraction X2 = \ 1000 mL = ´ 1.060 ´ 1000
1000 + mM1 100
Molality = moles of solute in 1000 gm of solvent = m = 10.6 ´ 6 = 63.6 g/L
1000 Example 2:
moles of solvent = where M1 is molar mass of solvent
M1
(i) Which type of solution is milk?
m mM1 (ii) Name a solid - solid type solution.
mole fraction X2 = =
1000 1000 + mM1 (iii) Which type of solution is smoke?
+m
M1 Identify the correct matching
md ×1000
6. Molality into molarity M = (i) (ii) (iii)
1000 + mM 2
Molality = m moles of solute in 1000 gm of solvent (a) Liquid in solid Atmosphere Gas in liquid
mole of solute = m & weight of solute = mM2 (b) Liquid in gas Alloys Liquid in solid
Weight of solution = 1000 + mM2
1000 + mM 2 (c) Liquid in liquid Rubber Solid in gas
volume of solution = mL = 1000 + mM 2 L
d d ´ 1000 (d) Gas in liquid Rubber Liquid in liquid
m ´ d ´ 1000
molarity = Sol. (c) Liquid in liquid – Rubber – Solid in gas
1000 + mM 2

3 JEE (XII) Module-1 CHEMISTRY PW

 (iii) Factors affecting solubility:
Example 3: A storage battery contains a solution of H2SO4 (a) Nature of solute and solvent: Like dissolves like.
30% by weight. Find Polar solutes dissolves in polar solvents and non polar
(i) Molality (ii) Molarity solutes dissolve in non polar solvents. NaCl dissolves
(iii) Normality (iv) Mole fraction of H2SO4 in water because NaCl and water both are polar. CS2
dissolves in benzene because CS2 and C6H6 both are
 (Given density of solution = 1.2 gm/cm3)
non polar.
Sol. 30% by weight ⇒ Wsolute = 30 gm, Wsolution = 100 gm, (b) Size of solute particles: Dissolution is a surface
Wsolvent = 70 gm phenomenon like the evaporation. So, increase
100 of surface area of the solute increases the rate of
Vsolution = mL
1.2 dissolution. The surface area of a solid solute can be
30 70 increased by converting it into powder. The powdered
nsolute = = 0.306 nsolvent = = 3.889 solute dissolves more easily than the large crystals,
98 18
as in the former case, larger surface area is in contact
n solute ´ 1000 0.306 ´ 1000 with the solvent.
(i) Molality = = = 4.37 m
Wsolvent 70 (c) Effect of Temperature: Solubility may increase or
n solute ´ 1000 0.306 ´ 1000 decrease with increase of temperature. This depend
(ii) Molarity = = = 3.67 M on the enthalpy change of the solution. If the solute
Vsolution 100
dissolves with the evolution of heat, solubility
1.2
decreases with increase of temperature. On the other
(iii) Normality = W solute ´ 1000 30 ´ 1000 = 7.34 N hand if the solute dissolves with the absorption of
=
Esolute ´ Vsolution 100 heat, solubility increases with rise in temperature.
49 ´
1.2 Example: When ammonium chloride or silver nitrate
Alternatively
is dissolved in water, the solution gets cooled.
Normality = n-factor × Molarity
= 2 × 3.67 = 7.34 NH 4 Cl(s) + H 2 O() ¾¾ ® NH 4 Cl(s) - heat

X H 2SO4 0.306 For such solutions, solubility increases on increase of

(iv) X H 2SO4 = n =
0.306 + 3.889 = 0.073
temperature.
H 2SO 4 + n H 2 O
Example: When calcium oxide or lithium carbonate
is placed in water the solution gets heated.
CaO(s) + H 2 O ¾¾ ® Ca(OH) 2 (aq) + Heat

Concept Application For such solutions, solubility decreases on increase of

temperature.

1. A sample of H2SO4 (density 1.8 g/mL) is labelled as Key Note

74.66% by weight. What is the molarity of acid?
The amount of heat change during the formation of a solution
(a) 15.2 M (b) 16.3 M
depends mainly on two factors:
(c) 17.5 M (d) 13.7 M
™Lattice energy: It is the amount of heat required to
separate one mole of the ionic substances into its
component positive and negative ions. This is an
SOLUTIONS OF SOLID/ LIQUID IN LIQUID endothermic process.
™ Heat of hydration: These ions get hydrated. The ions
Solubility of a solid in liquid
hold the water molecules by ion dipole attraction. Heat
(i) Introduction: Different solutes dissolve to a different
is liberated during the process of hydration. Thus it is an
extent in the same mass of a solvent i.e., they have different exothermic process.
solubilities. Solubility is thus the ability of a solute to (a) If lattice energy > hydration energy, the system cools
dissolve in a particular solvent. down.
(ii) Definition: The solubility of a particular solute in a solvent Examples: NaNO3, KNO3, KCl, NH4Cl etc,
is the maximum amount of solute that will dissolve in 100 g (solubility increases with rise in temperature are).
solvent. (b) If lattice energy < hydration energy, the system heats up.
Wt. of solute Examples: NaOH, Na2CO3, Na2SO4, all gases, etc,
Solubility = ´ 100 (solubility decreases with rise in temperature are).
Wt. of solvent

4 JEE (XII) Module-1 CHEMISTRY PW

 Partial pressure of HCl/torr
1000
(c) If lattice energy = hydration energy, no heat
exchange. In such cases, temperature has little effect
on solubility.
500
Example: NaCl, Li2SO4 (solubility fairly increases slope = KH
or no change with rise in temperature).
™ Pressure has no effect on solubility for solid- liquid
solutions. 0.01 0.02
Mole fraction of HCl in its
solution in cyclohexane

SOLUBILITY OF GASES IN LIQUID Figure: Plot of p Vs X for solution of HCl in cyclohexane.

(iii) The KH value of a gas is different in different solvents and
SOLUTIONS it increases with the increase in temperature.
Henry’s law deals with effect of pressure on the solubility of gas. (iv) Higher the value of KH of a gas, lower will be its solubility.
Statement (v) Plot of p Vs X is a straight line passing through the origin
with slope equal to KH
The solubility of a gas in a liquid at a given temperature is directly
proportional to the partial pressure at which it is dissolved. Limitation of Henry’s Law
Let X = Mole fraction of gas at a given temperature as a Henry’s law is valid only for following conditions:
measure of its solubility. (i) The pressure of gas is not too high.

P = Partial pressure of gas in equilibrium with the (ii) The temperature is not too low.
solution. (iii) The gas should not undergo any chemical reaction with the
Then according to Henry’s law, solvent.
X ∝ P (iv) The gas should not undergo dissociation/association in
solution.
or P ∝ X
or P = KHX Application of Henry’s Law
where KH = Henry law constant. Several applications in biological and industrial phenomenon:
(i) To increase the solubility of CO2 in soft drinks and soda
water, the bottle is sealed under high pressure.
Key Note
(ii) Scuba divers must cope with high concentrations of
(i) If a mixture of gases is brought in contact with solvent, dissolved gases while breathing air at high pressure
each constituent gas dissolves in proportion to its underwater. Increased pressure increases the solubility of
partial pressure. It means Henry’s law applies to each atmospheric gases in blood. When the divers come towards
gas independent of the presence of other gas. surface, the pressure gradually decreases. This releases the
dissolved gases and leads to the formation of bubbles of
(ii) Henry’s law can also be applied by expressing the
solubility of the gas in terms of mass per unit volume. nitrogen in the blood. This blocks capillaries and creates
a medical condition known as bends, which are painful
(iii) Mass of the gas dissolved per unit volume of a solvent and dangerous to life. To avoid bends, as well as, the toxic
at a given temperature is directly proportional to effects of high concentrations of nitrogen in the blood, the
the partial pressure of a gas in equilibrium with the tanks used by scuba divers are filled with air diluted with
solution. helium (11.7% helium, 56.2% nitrogen and 32.1% oxygen).
m ∝ p, m=K×p (iii) At high altitudes, the partial pressure of oxygen is less than
where, that at the ground level. This leads to low concentrations
of oxygen in the blood and tissues of people living at high
m = mass of gas dissolved in unit volume of solvent.
altitudes or climbers. Low blood oxygen causes climbers
p = pressure of gas in equilibrium with solution. to become weak and unable to think clearly, symptoms of a
Where K is the constant of proportionality that depends condition known as anoxia.
on nature of gas, temperature and unit of pressure.
Effect of Temperature & Le-Chatelier’s Principle
Solubility of gases in liquids decreases with rise in temperature.
Characteristics of Henry’s Law Constant (KH) When dissolved, the gas molecules are present in liquid phase
(i) Unit same as those of pressure i.e. torr or bar. and the process of dissolution can be considered similar to
condensation and heat is evolved in this process. We have learnt
(ii) Different gases have different values of KH.
5 JEE (XII) Module-1 CHEMISTRY PW
that dissolution process involves dynamic equilibrium and
thus must follow Le Chatelier’s principle. As dissolution is an Sol.
exothermic process, the solubility should decrease with increase (i) We know that solubility of exothermic solutions
of temperature. decreases on increase of temperature (heating).
Therefore the given statement is true.
™ KH values for both N2 and O2 increase with increase
(ii) We know that solubility increases with increase of
of temperature indicating that the solubility of gases
temperature (heating). Therefore the given statement
increases with decrease of temperature. It is due to this
is true.
reason that aquatic species are more comfortable in
cold water rather than in warm water. (iii) (c) T, T

Train Your Brain Concept Application

2. The boiling point of C6H6, CH3OH, C6H5NH2 and

Example 4. If N2 gas is bubbled through water at 293K, how
C6H5NO2 are 80º, 67°, 180° and 210°C respectively.
many millimoles of N2 gas will be dissolved in 1L of water.
Which will show highest vapor pressure at room
Assume partial pressure of N2 = 0.987 bar. temperature?
(Henry’s Law constant for N2 at 293K is 76.48 k bar) (a) C6H6 (b) CH3OH
Sol. PN 2 = K H .X N 2 (c) C6H5 NH2 (d) C6H5 NO2
0.987 bar 3. Solubility of a substance remains unchanged on
XN = = 1.29 ´ 10-5 heating or cooling. Identify its solubility curve.
2 76480 bar
(a) (b)
1L water contains 55.5 moles of water. Let, n be the
number of moles of N2 in solution

Solubility

Solubility
n mol n
XN = »
2 n mol + 55.5mol 55.5
= 1.29 × 10–5 Temperature Temperature
∴ n = (1.29 × 10–5 × 55.5) mol (c) (d)
= 7.16 × 10–4 mol
Solubility

Solubility
= (7.16 × 10–4 × 1000) m mole
= 0.716 m mole
Example 5. Henry’s Law constant of CO2 in water at 298 K
is 5/3 k bar. If pressure of CO2 is 0.01 bar, then find its Temperature Temperature
solubility in terms of mole fraction.
4. On cooling, solubility of a substance decreases.
Sol. P = KH.X Identify its solubility curve.
or, PCO2 (g) = K H .X CO2 (a) (b)
or, 0.01 = (5/3) × 1000 × X CO2
Solubility

Solubility

∴ X CO2 = 6 × 10–6
Example 6. Identify following statement as true or false
and identify correct match.
(i) Cooling favours the solubility of exothermic solutions.
Temperature Temperature
(ii) Heating favours the solubility of endothermic solutions.
(iii) (c) (d)
(i) (ii)
Solubility

Solubility

(a) T F
(b) F T
(c) T T
(d) F F Temperature Temperature

6 JEE (XII) Module-1 CHEMISTRY PW

VAPOUR PRESSURE (b) Nature of liquid:
When a liquid is placed in a closed container, it evaporates and Vapour pressure of liquid ∝
converts into vapour. After some time, the liquid and the vapour 1
reaches equilibrium, i.e., the rate of evaporation becomes equal to The strength of intermolecular forces
the rate of condensation. At this point of time, the pressure exerted acting between molecules
by the vapours of the liquid on the surface of the liquid and on the
walls of the container is called the vapour pressure of the liquid. For example, CCl4 has higher vapour pressure because
of the weak intermolecular forces acting between its
molecules than water which has stronger intermolecular
forces acting between water molecules.

ADVANCED LEARNING
DETERMINATION OF VAPOUR PRESSURE
OF A LIQUID
Does the vapour pressure of a liquid depend on the volume of the Experimental determination of vapour pressure involves two
vessel, shape of the vessel or the amount of liquid taken in the methods:
container? a. Static method:
These questions can be answered by involving the concept of 1. Barometric method
equilibrium constant. For the equilibrium, liquid  vapour, 2. Manometric method
the KP for the equilibrium would be equal to Pvap, since b. Dynamic method or Ostwald Walker method (to be
this is the pressure exerted by the vapours at equilibrium discussed later):
(by definition). We know Kp depends only on temperature. This
means that vapour pressure of a liquid will also be constant at a VAPOR PRESSURES OF IMMISCIBLE
given temperature and will depend only on temperature and the LIQUIDS
nature of liquid.
Since immiscible liquids are mutually insoluble, addition of one
Therefore, it should be noted that the vapor pressure of a liquid liquid to the other does not affect the properties of either liquid.
is independent of whatever be the volume or shape of the vessel, Hence each will behave as if the other were not present.
or the amount of liquid in it (assuming it to be more than the Consequently, in a mixture of two immiscible liquids, each
minimum amount required). will exert the vapor pressure corresponding to the pure liquid
Moreover, on addition of any substance to the liquid, as long as the at the given temperature, and the total vapor pressure above the
substance does not dissolve in the liquid and completely covers mixture will be the sum of the vapor pressures of the two pure
the surface, the vapour pressure of a liquid remains constant. constituents, namely,
Factors affecting vapour pressure P = P°A+ P°B
(a) Temperature: Vapour pressure ∝ Temperature where P is the total vapor pressure, and P°A, P°B are the vapor
pressures of the two pure liquids A and & B. If we let X′A and
X′B be the mol fractions of the two constituents in the vapor,
Vapour pressure

then P°A = X′AP, P°B = X′BP, and hence,

PA° X ¢A P X ¢A
= =
PB° X ¢B P X ¢B
But X′A = nA/(nA + nB), and X′B = nB/(nA + nB), where nA and
Temperature
nB are the number of moles of A and B in any given volume of
Higher the temperature, higher will be the vapour pressure
because a larger fraction of molecules have sufficient vapor.
kinetic energy to escape. The total vapor pressure exerted by a mixture of immiscible
liquids at a given temperature is the sum of the vapor pressures
ADVANCED LEARNING
of the individual components at that temperature.
Clausius-Clapeyron Equation The boiling point of any system is the temperature at which the
P DH é 1 1 ù total vapor pressure is equal to the confining pressure. Since
2.303 log 2 = ê - ú
P1 R ë T1 T2 û the two liquids together can reach any given total pressure at a
lower temperature than either liquid alone, it must follow that
Here P1 and P2 are V.P. at temperature T1 and T2 respectively
any mixture of two immiscible liquids must boil at a temperature
and ∆H = Enthalpy of evaporation / vapourisation and is always
positive, thus if T1 < T2, then P1 < P2. lower than the boiling point of either of the two liquids.

7 JEE (XII) Module-1 CHEMISTRY PW

 PT = PA + PB
Ratio of Distillate to Residue Compositions
The relative proportions of the two liquids in the distillate can
be calculated on the basis that the number of moles of each Here
component present in the vapour phase is proportional to its PAº > PBº i.e.
vapour pressure. If n′A and n′B are the number of moles of the (A is more volatile than B)
components A and B in the vapour phase, then
n′A/n′B = p°A/n°B … (i)
If wA and wB represent the actual masses of the two
Relation between Mole Fraction of
components in the distillate and MA and MB their respective Vapour Phase and PT
molecular masses, then Eq. (i) may be written as XA′ = mole fraction of A in vapour above the liquid / solution.
XB′ = mole fraction of B in vapour above the liquid / solution.
w A n A M A PAº M A w pº M
= = º Þ A = Aº A Dalton’s law for gaseous mixture,
w B n B M B pB M B w B pB M B
PA = X'A PT
Weight fraction of A in the distillate is
Raoult’s law when liquid and vapour are in equilibrium
wA= PAoMA/ ( PAoMA + PBoMB) PA = XAPAº = X'A PT
PB = XBPBº = X'B PT
RAOULT‘S LAW FOR MIXTURE OF TWO
X 'A PT X 'B PT
VOLATILE LIQUIDS X A + XB = 1 =
PAo
+
PBo
1 X X¢
= °A + °B
PT PA PB

RAOULT’S LAW IS A SPECIAL CASE OF

HENRY’S LAW
mole fractions of A and According to Henry’s law
B in liquid solution
p = kHx ...(i)
Figure: Let A, B be two volatile liquids where, x is the mole fraction of the gas (solute) in the solution
which is in contact with the gas above having pressure equal to p.
Partial pressure of A = PA and Partial pressure of B = PB
Here, it may be mentioned that Raoult’s law holds good for ideal
According to Raoult’s law (experimentally) solutions in which both solute and solvent are volatile liquid. In
PA ∝ XA the above example, we can regard p as the vapour pressure of
volatile solute (gas) when it is present to the extent of x2 mole
PA = XAPAº
fraction in the solution.
Here PAº & PBº are vapour pressure of pure liquid A & B at
Applying Raoult’s law
given temperature
Similarly. PB ∝ XB P = p°x ...(ii)
∴ PB = XBPBº where p° is the vapour pressure of pure solute (dissolved gas in
the present case) at the temperature of the solution.
if PAº > PBº Eqs. (i) and (ii) are quite similar. In fact, both become identical if

∴ A is more volatile than B kH becomes equal to p°. Therefore. Raoult’s law can be taken as a

∴ boiling point of A < boiling point of B special case of Henry’s law.

∴ According to Dalton’s law,
IDEAL SOLUTIONS
PT = PA + PB = XAPAº + XBPBº
The mixtures which follow Raoult’s law at all temperatures
Graphical Representation and at all compositions are known as ideal mixtures / ideal
solution.
PA= XAPAº and PB = XB PBº
Characteristic of an ideal solution:
PT = XAPAº + XB PBº
™ Ideal solution are obtained only when the forces of attraction
PT = XAPAº + (1 – XA) PBº = ( PAº – PBº ) XA + PBº between the liquid molecules are exactly of same nature and
PT = (1 – XB) PAº + XBPBº = ( PBº – PAº ) XB + PAº almost of same magnitude.

8 JEE (XII) Module-1 CHEMISTRY PW

 A --- A » A --- B » B --- B
For Ideal Solution
™ ∆Hmix = 0, ∆Vmix = 0
™ ∆Smix = + ve
™ ∆Gmix = – ve TA° Vapour
Example:
Liquid
(1) Benzene + Toluene. TB°

pressure
Vapour
(2) n-Hexane + n-Heptane.
a′′
(3) C2H5Br + C2H5Ι.
(4) Chlorobenzene + Bromobenzene; (b) (a) (a′)
cB = 1
cA = 1 Mole Distillate
Residue from fraction richer in B
™ In case of ideal solution the vapour phase is richer with distillation of a Mixture composition
more volatile component (i.e., the one having relatively ‘a’ richer in A
greater vapour pressure) in comparison to that in
solution phase. Graph for boiling point vs composition for ideal solution
™ Point 1: Mixture composition (a) is taken richer in a
component (A)
ADVANCED LEARNING ™ Point 2: Mixture composition (a) boils at Tb(a) temperature
™ Point 3: Distillate (a′) of (a) is the mixture composition
CONDENSATION OF VAPOURS OF
richer in component B.
SOLUTION ™ Point 4: ‘b’ is residue during distillation of mixture
composition ‘a’.
When the vapours of ideal solution (containing liquids
Hence such solution can be successfully solution separated
A and B) is condensed , the composition of liquids A and B in into pure A and pure B.
the condensate remains same. The vapours over condensate Successive distillation of a′ give a′′ and then finally pure B,
can again be recondensed and the composition of A and B in as distillate.
condensate (2) remains same as it was in vapour phase over
condensate (1).

Train Your Brain

Vapour
Example 7: The vapour pressures of ethanol and methanol
are 44.5 mm Hg and 88.7 mm Hg respectively. An ideal
Liquid
solution is formed at the same temperature by mixing 60 g
of ethanol with 40 g of methanol. Calculate the total vapour
Solution Condensate(1) Condensate(2) pressure (in mm Hg) of the solution and mole fraction of
methanol in the vapour.
FRACTIONAL DISTILLATION
60
Repeated boiling of any mixture of two volatile liquids, as Sol. Number of moles of C2H5OH = = 1.304
46
in fractional distillation, always results in the separation of
40
the mixture. The liquid in the mixture with the lower boiling Number of moles of CH3OH = = 1.25
32
point (and higher vapour pressure) comes off the top of the
1.304
fractionating column, while the other liquid is left in the Mole fraction of C2H5OH = = 0.5107
1.304 + 1.25
flask.
1.25
Mixtures which behave like this with both components obeying Mole fraction of CH3OH = = 0.4893
1.304 + 1.25
(or nearly obeying) Raoult's law are called ideal mixtures and
Partial pressure of C2H5OH = XA.PºA
can be completely separated by fractional distillation.
= (0.5107 × 44.5) mm Hg
Examples are: liquid air (a mixture of nitrogen and oxygen) and
petroleum. = 22.73 mm Hg

9 JEE (XII) Module-1 CHEMISTRY PW

 Partial pressure of CH3OH = X B .PBº  
(ii) Here, the solute is CH2Cl2
402 ´ 13 134
= (0.4893 × 88.7) mm Hg X ¢CH 2Cl2 = =
494 494
= 43.40 mm Hg
540 ´ 23 360
Total vapour pressure of solution = (22.73 + 43.40) mm Hg
X ¢CH3Cl = =
494 494
= 66.13 mm Hg
Mole fraction of CH3 OH in vapour n¢CH 2Cl2 nsolute 134
now, = = = 0.372
Partial pressure of CH3OH n¢CHCl3 nsolvent 360
=
Total vapour pressure Example 10: At 25°C, the vapour pressure of methyl
alcohol is 96.0 torr. What is the mole fraction of CH3OH in
43.40
= = 0.6563 a solution in which the (partial) vapor pressure of CH3OH
66.13 is 23.0 torr at 25°C?
Example 8: Liquids ‘A’ and ‘B’ form ideal solution. At PCH3OH 23
Sol. XCH OH = 0 = = 0.24
80°C, PAº = 0.4 bar and PBº = 0.8 bar. All the vapour above 3 PCH3OH 96
the liquid solution containing equal moles of both the liquids
at equilibrium is collected in another empty vessel and
condensed. Now, the condensate is heated to 80°C and all
the vapours above the liquid solution at equilibrium is again Concept Application
collected in another empty vessel and condensed. What is
the mole fraction of ‘B’ in new condensate? 5. Two liquids A and B form an ideal solution. At 300K, the
vapour pressure of a solution containing 1 mole of A and
Sol. For the first condensate,
3 mole of B is 550 mm Hg. At the same temp, if one more
n X Y X . Pº n Pº mole of B is added to the solution, the vapour pressure
B = B ; B = B Bº = B ´ Bº
nA X A YA X A .PA nA PA of the solution is increased by 10 mm Hg. Determine the
For second condensate, vapour pressure of A and B in the pure state (in mm Hg).
2
nB¢¢ X ¢¢B YB¢ æ YB ö PBº n æ Pº ö
= ; =ç ÷ = B ´ ç Bº ÷÷
nA¢¢ X ¢¢A YA¢ è YB ø PAº nA çP
è A ø
2
NON-IDEAL SOLUTIONS
x æ 0.8 ö
= .ç ÷ = 4  [As moles of both liquids are equal] In terms of Raoult’s law, a non-ideal solution is defined as the
x è 0.4 ø
one which does not obey Raoult’s law. These are divided into two
nB¢¢ nB¢¢ 4n ¢¢A types as explained below:
= 4 Þ n ¢¢B = 4n ¢¢A ⇒ X B = =
nA¢¢ nA¢¢ + nB¢¢ nA¢¢ + 4nA¢¢
4 (1) N
 ON-IDEAL SOLUTIONS SHOWING POSITIVE
∴ Mole fraction of B = = 0.8 DEVIATIONS
5
Example 9: Vapour pressure of CH3 Cl and CH2 Cl2 are These can be defined on the basis of
540 mm Hg and 402 mm Hg respectively. 101 g of CH3 Cl (a) Molecular interactions
and 85 g of CH2Cl2 are mixed together. Determine A non-ideal solution showing positive deviation is defined as the
(i) The pressure (in mm Hg) at which the solution one in which the intermolecular forces of interactions between
starts boiling. the molecules is weaker than the interactions found in either of
(ii) Molar ratio of solute vs solvent in vapour phase in the pure components.
equilibrium with solution.
Sol. (i) Solution boils when atmospheric pressure becomes (b) Thermodynamics
equal to vapour pressure. A non-ideal solution is defined as the one in which there is a slight
∴ Boiling atmospheric pressure = vapour pressure increase in volume on mixing and absorption of heat takes place
°
= PA X A + PB X B
° on mixing. ∆Vmixing = positive, ∆Hmixing = positive.

æ 2ö æ 1ö In general, the trend of molecular interactions in the molecules are

Total pressure = ç 540 ´ ÷ + ç 402 ´ ÷ hydrogen bonding > dipole−dipole interactions > van der Waal’s
è 3 ø è 3ø
interaction (for compounds having similar molar mass). Hence,
= (360 + 134) mm Hg = 494 mm Hg replacement of any one of the stronger interactions by the weaker
one would result in positive deviation.
10 JEE (XII) Module-1 CHEMISTRY PW
 ™ PTexp. > ( XAPºA + XBPºB) For one intermediate composition, the total vapour pressure of
such a solution will be the highest and the boiling point will be
A - - - -A the lowest. This solution acquires the property of boiling at a
™ or > A ---- B
B - - - -B constant temperature and its composition in liquid phase remains

→
unchanged because the composition in vapour phase is also same
Weaker force of attraction as in liquid phase. Liquid mixtures, which boil out without any
™ ∆Hmix = +ve
change in the composition are called azeotropes or azeotropic
mixtures. In case of positive deviation from Raoult's law, we get
™ ∆Vmix = +ve (1L + 1L, then final volume of solution is greater
minimum boiling azeotrope.
then 2L)
™ ∆Smix = +ve (2) N
 ON-IDEAL SOLUTIONS SHOWING NEGATIVE
™ ∆Gmix = –ve DEVIATIONS
Example: These can be defined on the basis of
(i)Acetone (dipole) + carbon disulphide (van der Waals) (a) Molecular Interactions
(ii)Acetone (dipole) + ethyl alcohol (hydrogen-bond)
Solutions in which forces of interactions between the components
(iii)Acetone (dipole) + benzene (van der Waals) is stronger than that in between both the pure components are the
(iv) Carbon tetrachloride (van der Waals) + Chloroform ones showing negative deviation from Raoult’s law.
(dipole)
(b) Thermodynamics
(v) Methyl alcohol + water
In the case of such solutions, a slight decrease in volume and
(vi) Ethyl alcohol + water
evolution of heat takes place on mixing i.e.,
In the given examples from (i) to (vi), the molecules possessing ∆Vmixing = negative and ∆Hmixing = negative
weaker interactions get in between the molecules possessing
™ PT exp < XAPºA + XBPºB
stronger one and thereby reducing the overall interactions.
A - - - -A
In examples (v) and (vi), though both the components have ™ and <A ------ B
hydrogen bonding but the extent of hydrogen bonding in B - - - -B

→
the case of water is more than that in the case of alcohols
(methanol or ethanol) or alcohol-water. stronger force of attraction.
Graphical Representation ™ ∆Hmix = –ve
V.P. = max. ™ ∆Vmix = –ve (1L+1L, then final volume of solution is less
B.P. = min. then 2L)
P> ∆Smix = +ve
PA + ™
PB
Vapour pressure

™ ∆Gmix = –ve

P Examples
>
P AX
0 A A
P (i) Chloroform (dipole) + acetone (dipole)
> B 0X
PA (ii) Acetone(dipole) + aniline (weak hydrogen bond)
B
(iii) Pyridine (van der Waal’s) + Acetic acid (hydrogen
XA = 0 Mole fraction XA = 0 bonding)
XB = 1 XB = 1 (iv) HCl + water
(v) HNO3 + water
Cl
CH3
(vi) acetone + chloroform; Cl C H O C
Cl CH3
In the above examples from (i) to (ii), the weak interactions are
being replaced by strong hydrogen bonds, thus reducing the
escaping tendency of the molecules. In case of (iii), one of the
constituents is basic while the other is acidic. Whereas (iv) and
(v) involve an aqueous solution of a strong volatile acid such as
a halogen acid. In these cases, non-volatile ions are formed as a
Positive deviation from Raoult’s law result of interaction of ions of the acid with water.

11 JEE (XII) Module-1 CHEMISTRY PW

Graphical Representation ADVANCED LEARNING
V.P. = min. Point 1: Here when mixture composition ‘a’ is boiled, then
the distillate (a′) becomes more rich in ‘B’ but, successive
B.P. = max.
distillation of a′ will finally lead to compositions (‘d’) where
Vapour pressure

+ PB vapour phase and liquid phase compositions are same. Hence

P < PA d(D) is a solution which cannot be separated into pure A and B.
0XA
Hence it is a –ve boiling azeotropic mixture. But the residue ‘b’
P > PA
A > PA becomes richer in ‘A’.
P
B 0X Point 2: When mixture composition ‘c’ is boiled then distillate
A is (c′) richer in ‘A’ but successive distillation makes it to
composition d(D) i.e. –ve boiling azeotropic mixture.
XA = 0 Mole fraction XA = 0 The distillate is ‘e’ richer in (B) component
XB = 1 XB = 1 B) –ve Deviation solutions (+ve Boiling azeotropic)
When temperature versus composition are drawn for the
solutions showing –ve deviation the graph obtained is

Maximum boiling D
azeotropic mix V V
P
TB°
(Azeotropic composition)
TA° L
X d
a′ a b c c′

Negative deviations from Raoult’s law XA = 1 d e XB = 1

Mole fraction
For one intermediate composition, the total vapour pressure of (Graph of Boiling point Vs composition for non-ideal solution
such a solution will be the lowest and the boiling point will be the –ve deviation)
highest. This solution acquires the property of boiling at a constant
Point 1: When mixture composition ‘a’ is taken, then on boiling.
temperature and its composition remains unchanged because the
composition in vapour phase is also same as in liquid phase. (i) Distillate a′ is obtained which is richer in component A
In case of negative deviation from Raoult's law, we get maximum (ii) Residue is ‘b’
boiling azeotrope. Successive distillation of ‘b’ leads to azeotropic
solution D. (+ve boiling azeotropic mixture)
ADVANCED LEARNING (iii) Successive distillation of a′ will lead to pure (A)
TEMPERATURE VERSUS COMPOSITION Point 2: When mixture composition c is taken and boiled.
(i) Distillate is c′ which is richer in component B and
CURVES successive distillation of distillates lead to solution
For non Ideal Solutions becoming pure ‘B’
A) +Deviation solution or (–ve boiling azeotropes) (ii) The residue of ‘c’ is ‘e’ successive distillation of ‘e’
makes the residue richer in ‘D’ which is +ve boiling
When temperature versus composition graphs are drawn
azeotropic mixtures.
for +ve deviation solution we get

Train Your Brain

TA° Vapour
Liquid V Example 11: The boiling point of an azeotropic mixture of
TB°
water and ethanol is less than that of water and ethanol. The
Vapour L mixture shows
pressure D (a) No deviation from Raoult’s Law
e (b) Positive deviation from Raoult’s Law
b a a′ c′ (c) Negative deviation from Raoult’s Law
c cB = 1
d (d) That the solution is unsaturated
cA = 1
Mole Sol. Positive deviation is noticed, because, water-ethyl
fraction alcohol interaction is weak, hence boiling point is low.
(Graph for boiling point vs to composition for non-ideal That means higher vapour pressure. Hence, positive
solution showing +ve deviation) deviation is shown.

12 JEE (XII) Module-1 CHEMISTRY PW

 PS = PºA (1 – XB)
Concept Application PS = PºA – PºA XB

6. A non-ideal solution was prepared by mixing 30 mL PºAXB = PºA – PS (Lowering in V.P. = PºA – PS= ∆P)
chloroform and 50 mL acetone. The volume of mixture
PºA – PS DP DP
will be < ________ mL. XB = = (Relative lowering in V.P. = )
PºA PºA PºA
™ Raoult’s law: (For non – volatile solutes)
COLLIGATIVE PROPERTIES AND
CONSTITUTIONAL PROPERTIES Experimentally relative lowering in Vapour pressure = mole
fraction of the non volatile solute in solution.
Colligative Properties
The properties of the solution which are dependent on the total PºA – Ps
RLVP =
no. of solute particles or total concentration of solute particles in PºA
the solution and are not dependent on the nature of solute particle
n
i.e., shape, size, charge etc. of the particles. RLVP = XSolute =
n+N
There are 4 colligative properties of solution.
PºA n+N N
æ DP ö Þ = = 1+
Relative lowering in vapour pressure ç PºA – Ps n n
™ ÷
è Pº ø
™ Elevation in boiling point (∆Tb) (Here n = Moles of solute and N = Moles of solvent)
™ Depression in freezing point (∆Tf) PºA Pº – PºA + Ps Ps
Osmotic pressure (π) N = –1 = A =
™
n PºA – Ps PºA – Ps PºA – Ps
To be more accurate, the colligative property depends upon the Pº – Ps n PºA – Ps w M
fraction of solute and solvent particles in solution. A = ; = ×
Ps N Ps m W
RELATIVE LOWERING IN VAPOUR (Here m = Molar mass of solute and M = Molar mass of solvent)
PRESSURE (RLVP) P° - PS w M 1000 w 1000 M
A = × × = × ×
Lowering in Vapour Pressure of a Solution PS m W 1000 m W 1000
Vapour pressure of a solution of a non-volatile solute (solid solute)
P ° – Ps M
is always found to be less than the vapour pressure of pure solvent. A = (molality)× (M = molar mass of solvent)
Ps 1000
Reason
This indicates that equimolecular quantity of any non-volatile
Some of the solute molecules will occupy some surface area of
the solutions, so tendency of the solvent particles to go into the solute dissolve in same quantity of the same solvent will produce
vapour phase is slightly decreased because A is volatile solvent the equal lowering of vapour pressure. Hence, this is colligative
and B is non-volatile solute. Vapour pressure of B = 0 (i.e. PºB = 0)
property.
because B is non-volatile.

Key Note

™ (PºA– PA) is the lowering of vapour pressure whereas

æ PA0 - PA ö
çç 0 ÷÷ is called relative lowering of vapour
è PA ø
pressure.
™ Mole fraction of solute
Vapour pressure of pure solvent - Vapour pressure of solution
=
Vapour pressure of pure solvent

Figure: PS < PoA ™ Vapour pressure of solutions having non volatile solute
From Raoult’s law will always be less than that of solvent, however vapour
PS = PºA XA + PºB XB pressure of solutions with volatile solute may be more or
less than that of pure solvent.
PS = PºA XA  (As PºB = 0, So PºB XB= 0)

13 JEE (XII) Module-1 CHEMISTRY PW

 ADVANCED LEARNING
Train Your Brain
Dynamic Method
Measurement of Relative Lowering of Vapour Pressure Example 12: 1 mole of a non-volatile solute is dissolved
using Ostwald and Walker’s Method in 2 moles of water. The vapour pressure of the solution
Ostwald and Walker apparatus is the arrangement to calculate relative to that of water is ________
º
relative lowering in vapour pressure. In this method, a stream Psolvent - Psolution 1 1
Sol. = =
º
of dry air is bubbled successively through (i) the solution Psolvent 1+ 2 3
(ii) the solvent and (iii) a reagent which can absorb the vapours
P 1 2
of the solvent. Generally solvent is water and thus the reagent solution = 1 - =
º
Psolvent 3 3
used is anhydrous CaCl 2.
Example 13: The vapour pressure of pure liquid solvent A
is 0.80 atm. When a nonvolatile substance B is added to the
solvent its vapour pressure drops to 0.60 atm. What is the
mole fraction of component B in the solution?
Sol.
PA0 - Psol 0.80 - 0.60
CaCl 2-U-tube XB = = = 0.25
PA0 0.80

The first three bulbs contain a weighed amount of the solution Example 14: Dry air is passed through a solution containing
and the next three bulbs contain a weighed amount of the pure 20 g. of an organic non-volatile solute in 250 ml of water.
Then the air was passed through pure water and then
solvent. A weighed amount of anhydrous CaCl2 is taken in the
through a U-tube containing anhydrous CaCl2. The mass
U tube. All the bulbs must be kept at the same temperature and
lost in solution is 26 g and the mass gained in the U-tube is
dry air must be bubbled gradually to ensure that it gets saturated 26.48 g. Calculate the molar mass (in g/mol) of the organic
with the vapours in each bulb. solute. (dsolution = 1 g/ml)
The dry air, as it passes through the solution, takes up an amount Sol. Loss in mass in solution = 26g
of vapour which is proportional to the vapour pressure of the Gain in mass in U-tube = 26. 48 g
solution at the prevailing temperature. This moist air when Therefore, Loss in mass in solvent = 0.48 g
passes through water (solvent), it takes up a further amount of Loss in mass of solvent p° - p
vapour which is proportional to the difference in vapour pressure We know that = =
gain in ma ss of U - tube P°
of pure solvent and vapour pressure of the solution.
(i) Loss in mass of solution ∝ vapour pressure of solution 0.48 P° - P
= = mole fraction of solute in the solution
∝ PS 26.48 P°

(ii) Loss in mass of solvent ∝ vapour pressure of pure 0.48 n solute n solute
= =
solvent - vapour pressure of solution ∝ Pº – PS 26.48 n solute + n solvent n solute + 250 / 18
(iii) Loss in mass of solution + loss in mass of solvent 250 ´ 0.48
∝ PS + Pº – PS ∝ Pº nsolute =
18 ´ 26
This moist air is then passed through CaCl2 taken in U-tube. 25 ´ 18 ´ 26
Msolute = = 78 g / mol
The CaCl2 tubes are weighed at the end of the experiment. The 250 ´ 0.48
gain in mass should be equal to the total loss in mass of the
Example 15: Dry Air was passed through a solution
solution and solvent bulbs which is proportional to Pº. containing 20 gm. of substance in 100 gm of water and then
o through pure water. The loss in mass of the solution was 2.9
i.e., loss in mass of solvent = P – PS gm and that of pure water was 0.06 gm. Calculate the molar
gain in mass of CaCl 2 Po mass (in g/mol) of the substance.
Important. When a dry gas is bubbled slowly through a pure Sol. Ps ∝ loss in mass of solution
liquid or a solution, the gas gets saturated with respect to that p0 – Ps ∝ loss in mass of pure water
liquid or solvent. e.g. If V litres are bubbled through a pure Then, Ps ∝2.9
liquid having molecular weight M and a vapor pressure P° at p0 – Ps ∝ 0.06
that temperature, T, and if this leads to a reduction in w grams or, P0 ∝ (2.9 + 0.06) ∝ 2.96 = 3
of the liquid then P° = wRT/MV

14 JEE (XII) Module-1 CHEMISTRY PW

 Normal Boiling Point
Now, The temperature at which boiling occurs when the external
p0 - ps 0.06 pressure is exactly 1 atm is called the normal boiling point of the
= = x2
p0 3 liquid. (Tb)
n2 n w / M 2 w 2 / M1 20 ´ 18 H2O()  H2O(g) ∆H = +ve
» 2 = 2 = = 100 ´ M
n1 + n 2 n1 w1 / M 2 w1 / M 2 2
Standard Boiling Point
or, M2 = 180 gm/mole
Example 16: The vapour pressure of water at 293 K is The temperature at which boiling occurs when the external
17.54 mm of Hg and the vapour pressure of solution at pressure is exactly 1 bar is called the standard boiling point of
the liquid. (Tb)
the same temperature is 17.35 mm of Hg. The solution is
prepared by dissolving 100 gm. of non-volatile solute in one Elevation in Boiling Point
litre water. Calculate the molar mass (in g/mol) of solute. Since vapour pressure of solution is smaller than the vapour
Dp pressure of pure solvent at any temperature, hence to make it
Sol. = X2
p10 equal to Pext, we have to increase the temperature of solution by
some amount in comparison to that of pure solvent.
Now, P10 = 17.54 mm of Hg
Dp = (17.54 – 17.35) = 0.19 mm of Hg 1atm

Vapor Pressure
n2 n w / M2
Now, X 2 » » 2 = 2 Psolv Tb

(atm)
n1 + n 2 n1 n1
Psoln
wt. of solute in gm 1000 bpsolv bpsoln
n1 = Mole wt. of solvent = 18 = 55.56 Temperature (°C)

w2 = mass of solute in gm = 100 gm Graphical Representation

M2 = Molar mass of solute
0.19 100 1
= ´
17.54 M 2 55.56
⇒ M2 = 166 g/mol

Concept Application
™ If solution are dilute then BE and CD can be approximated
as straight lines.
7. The vapour pressure of pure benzene at a certain temp
is 640 mm Hg. A non-volatile solid weighing 2.175 g ∴ ∆ABE and ∆ACD will be similar. Using property of
is added to 39.0 g of benzene. The vapour pressure of similar triangles, we can write
solution is 600 mm Hg. What is molecular weight AB AE DTb1 DP1
= ⇒ =
(in g/mol) of solid substance? AC AD DTb2 DP2
8. Vapour pressure of solution containing 6 gm of ∴ ∆Tb α ∆P
non-volatile solute in 180 gm of water is 20 Torr.
n
If 1 mole of water is further added, then the vapour DTb µ DP µ
pressure increases by 0.02 Torr. Calculate vapour N
pressure (in Torr) of pure water and molecular weight n w´M
∴ DTb µ = (for a given solvent P° and M = constant)
of non-volatile solute? N m´ W
9. In Ostwald and Walker’s Apparatus, if the loss in wt. w K´w
DTb µ or DTb =
of solution is 6 unit and loss in wt of solvent is 3 unit, m´ W m´ W
then calculate the mole fraction of the solute.
ìïTbs ® b × p × of solution
∆ Tb = TbS – Tb° í o
ïîTb ® b × p × of solvent
ELEVATION IN BOILING POINT (∆Tb)
w
Boiling Point of a Liquid If = 1 mole and W = 1000 gm, then ∆Tb = Kb
m
The temperature at which vapour pressure of a liquid becomes
equal to the external pressure present at the surface of the liquid is K
∴ = Kb (Molal elevation constant or Ebullioscopic
called boiling point of liquid at that pressure. 1000 constant)

15 JEE (XII) Module-1 CHEMISTRY PW

 w 1000 For water, Tf = 273 K and Lfusion = 80 cal/gm
∆Tb = × × Kb
m W 2 ´ 273 ´ 273
Kf = = 1.86 K kg mol–1
∴ ∆Tb = molality × Kb ∴ ∆Tb ∝ molality 1000 ´ 80
Hence, elevation in boiling point (∆Tb) is a colligative property. ™ Now, at freezing point or below temperature only solvent
molecules will freeze, no solute molecules will be present in
Using thermodynamics the solid formed (solid phase will only contain pure solvent).
RTb 2 ™ From room temperature to the state of freezing point of
™ Kb =
1000× L vap solution, we will always assume that the molality of solution
will remain same but if the temperature of solution goes
∴ LVap = latent heat of vapourisation in cal/g or J/g
below its freezing temperature, then some solvent will freeze
R = 2 cal mol–1 K–1 or 8.314 J mol–1 K–1. suddenly to change the molality of solution, and the molality
Tb = boiling point of liquid (in kelvin) of remaining solution increases.
Unit of Kb = K kg mol–1
Key Note
RTb2 M
Kb =
1000 ´ DH vap DTb(1) K b(1)

∆Hvap – molar enthalpy of vapourisation in cal/mole or J/mole (i) Also = when concentration is same but
DTb(2) K b(2)
Here, M is molecular wt. of solvent solvent different
æ DH vap ö DTb(1) m(1)
Lvap = ç ÷ =
è M ø (ii) DT m when solvent is same but concentration
b(2) 2

different
DEPRESSION OF FREEZING POINT (∆Tf)
DTb(1) M o(2)
Freezing Point (iii) DT =
b(2) M o(1) ⇒ (Mo = Molar mass of solute) when
Temperature at which vapour pressure of solid phase becomes solvent is same and amount of solute is same
equal to vapour pressure of corresponding liquid phase is called
freezing point of liquid.
ANTIFREEZE SOLUTIONS
Normal Freezing Point Water is used in radiators of vehicles as cooling liquid.t If the
The temperature at which the liquid/solution is in equilibrium vehicle is to be used at high altitudes where temperature is sub-
with its solid state at an external pressure of 1 atm is called normal zero. water would freeze in radiators. To avoid this problem. a
freezing point of the liquid. (Tf) solution of ethylene glycol in water is used in radiators which will
lower the freezing point lower than zero.
H2O()  H2O(s) ∆H = –ve
Kb, Kf for various Solvents (k.kg mol– 1)
Standard Freezing Point Solvent B.P. Kb F.P. Kf
The temperature at which the liquid/solution is equilibrium with Acetic acid 118.1°C 2.93 17°C 3.9
its solid state at an external pressure of 1 bar is called standard Benzene 80.2°C 2.53 5.4°C 5.13
freezing point of the liquid. (Tf)
Water 100°C 0.53 0ºC 1.86
Graphical Representation

Train Your Brain

Pressure
Vapor

Example 17: The boiling point of pure acetone is 56.38ºC. When

0.707 g of a compound is dissolved in 10 g of acetone, there
™For dilute solutions, BE and CD can be assumed to be straight is b.p. elevation to 56.88°C, what is the M.W. (in g/mol)of the
lines. compound? (K b(CH CO CH ) ) = 1.72 K kg mole–1
3 3
∴ using similar triangles ∆Tf a ∆P
Sol. ∆ Tb = Kb × m
∴ ∆Tf = Kf . molality
0.707 1000
™ Kf = molal depression constant = cryoscopic constant = (56.88 – 56.38) = 1.72 ´ ´
MB 10
RTf 2 RTf 2 M
Kf = = ∴ MB = 243.2 g/mol
1000 ´ Lfusion 1000 ´ DH fusion

16 JEE (XII) Module-1 CHEMISTRY PW

 Example 18: If freezing point of a solution prepared Concept Application
from 1.25 g of non electrolyte and 20g water is
10. Pure benzene freezes at 5.45°C. Solution containing
271.9 K, then molar mass of the solute (in g/mol) will be
7.24 g C 2H 2Cl 4 in 115.3 g benzene was observed
(Kf (H2O) = 1.86 K kg mol–1) (Tf° = 273.15 k)
to freeze at 3.55°C. What is molal freezing point
Sol.   Tf = 271.9 K (in °C/m) of benzene.
  w = 1.25 g, W = 20 g, Kf = 1.86
∆ Tf = Tºf – Tf = 273.15 – 271.9 = 1.25 K

OSMOSIS AND OSMOTIC PRESSURE
w OSMOSIS: Osmosis is defined as the spontaneous flow of

DT f = ´ 1000 ´ K f
m´ W solvent molecules through semipermeable membrane from pure
w ´ 1000 ´ K f solvent side to the solution side or from a dilute solution to the

∴ m=
DT f ´ W concentrated solution.

1.25 ´ 1000 ´ 1.86

m= = 93 g/mol.
1.25 ´ 20

Example 19: 18 g glucose (C6H12O6) is dissolved in

1 kg of water in a saucepan. At what temperature (in kelvin)
will the water boil (1.013 bar pressure)? Kb(H2O) (Tb° =
373.15)= 0.52 K kg mol –1.
w B ´ 1000
Sol. ∆ Tb = Kb ×
mB ´ w A
18 ´ 1000
∆ Tb = 0.52 ×
180 ´ 1000
OSMOTIC PRESSURE (p)– When a solution is separated from
Tb–T0 = 0.052 the pure solvent with the help of a semipermeable membrane.
Tb – 373.15 = 0.052 There occurs the flow of solvent molecules from the pure solvent
to the solution side. The flow of solvent molecules from a
Tb = 373.15 + 0.052 = 373.202 K
region of higher concentration of solvent to the region of
Example 20: A 0.5 percent aqueous solution of Potassium lower concentration of solvent is termed as the phenomenon
chloride was found to freeze at 0.24°C. Calculate the Van’t of osmosis. This also happens when two solution of different
Hoff factor and degree of dissociation of the solute at this concentra­tions are separated by a semipermeable membrane.
concentration (kf for water is 1.86). As a result of osmosis a pressure is developed which is
termed as osmotic pressure. It is defined as.
i ´ 1000k f w
Sol. DTf = (1) The excess hydrostatic pressure which builds up as a result
W.M
of osmosis is called osmotic pressure.
i ´ 1000 ´ 0.5 ´ 1.86 (2) The external pressure which must be applied on the solution
0.24 =
100 ´ 74.5 side in order to just stop the flow of the solvent molecule
0.24 ´ 100 ´ 74.5 into the solution side through semipermeable membrane.
i= = 1.923;
1000 ´ 0.5 ´ 1.86 (3) Osmotic pressure of a solution is equal to the negative
pressure which must be applied to the sol­vent in order to
i = 1 + ( n –1 ) α
just stop the osmosis.
1.923 = 1 + ( 2 –1 ) α ⇒ osmotic pressure = hydrostatic pressure
1.923 = 1 + α
p = hdg
α= 1.923 – 1 = 0.923
h = increase in level in the tube of unit cross section.
or α = 0.923 or 92.3 % d = density of solution,
g = acceleration due to gravity

17 JEE (XII) Module-1 CHEMISTRY PW

 OR
ISOTONIC OR ISO-OSMOTIC SOLUTION
Solutions which have the same osmotic pressure are termed
isotonic or iso-osmotic solutions.
p1 = p2 i.e., C1ST = C2ST; C1 = C2
If two such solutions are separated by a semipermeable membrane,
there will be net zero transference of solvent from one solution to
the other.
0.85% NaCl solutions is found to be isotonic with blood, while
0.9% NaCl solution is isotonic with human RBCs.
Van’t Hoff law for a dilute solution:
(i) When placed in water or hypotonic solutions, cell swell and
The osmotic pressure (p) of a solution is directly proportional to burst (haemolysis).
its concentration(C) when the temperature is kept constant.
(ii) When placed in hypertonic solutions, the fluid from the
Gay Lussac – Van’t Hoff law – p V = nST plant cells comes out and thus the cells contract in size
Here, p = Osmotic pressure (plasmolysis). e.g. When excess of fertilizers (like urea) are
V = Volume of solution (in lit.)
applied, plasmolysis takes place and plants dry up (wilt).
n = No. of moles of solute
S= Molar solution constant (0.082 lit atm K–1 mol–1) Hypotonic and Hypertonic Solutions
T = Temperature (in K) A solution having lower osmotic pressure then other solution is
n said to be hypotonic with respect to other solution.
p = ST or p = CST
V A solution having higher osmotic pressure than other solution
n is said to be hypertonic with respect to other solution.
[ C = = molar concentration of solution]
V
Important: Osmotic pressures can be determined quite accurately, REVERSE OSMOSIS (R.O.)
hence it is used in the determination of molecular weights of large
If external pressure greater than osmotic pressure is applied on the
proteins and similar substances.
solution side, the flow of solvent molecules can be made to proceed
from solution side towards pure solvent side, i.e., in reverse direction
SEMIPERMEABLE MEMBRANE of the ordinary osmosis.
™ A membrane which allows the passage of solvent molecules
but not that of solute. Reverse osmosis is used for the desalination of sea water for
e.g. Copper ferrocyanide Cu2[Fe(CN)6]; getting fresh drinking water.
The most frequently used semipermeable membrane in
laboratory is that of copper ferrocyanide, Cu2[Fe(CN)6] Train Your Brain
because it is very strong and can withstand very high
pressure. Remember that semipermeable membrane of
Cu2[Fe(CN)6] does not work in non-aqueous solution Example 21: A cane sugar solution has an osmotic pressure
because it gets dissolved in non-aqueous solvents. Other of 2.46 atm at 300 K. What is the molar concentration of
synthetic semipermeable membrane is that of calcium the solution?
phosphate. Natural semipermeable membranes are n
Sol. π V = nST or p = ST = CST
parchment paper, cell walls, pig’s bladder, skin surrounding V
white of an egg, membrane surrounding RBCs etc.
p 2.46
or C = = = 0.1 M
Key Note ST 300 ´ 0.0821

(a) Exosmosis is the outward flow of water from a

cell containing an aqueous solution through a Concept Application
semipermeable membrane, e.g. grape in NaCl solution.
(b) Endosmosis is the inward flow of water into a 11. What is the osmotic pressure (in atm) of 12% w/v
cell containing an aqueous solution through a solution of cane sugar (molecular weight 342) at 17°C.
semipermeable membrane, e.g. grape in water.
12. A solution containing 8.6 g urea in one litre solution was
™ If a number of solutes are present in the solutions and found to be isotonic with 0.5% (weight/volume) solution
p1, p2, p3 etc. are their individual osmotic pressures, then of an organic, non-volatile solute at same temperature. The
Total osmotic pressure = p1 + p2 + p3 + ..... molecular weight (in g/mol) of the solute is ______

18 JEE (XII) Module-1 CHEMISTRY PW

ABNORMAL COLLIGATIVE PROPERTIES where n = x + y = total sum of no. of cations and anions given by
1 molecule of solute.
It has been observed that difference in the observed and calculated
molecular masses of solute is due to association or dissociation of Observed colligative property is proportional to observed number
solute molecules in solution. It results in a change in the number of solute particle = (1 – α + nα).
of particles in solution.
1 - a + na
i=
Association of solute particles 1
The formation of a bigger molecule by the union of two, three i = 1 + (n – 1)α
or more solute molecules is called association. Let ‘n’ simple
molecules combine to give an associated molecule as: where α is the degree of dissociation of solute
non polar For strong electrolytes:
¾¾¾¾
n( X ) ¬¾¾¾ ¾®( X ) n
solvent if α = 1 or 100 % ⇒ then, i = n
As a result, the total number of particles in solution becomes less Example: NaCl, n = 2 ⇒ i = 2, for α = 100 %
than the number of molecules initially dissolved in the solution and K2SO4, n = 3 ⇒ i = 3, for α = 100 %
hence the colligative properties will have lower value. Example: K4[Fe(CN)6], n = 5 ⇒ i = 5, for α = 100 %
As the molar mass of solute is inversely proportional to the For α = 50%, i = 1 + (n – 1) α = 3
colligative properties, so the molar mass of solute will be greater
than theoretical value. Van’t Hoff factor and degree of association: The fraction of
the total number of molecules of the substance which is present
Dissociation of solute molecules:
as associated molecules is known as the degree of association.
Molecules of electrolytes undergo ionization or dissociation in
ionizing solvents to give two or more particles in solution. For nA ® [A]n
Initially 1 0
example, AB ionizes in solution to give two particles. a
ionizing
After association (1 - a)
¾¾¾® A+ + B –
AB ¬¾¾¾ n
solvent

This dissociation results in an increase in the total number of Total number of solute particles after association
particles, and therefore the value of colligative properties of such æ aö
solutions will be higher. = ç1 - a + ÷ mol
è nø
As the colligative properties are inversely related to molecular
weight, so the molecular weight of ionizable solute will be less Observed C.P. µ observed number of solute particles
than the theoretical value. æ aö
Van’t Hoff factor (i) : Van’t Hoff in 1886 introduced a factor called =ç1 - a + ÷
è nø
Van’t Hoff factor (i). The Van’t Hoff factor (i) is defined as
a
Number of solute particles after dissociation / association 1- a +
i= i= n ⇒ i = 1- a + a
Number of solute particles before dissociation / association 1 n
observed colligative property α = Degree of association
i= ,
Normal colligative property n = Number of solute particles which are associated.
1
Normal or actual molecular weight (calculated ) If α = 100% or 1 or α is not specified ⇒ i =
i= n
observed molecular mass (experimental )
In case of association of solute particles in solution, the observed Key Note
molecular weight of solute being more than the normal, the value
of factor i, is less than unity, while for dissociation the value of i ™ One mole of a solute like glucose, cane sugar, urea, etc.
is greater than unity because the observed molecular weight has when dissolved in 1000 g of water depresses the freezing
lesser value than normal molecular weight. point of water by 1.86ºC. However, solution of one
Van’t Hoff factor and degree of dissociation: The fraction of mole of NaCl or BaCl2 in 1000 g of water depress the
the total number of molecules which dissociates in the solution freezing point of water by 3.72ºC (2 × 1.86) and 5.58ºC
into simple ions or molecules is called the degree of dissociation. (3 × 1.86) respectively because each molecule of NaCl
A x By ® xA y + + yBx - and BaCl2 dissociates to give 2 (Na+ & Cl–) and three
Initially 1 0 0 (Ba2+ and 2Cl–) ions respectively and each ion behaves
After dissociation (1 - a) xa ya as a particle in itself. Thus, among the 0.1 M solution
of the various substances like cane sugar, NaCl, BaCl2,
Total number of solute particle = 1 – α + xα+ yα Al2(SO4)3, etc. the colligative effect will be maximum in
After dissociation = 1 – α + (x + y) α Al2(SO4)3 solution giving 5 ions per molecule.
= (1 – α + nα) mol
19 JEE (XII) Module-1 CHEMISTRY PW
 ™The ideal solutions relations can be modified in
Similarly, there are certain substances which associate when
abnormal solution as given below:
dissolved in a particular solvent. Hence the molecular weight
of such substances as determined with the help of colligative Dp
0 = i x 2 , DTb = i Kb m
properties will be more than the theoretically calculated p1
value from the molecular formula. For example, the observed DTf = i kf m and p = i CRT
molecular weight of acetic acid when dissolved in benzene ™ The value of i is taken as one when solute is non
is found to be 118 which is nearly double the value (60) electrolyte e.g. glucose, sucrose, urea etc.
calculated from its molecular formula, CH3COOH. This is ™ All the 4 colligative properties are calculated by formula,
due to the fact that acetic acid, in benzene, does not exist as only for solution containing non-volatile solutes in a
CH3COOH but as a dimer, i.e. (CH3COOH)2. dilute solution.

ABNORMAL MOLECULAR MASSES Train Your Brain

The molecular mass of a solute is inversely proportional to its
concentration or value of colligative properties. Example 22: A 5% solution of anhydrous CaCl2 at 0°C
(i) The extent of dissociation and colligative property: developed 15 atm osmotic pressure. What is the degree of
dissociation of CaCl2.
A solute which dissociates completely or partially in solution
makes available more particles than would otherwise be present in Sol. 5 g of CaCl2 is present in 100 mL, so 111 g (MW of
solution and therefore, a colligative property shows an increased 100 ´ 111
CaCl2) will be present in = 2.22 litre
effect. For example, molecular masses obtained of strong acids, 5 ´ 1000
bases and salts are much less than their normal values. As an Now, π V = ST { n = 1}
example, one particle of potassium chloride on dissociation in
0.082 ´ 273 22.47
water gives two particles, K+ and Cl– and therefore, the molecular or p = = = 10.09 atm
mass obtained by a colligative property is half of its normal 2.22 2.22
molecular mass. We know that Van’t Hoff factor
K + Cl(s)
-
+ nH 2 O ¾¾ +
® K (aq) +
+ Cl(aq) observed colligative property 15
i= =
1 mol 1 mol 1 mol Normal colligative property 10.09
(ii) The extent of association and colligative property: i -1
CaCl2 → Ca2+ + 2Cl–, n = 3 and a = or
A solute that associates in solution provides less particles n -1
that would otherwise be present in solution and therefore, the 15
-1
colligative property shows the decreased effect. For example, 10.09 4.91
a= =
benzoic acid in benzene is found to have molecular mass which is 3 -1 10.09 ´ 2
just twice its normal molecular mass. = 0.2433 or 24.33%
It is found that compounds which are capable of forming Example 23: Molal elevation constant for water is
hydrogen bonds, e.g., phenols, carboxylic aids, alcohols: because 0.52 K/m. 0.1 m solution of NaCl will boil at _____°C?
of association show decreased effect of colligative property. Sol. If van’t Hoff factor is i, then
∆Tb = i. Kb. m (for NaCl, i = 2)
O H O
∆Tb = 2 × 0.52 × 0.1 = 0.104
H5C6 C6H5
O H O ∆Tb = TbS – Tb° ⇒ 0.104 = TbS – 100
0.104 + 100 = TbS ⇒ 100.104 = TbS
A dimer of benzoic acid
∴ B. P. of solution is 100. 104°C
Key Note

Experimental value of colligative property

™ i=
Calculated value of this property when the solution behaves ideally Concept Application
(DTb )obs (DTf )obs (Dp / p1º )obs pobs M cal
= = = 13. 19.5 g CH2FCOOH is dissolved in 500 g water. The
™ (DTb )cal (DTf )cal = (Dp / p1º )cal pobs M obs
depression in freezing point of water observed is 1.0ºC.
Where M is the molar mass of solute.
Calculate the van’t Hoff factor and dissociation constant
™ Knowing , the observed molar mass and the Van’t Hoff factor,
of CH2 FCOOH. kf(H2O) = 1.86 K kgmol– 1
i, the degree of dissociation, α can be easily calculated.

20 JEE (XII) Module-1 CHEMISTRY PW

 Aarambh (Solved Examples)

1. If 20 mL of 0.5 M Na2SO4 is mixed with 50 mL of (c) 5.852 g/mL

0.2 M H2SO4 and 30 mL of 0.4 M Al2(SO4)3 solution. (d) 1.288 g/mL
Calculate [Na+], [H+], [Al3+], and [SO42–]. [Assuming  (Lakshya JEE Chemistry M-1
100% dissociation]
Sol. Let V = 1 lt, then moles of solute = 6.9
 (Lakshya JEE Chemistry M-1)
wt. of solute = 6.9 × 56 gm
moles
Sol. Molarity = M solute
volume % by mass = × 100
M solution
(i) Na2SO4 → 2Na+ + SO42– 6.9 ´ 56
So, = ´ 100 = 30
10 m mol d ´ 1000
— 20 10 d = 1.288 g/mL
Total volume = 100 mL Therefore, option (d) is the correct answer.
20 4. The density of 3M solution of Na2S2O3 is 1.25 g mL–1.
\ [Na+] = = 0.2 M
100 Calculate.
(ii) H2SO4 → 2H+ + SO42– (a) The % by weight of Na2S2O3
10 m mol (b) Mole fraction of Na2S2O3
— 20 10  (Lakshya JEE Chemistry M-1
Total volume = 100 mL Sol. (a) mass of solution = 1000 × 1.25 = 1250 gm
20 mass of Na2S2O3 = 3 × 158 = 474
[H+] = = 0.2 M
100 474
% (w/w) = × 100 = 37.92
1250
(iii) Al2(SO4)3 → 2Al3+ + 3SO42–
Therefore, 37.92 is the correct answer.
12 m mol
— 24 36 3
(b) X Na 2S2O3 = = 0.065.
Total volume = 100 mL 3 + 43.11
1250 - 474
24 Mole of water solvent = = 43.11
[Al3+] = = 0.24 M 18
100
Therefore, 43.11 is the correct answer.
(iv) Total m mol of SO42– = m.m of SO42– from (Na2SO4 + H2SO4 5. Calculate molality of aqueous urea solution which has
+ Al2(SO4)3) = (10 + 10 + 36) = 56 Xurea = 0.2.
Total volume = 100 mL (a) 15.99 (b) 13.88
(c) 10.99 (d) 19.76
10 + 10 + 36 56
[SO42–] = = = 0.56 M  (Lakshya JEE Chemistry M-1
100 100
Sol. Xu + Xw = 1
2. Calculate molality of 1.2 M H2SO4 solution. If its density
Xw = 1–0.2 = 0.8
(ρ) = 1.4 g/mL?
(a) 0.936 (b) 0.562 Let total moles = 1
(c) 0.386 (d) 0.425 nu = 0.2
 (Lakshya JEE Chemistry M-1 nw = 0.8
wwater = 0.8 × 18 = 14.4
1.2 ´ 1000
Sol. Molality = = 0.936 Number of moles of solute
1000 ´ 1.4 -1.2 ´ 98 Molality (m) =
Weight of solvent (kg)
Therefore, option (a) is the correct answer.
3. A 6.90 M solution of KOH in water has 30% by weight of 0.2
= = 13.88
KOH. Calculate density of solution (in g/mL). 14.4 / 1000
(a) 9.345 g/mL Therefore, option (b) is the correct answer.
(b) 2.445 g/mL
21 JEE (XII) Module-1 CHEMISTRY PW
 6. 10 gm of a solute is dissolved in 80 gm of acetone. Vapour
pressure of this solution = 271 mm of Hg. If vapour pressure
of pure acetone is 283 mm of Hg, then calculate molar mass
of solute?
(a) 173 g/mol (b) 163 g/mol
(c) 143 g/mol (d) 183 g/mol
ice
 (Lakshya JEE Chemistry M-1
P o – Ps w M
Sol. = × solute
Ps m W (a) 900 gm (b) 600 gm
283-271 10 58 (c) 800 gm (d) 700 gm

Þ = ×
271 m 80  (Lakshya JEE Chemistry M-1
m = 163 g/mol. 0.1
Sol. ∆Tf = 0.2 = Kf × × 1000 … (i)
Therefore, option (b) is the correct answer. 1000
7. 1 L of aq. solution containing 60 g urea having density = 0.1
1.060 gm/mL is found to have ∆Tb = 0.5ºC. If temperature
∆Tf = 2 = Kf × × 1000 … (ii)
wt. of solvent
of this solution increases to 101.5ºC, then calculate amount
of water which must have gone in vapour state upto this on dividing eqn. (i) by (ii) we get,
point. [Given: Kb = 0.5 K kg mol–1 for water] wt. of solvent 0.2
= .
(a) 666.67 g (b) 999.97 g 1000 2
(c) 777.77 g (d) 888.87 g weight of remaining H2O is 100 gm and weight of ice
 (Lakshya JEE Chemistry M-1 formed is 900 gm.
Sol. Mass of solution = 1.060 × 103 = 1060 gm Therefore, option (a) is the correct answer.
mass of solvent = mass of solution – mass of solute 9. If 200 mL of 0.1 M urea solution is mixed with 300 mL of
w = 1060 – 60 = 1000 g 0.2 M glucose solution at 300 K, then calculate osmotic
∆Tb = i × Kb × m pressure due to solution.
n (a) 4.84 atm (b) 5.74 atm
m = × 1000 (c) 6.74 atm (d) 3.94 atm
W (g )
 (Lakshya JEE Chemistry M-1
60 / 60
m = × 1000 C1V1 + C2 V2
1000 Sol. Cnet =
V1 + V2
m = 1
Now, π = Cnet RT

∆Tb = i × Kb × m

p = (0.04 + 0.12) × 0.0821 × 300 = 3.94 atm.
0.5 = i × 0.5 × 1
Therefore, option (d) is the correct answer.
i = 1
10. An aqueous solution of glucose boils at 100.01°C. The
If temp. of solution increases, let w is wt. of water gone in
molal elevation constant for water is 0.5 K mol–1 Kg. The
vapour state
number of molecules of glucose in the solution containing
∆ Tb = TbS – Tb° = 101.5 – 100 = 1.5
100 g of water is

∆Tb = i × Kb × m (a) 6.022 × 1023 (b) 6.022 × 1022
60 (c) 12.046 × 1020 (d) 12.046 × 1023
1.5 = 1 × 0.5 × × 1000
60(1000 - w)  (Lakshya JEE Chemistry M-1
⇒ Wwater = 666.67 g DTb 0.01
Sol. ∆Tb = Kb.m Or m = = = 0.02 mole Kg–1 of water
Therefore, option (a) is the correct answer. Kb 0.5
8. 1000 gm H2O have 0.1 mole urea and its freezing point So, the number of moles of glucose in 100 g of water
is – 0.2ºC and now it is freezed upto – 2ºC, then how much 0.02 ´ 100
amount of ice (in g) will form? = = 0.002 moles of glucose
1000
= 0.002 × 6.022 × 1023 = 2 × 6.023 × 1020
Therefore, option (c) is the correct answer.

22 JEE (XII) Module-1 CHEMISTRY PW

 11. What is the percent by mass of iodine needed to reduce the (a) 23.14K kgmol– 1 (b) 30.14K kgmol– 1
freezing point of benzene to 3.5°C? The freezing point and
(c) 55.14K kgmol– 1 (d) 44.14K kgmol– 1
cryoscopic constant of pure benzene are 5.5°C and 5.12
 (Lakshya JEE Chemistry M-1
K/m respectively.
(a) 9.01% (b) 6.01% 20 / 65 20 ´ 1000
(c) 8.01% (d) 7.01% Sol. Molality of solid solution m = 80
=
65 ´ 80
 (Lakshya JEE Chemistry M-1 1000
Sol. ∆Tf = Tf0 – Tf = Kf . m
DTf = 1357 – 1268 = 89 = kf × m
5.5°C – 3.5°C = 5.12 × m
89 89 ´ 65 ´ 80
2 or, k f = = = 23.14k kgmol- 1
m= = 0.39 molal m 20 ´ 1000
5.12 Therefore, option (a) is the correct answer.

∴ Mass of iodine needed for 1000g of benzene 14. Molal elevation constant Kb for water is 0.52 K/m. 0.1 molal
= m × molecular mass of iodine I2 solution of NaCl will boil at
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg (a) 100.52°C (b) 100.052°C

∴ 1000g + 99.06g solution contains 99.06g I2 (c) 101.04°C (d) 100.104°C
99.06g ´ 100  (Lakshya JEE Chemistry M-1
100g solution contains = 9.01% Sol. If vant Hoff factor is i, then
1099.06g
DTb = i Kb.m (for NaCl i = 2)
Therefore, option (a) is the correct answer.
= 2 × 0.52 × (0.1) = 0.104.
12. The B.P of chloroform was raised by 0.325 K when 0.5 gm of
a compound was dissolved in 35 gm of chloroform. Calculate And, so the boiling point of solution will be 100.104°C.
the molar mass of the compound (Kb for chloroform = Therefore, option (d) is the correct answer.
3.9 K.kg/mole) 15. A solution is prepared by dissolving 26.3g of CdSO4 in
(a) 181.5 gm/mole (b) 171.4 gm/mole 1000g water. The depression in freezing point of solution
(c) 192.7 gm/mole (d) 199.6 gm/mole was found to be 0.284K. Calculate the Van’t Hoff factor. The
cryoscopic constant of water is 1.86K kg mol–1.
 (Lakshya JEE Chemistry M-1 (a) 1.21 (b) 3.41
(c) 4.77 (d) 7.44
0.5 / M 0.5 ´ 1000
Sol. Molality of Solution, m ==  (Lakshya JEE Chemistry M-1
35 35 M
1000 Sol. Molecular mass (CdSO4) = 112.4 +32 + 4 × 16 = 208.4 g/mol
Where M is the molar mass of compound. Molality CdSO4
Mass CdSO 4
Now DTb = Kbm =
Molecular mass CdSO 4 ´ Mass solvent in kg
0.5 ´ 1000 26.3g
or, 0.325 = 3.9 ´ = 0.216m
35 M æ 1000 ö
(208.4g / mol) ´ ç kg ÷
or, M = 171.4 gm/mole è 1000 ø
Therefore, option (b) is the correct answer. DTf 0.284 K
DTf = i.Kf.m or i = = = 1.21
13. A brass sample composed of 20% Zinc and 80% copper by K f m 1.86K / m ´ 0.126m
mass melts at 1268K. Pure copper melts at 1357K. What is Therefore, option (a) is the correct answer.
the molal freezing point constant for copper?

“Resilience is not about

avoiding stress but
learning to thrive in it.”

23 JEE (XII) Module-1 CHEMISTRY PW

 Board Level Problems

SINGLE CORRECT TYPE QUESTIONS (b) Water will move from side (B) to side (A) if a pressure
greater than osmotic pressure is applied on piston (B).
1. A 1% solution of solute 'X' is isotonic with a 6% solution
of sucrose (molar mass = 342 g mol–1). The molar mass of (c) Water will move from side (B) to side (A) if a pressure
solute 'X' is: equal to osmotic pressure is applied on piston (B).
(a) 34.2 g mol–1 (b) 57 g mol–1 (d) Water will move from side (A) to side (B) if pressure
–1 equal to osmotic pressure is applied on piston (A).
(c) 114 g mol (d) 3.42 g mol–1
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
7. Van’t Hoff factor for Na2SO4.10H2O solution, assuming
2. Low concentration of oxygen in the blood and tissues of
complete ionization is
people living at high altitudes is due to:
(a) 1 (b) 3 (c) 13 (d) 2
(a) Low temperature
 (Lakshya JEE Chemistry M-1
(b) Low atmospheric pressure
(c) High atmospheric pressure 8. We have three aqueous solutions of NaCl labelled as ‘A’,
‘B’ and ‘C’ with concentrations 0.1M, 0.01M and 0.001M,
(d) High temperature respectively. The value of van’t Hoff factor for these
 (Lakshya JEE Chemistry M-1 solutions will be in the order______.
3. Which of the following solutions would have the highest (a) i A < i B < i C (b) i A > iB > iC
osmotic pressure:
(c) i A = i B = i C (d) i A < i B > i C
M M
(a) NaCl (b) Urea  (Lakshya JEE Chemistry M-1
10 10
9. The relative lowering of vapour pressure of an aqueous
M M solution containing non-volatile solute is 0.0225. The mole
(c) BaCl2 (d) Glucose
10 10 fraction of the non-volatile solute is:
 (Lakshya JEE Chemistry M-1 (a) 0.80 (b) 0.725 (c) 0.15 (d) 0.0225
 (Lakshya JEE Chemistry M-1
4. For an electrolyte undergoing association in a solvent, the
van't Hoff factor: 10. Which of the following statements is false?
(a) is always greater than one (a) Two different solutions of sucrose of same molality
prepared in different solvents will have the same
(b) has negative value depression in freezing point.
(c) has zero value (b) The osmotic pressure of a solution is given by the
(d) is always less than one equation Π = CRT ( where C is the molarity of the
 (Lakshya JEE Chemistry M-1 solution).
(c) Decreasing order of osmotic pressure for 0.01 M aqueous
5. Henry’s law constant K of CO2 in water at 25°C is 3 × 10–2
solutions of barium chloride, potassium chloride, acetic
mol/L atm–1. Calculation the mass of CO2 present in 100 L
acid and sucrose is BaCl2 > KCl > CH3COOH > sucrose.
of soft drink bottled with a partial pressure of CO2 of 4 atm
at the same temperature. (d) According to Raoult’s law, the vapour pressure exerted
by a volatile component of a solution is directly
(a) 5.28 g (b) 12.0 g (c) 428 g (d) 528 g proportional to its mole fraction in the solution.
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
6. Consider the following figure and mark the correct option.
Piston (A) Piston (B) ASSERTION AND REASON TYPE
SPM QUESTIONS
11. Assertion : Addition of ethylene glycol to water lowers its
freezing point.
Concentrated
sodium chloride Reason : Ethylene glycol is insoluble in water due to lack
Fresh water (A) of its ability to form hydrogen bonds with water molecules.
solution in
water (B) (a) Both Assertion and Reason are true and Reason is correct
explanation of Assertion.
(a) Water will move from side (A) to side (B) if a pressure (b) Both Assertion and Reason are true but Reason is not a
lower than osmotic pressure is applied on piston (B). correct explanation of Assertion.

24 JEE (XII) Module-1 CHEMISTRY PW

 (c) Assertion is true but Reason is false. (Kb for water = 0.52 K kg mol–1)
(d) Assertion is false but Reason is true.  (Lakshya JEE Chemistry M-1
 (Lakshya JEE Chemistry M-1 16. The vapour pressure of a solvent at 283 K is 100 mm Hg.
12. Assertion: When NaCl is added to water a depression in Calculate the vapour pressure of a dilute solution containing
freezing point is observed. 1 mole of a strong electrolyte AB in 50 moles of the solvent
Reason: The lowering of vapour pressure of a solution causes at 283 K (assuming complete dissociation of solute AB).
depression in the freezing point.  (Lakshya JEE Chemistry M-1
(a) Both Assertion and Reason are true and Reason is correct
17. An aqueous solution of 2% non-volatile solute exerts a
explanation of Assertion.
pressure of 1.004 Bar at the normal boiling point of the
(b) Both Assertion and Reason are true but Reason is not a
solvent. What is the molar mass of the solute?
correct explanation of Assertion.
(c) Assertion is true but Reason is false.  (Lakshya JEE Chemistry M-1
(d) Assertion is false but Reason is true.
 (Lakshya JEE Chemistry M-1 LONG ANSWER TYPE QUESTIONS
18. (a) Ishan’s automobile radiator is filled with 1.0 kg of water.
MATCH THE COLUMN TYPE QUESTIONS How many grams of ethylene glycol (Molar mass = 62
g mol–1) must Ishan add to get the freezing point of the
13. Match the column and choose correct option
solution lowered to - 2.8 °C. Kf for water is 1.86 K kg
Vant’ Hoff factor Behaviour of compound mol–1.
(A) i=1 P. Impossible  (Lakshya JEE Chemistry M-1
(b) What type of deviation from Raoult’s law is shown by
(B) i>1 Q. Association is the solution
ethanol and acetone mixture ? Give reason.
(C) i<1 R. Dissociation in the solution  (Lakshya JEE Chemistry M-1
(D) i=0 S. No dissociation or association 19. A solution is prepared by dissolving 5 g of a non-volatile
(a) A–S, B–R, C–P, D–Q solute in 200 g of water. It has a vapour pressure of 31.84
(b) A–R, B–S, C–Q, D–P mm Hg at 300 K. Calculate the molar mass of the solute.
(c) A–S, B–P, C–R, D–Q (Vapour pressure of pure water at 300 K = 32 mm Hg)
(d) A–S, B–R, C–Q, D–P  (Lakshya JEE Chemistry M-1
 (Lakshya JEE Chemistry M-1 20. (a) What is the value of ‘i’ for Al2(SO4)3 when it is completely
14. Match the law given in column-I with expressions given in dissociated?
column-II.  (Lakshya JEE Chemistry M-1
Column-I Column-II (b) Calculate the boiling point of a solution prepared by
(i) Raoult’s law (a) DTf = Kfm adding 15.00 g of NaCl to 250 g of water. (Kb = 0.512 K
(ii) Henry’s law (b) Π = CRT kg mol–1 and molar mass of NaCl = 58.44 g mol–1)
(iii) Elevation of (c) p = x1p1o + x2p2o  (Lakshya JEE Chemistry M-1
boiling point 21. (a) What is the value of ‘i’ when solute is associated and
(iv) Depression in (d) ∆Tb = Kbm dissociated ?
freezing point
 (Lakshya JEE Chemistry M-1
(v) Osmotic pressure (e) p = KHx
(b) Calculate the freezing point of an aqueous solution
(a) (i)–(c), (ii)–(e), (iii)–(d), (iv)–(a), (v)–(b) containing 10.50 g of MgBr2 in 200 g of water. (Molar
mass of MgBr2 = 184, Kf = 1.86 K kg mol–1)
(b) (i)–(e), (ii)–(c), (iii)–(a), (iv)–(a), (v)–(d)
 (Lakshya JEE Chemistry M-1
(c) (i)–(d), (ii)–(a), (iii)–(c), (iv)–(e), (v)–(b)
(d) (i)–(b), (ii)–(d), (iii)–(e), (iv)–(a), (v)–(c) 22. (a) Outer shells of two eggs are removed. One of the egg is
placed in pure water and the other is placed in saturated
 (Lakshya JEE Chemistry M-1
solution of NaCl. What will be observed and why?
SHORT ANSWER TYPE QUESTIONS  (Lakshya JEE Chemistry M-1
15. Calculate the boiling point of the solution when 4 g of MgSO4 (b) A solution prepared by dissolving 8.95 mg of a gene
(M = 120 g mol–1) was dissolved in 100 g of water, assuming fragment in 35.0 ml of water has an osmotic pressure
MgSO4 undergoes complete ionization.

25 JEE (XII) Module-1 CHEMISTRY PW

 of 0.335 ton at 25ºC. Assuming the gene fragment is a depending on the solute’s identity. (Jayawardena, J. A. E. C.,
non-electrolyte, determine the molar mass? Vanniarachchi, M. P. G. & Wansapala, M. A. J. (2017).
 (Lakshya JEE Chemistry M-1 Freezing point depression of different Sucrose solutions and
coconut water.)
23. (a) Define reverse osmosis.
I. When a non volatile solid is added to pure water it
 (Lakshya JEE Chemistry M-1 will:
(b) Why are aquatic species more comfortable in cold water (a) Boil above 100°C and freeze above 0°C
in comparison to warm water ?
(b) Boil below 100°C and freeze above 0°C
 (Lakshya JEE Chemistry M-1 (c) Boil below 100°C and freeze below 0°C
(c) A solution containing 2 g of glucose (M = 180 g mol–1) (d) Boil above 100°C and freeze below 0°C
in 100 g of water is prepared at 303 K. If the vapour  (Lakshya JEE Chemistry M-1
pressure of pure water at 303 K is 32.8 mm Hg, what
II. Colligative properties are:
would be the vapour pressure of the solution ?
(a) Dependent only on the concentration of the solute and
 (Lakshya JEE Chemistry M-1
independent of the solvent’s and solute’s identity.
24. (a) At the same temperature, CO2 gas is more soluble in (b) Dependent only on the identity of the solute and the
water than O2 gas. Which one of them will have higher concentration of the solute and independent of the
value of KH and why? solvent’s identity.
 (Lakshya JEE Chemistry M-1 (c) Dependent on the identity of the solvent and solute and
thus on the concentration of the solute.
(b) How does the size of blood cells change when placed in
(d) Dependent only on the identity of the solvent and the
an aqueous solution containing more than 0.9% (mass/
concentration of the solute and independent of the
volume) sodium chloride? solute’s identity.
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
(c) 1 molal aqueous solution of an electrolyte A2B3 is 60% III. Assume three samples of juices A, B and C have glucose as
ionized. Calculate the boiling point of the solution. the only sugar present in them. The concentration of sample
(Given: Kb for H2O = 0.52 K kg mol–1) A, B and C are 0.1M, .5M and 0.2 M respectively. Freezing
 (Lakshya JEE Chemistry M-1 point will be highest for the fruit juice:
(a) A
CASE STUDY BASED QUESTIONS (b) B
Read the passage given below and answer the following questions: (c) C
(d) All have same freezing point
25. Boiling point or freezing point of liquid solution would
 (Lakshya JEE Chemistry M-1
be affected by the dissolved solids in the liquid phase. A
soluble solid in solution has the effect of raising its boiling IV. Identify which of the following is a colligative property:
point and depressing its freezing point. The addition of non- (a) Freezing point (b) Boiling point
volatile substances to a solvent decreases the vapor pressure (c) Osmotic pressure (d) All of the above
and the added solute particles affect the formation of pure  (Lakshya JEE Chemistry M-1
solvent crystals. According to many researches the decrease
in freezing point directly correlated to the concentration
of solutes dissolved in the solvent. This phenomenon is
expressed as freezing point depression and it is useful for
several applications such as freeze concentration of liquid
food and to find the molar mass of an unknown solute in
the solution. Freeze concentration is a high quality liquid
food concentration method where water is removed by
forming ice crystals. This is done by cooling the liquid
food below the freezing point of the solution. The freezing
point depression is referred as a colligative property and it is
proportional to the molar concentration of the solution (m),
along with vapour pressure lowering, boiling point elevation,
and osmotic pressure. These are physical characteristics of
solutions that depend only on the identity of the solvent
and the concentration of the solute. The characters are not

26 JEE (XII) Module-1 CHEMISTRY PW

 Prarambh (Topicwise)
CONCENTRATION TERMS Henry’s law constant?
(REVISION OF MOLE) (a) N2 (b) He

1. The amount of anhydrous Na2CO3 present in 250 mL of (c) H2 (d) CO2

0.25 M solution is  (Lakshya JEE Chemistry M-1
(a) 225 g (b) 66.25 g 9. The vapour pressure of water depends upon
(c) 6.0 g (d) 6.625 g (a) Surface area of container
 (Lakshya JEE Chemistry M-1 (b) Volume of container
2. 2.0 molar solution is obtained, when 0.5 mole solute is (c) Temperature
dissolved in
(d) All of these
(a) 250 mL solvent (b) 250 g solvent
 (Lakshya JEE Chemistry M-1
(c) 250 mL solution (d) 1000 mL solvent
10. A vessel has nitrogen gas and water vapours in equilibrium
 (Lakshya JEE Chemistry M-1 with liquid water at a total pressure of 1 atm. The partial
3. 36 g of water and 828 g of ethyl alcohol form an ideal pressure of water vapours is 0.3 atm. The volume of this
solution. The mole fraction of water in it, is vessel is reduced to one third of the original volume, at the
(a) 1.0 (b) 0.7 same temperature, then total pressure of the system is
(c) 0.4 (d) 0.1 (Neglect volume occupied by liquid water)
 (Lakshya JEE Chemistry M-1 (a) 3.0 atm (b) 1 atm (c) 3.33 atm (d) 2.4 atm
 (Lakshya JEE Chemistry M-1
4. An X molal solution of a compound in benzene has mole
fraction of solute equal to 0.2. The value of X is
V.P OF MIXTURE OF LIQUIDS
(a) 14 (b) 3.2
11. For a solution of two liquids A and B it was proved that
(c) 4 (d) 2
P = XA (PA0 - P B0 )+ PB0 . The solution is
 (Lakshya JEE Chemistry M-1
5. 4.0 gm of NaOH is contained in one decilitre of solution. Its (a) Ideal (b) Non-ideal
molarity would be (c) Semi ideal (d) None of these
(a) 4 M (b) 2 M  (Lakshya JEE Chemistry M-1
(c) 1 M (d) 1.5 M 12. 1 mole of n-heptane (V.P. = 92 mm of Hg) was mixed
 (Lakshya JEE Chemistry M-1 with 4 moles of n-octane (V.P = 31 mm of Hg), the vapour
pressure of the resulting ideal solution is
HENRY’S LAW AND BASICS OF VAPOUR (a) 46.2 mm of Hg (b) 40.0 mm of Hg
(c) 43.2 mm of Hg (d) 38.4 mm of Hg
PRESSURE
 (Lakshya JEE Chemistry M-1
6. Calculate the solubility of gaseous oxygen in water at a
13. Two liquids A and B form an ideal solution, What is the
temperature of 293 K when the partial pressure exerted by
vapour pressure of solution containing 2 moles of A and
O2 is 1 bar. (Given: KH for O2 34840 bar L mol–1) 3 moles of B at 300 K? [Given: At 300 K, Vapour pressure
(a) 2.87 × 10–5 mol/L (b) 4 × 10–4 mol/L of pure liquid A (PºA ) = 100 torr, Vapour pressure of pure
(c) 2.87 × 10–4 mol/L (d) 5 × 10–4 mol/L liquid B (PºB ) = 300 torr]
(a) 200 torr (b) 140 torr (c) 180 torr (d) 220 torr
 (Lakshya JEE Chemistry M-1
 (Lakshya JEE Chemistry M-1
7. Solubility of gas in water is x g/cm3 at 300 K temperature.
14. The vapour pressure of pure benzene and toluene are 160
When temperature increases to 400 K, then solubility of gas and 60 torr respectively. The mole fraction of toluene in
(a) Increases (b) Decreases vapour phase in contact with equimolar solution of benzene
1 and toluene is
(c) Remain same (d) x (a) 0.50 (b) 0.60 (c) 0.27 (d) 0.73
2
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1

8. Which one of the following gases has the lowest value of

27 JEE (XII) Module-1 CHEMISTRY PW

DIFFERENCE BETWEEN IDEAL AND solvent
 (Lakshya JEE Chemistry M-1
NON-IDEAL SOLUTION
23. The vapour pressure lowering caused by the addition of 100 g
15. Which pair from the following will not form an ideal of sucrose (molecular mass = 342) to 1000 g of water if the
solution? vapour pressure of pure water at 25ºC is 23.8 mm Hg, is
(a) CCl4 + SiCl4 (b) H2O + C4H9OH (a) 1.25 mm Hg (b) 0.125 mm Hg
(c) C2H5Br + C2H5I (d) C6H14 + C7H16 (c) 1.15 mm Hg (d) 00.12 mm Hg
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
16. An ideal solution is that which 24. According to Raoult’s law, the relative lowering of vapour
(a) Shows positive deviation from Raoult’s law pressure of a solution of non-volatile substance is equal to
(b) Shows negative deviation from Raoult’s law (a) Mole fraction of the solvent
(c) Has no connection with Raoult’s law (b) Mole fraction of the solute
(d) Obeys Raoult’s law (c) Weight percentage of a solute
 (Lakshya JEE Chemistry M-1 (d) Weight percentage of a solvent
 (Lakshya JEE Chemistry M-1
17. Which property is shown by an ideal solution?
25. The vapour pressure of water at 20°C is 17.54 mm Hg.
(a) It follows Raoult’s law (b) ∆Hmix = 0
When 20 g of a non-ionic, substance is dissolved in 100 g
(c) ∆Vmix = 0 (d) All of these of water, the vapour pressure is lowered by 0.30 mm Hg.
 (Lakshya JEE Chemistry M-1 What is the molecular weight (in g/mol) of the substance?
18. When two liquids A and B are mixed then their boiling (Do not consider solution as dilute)
points becomes greater than both of them. What is the (a) 210.2 (b) 206.88
nature of this solution? (c) 215.2 (d) 200.8
(a) Ideal solution  (Lakshya JEE Chemistry M-1
(b) Non-ideal solution with positive deviation
(c) Non-ideal solution with negative deviation ELEVATION OF BOILING POINT AND
(d) Normal solution DEPRESSION OF FREEZING POINT
 (Lakshya JEE Chemistry M-1 26. The latent heat of vapourisation of water is 9700 Cal/mole
19. All form ideal solution except and if the b.p. is 100° C, ebullioscopic constant of water is
(a) C2H5Br and C2H5I (b) C6H5Cl and C6H5Br (a) 0.513°C/molal (b) 1.026°C/molal
(c) C6H6 and C6 H5CH3 (d) C2H5I and C2H5OH (c) 10.26°C/molal (d) 1.832°C/molal
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
20. An azeotropic solution of two liquids has boiling point 27. If 0.15 g of a non-volatile solute dissolved in 15 g of solvent
lower than either when it has boiling point higher by 0.216°C than that of the pure
(a) Shows a negative deviation from Raoult’s law solvent, then molecular weight (in g/mol) of the substance
(b) Shows no deviation from Raoult’s law (molal elevation constant for the solvent is 2.16° K kg/mol) is
(c) Shows positive deviation from Raoult’s law (a) 1.01 (b) 10 (c) 10.1 (d) 100
(d) Is saturated  (Lakshya JEE Chemistry M-1
28. Mark the correct relationship between the boiling points of
 (Lakshya JEE Chemistry M-1
very dilute solutions of BaCl2, (T1) and KCl (T2), having
the same molarity
RELATIVE LOWERING IN V.P
(a) T1 = T2
21. For a solution of volatile liquids, the partial vapour pressure
(b) T1 > T2
of each component in solution is directly proportional to
(c) T2 > T1
(a) Molarity (b) Mole fraction
(d) T2 is approximately equal to T1
(c) Molality (d) Normality
 (Lakshya JEE Chemistry M-1  (Lakshya JEE Chemistry M-1
22. When a substance is dissolved in a solvent, the vapour 29. The molal freezing point constant for water is 1.86°C
pressure of the solvent is decreased. This results in kg mole–1. If 342 gm of canesugar (C12H22O11) are dissolved
(a) An increase in the b.p. of the solution in 1000 gm of water, the solution will freeze at
(b) A decrease in the b.p. of the solvent (a) –1.86°C (b) 1.86°C
(c) The solution having a higher freezing point than the (c) – 3.92°C (d) 2.42°C
solvent  (Lakshya JEE Chemistry M-1
(d) The solution having a lower osmotic pressure than the
28 JEE (XII) Module-1 CHEMISTRY PW
 30. The freezing point of one molal NaCl solution assuming 37. If a 0.1 M solution of glucose (mol. wt. 180) and 0.1 molar
NaCl to be 100 % dissociated in water is (molal freezing solution of urea (mol. wt. 60) are placed on the two sides of
point depression constant = 1.86 K kg mol–1) a semipermeable membrane to equal heights, then it will be
(a) – 1.86°C (b) – 3.72°C correct to say that
(c) + 1.86°C (d) + 3.72°C (a) There will be no net movement across the membrane.
 (Lakshya JEE Chemistry M-1 (b) Glucose will move across the membrane into urea
solution.
31. 1.00 gm of a non-electrolyte solute when dissolved in 50 gm
of benzene lowers the freezing point of benzene by 0.40 K. (c) Urea will flow across the membrane into glucose
solution.
Kf for benzene is 5.12 kg mol–1. Molecular mass of the
solute will be (d) Water will flow from urea solution into glucose
solution.
(a) 256 g mol–1
 (Lakshya JEE Chemistry M-1
(b) 2.56 g mol–1
38. A solution of urea contain 8.6 gm/litre (mol. wt. 60.0).
(c) 512×103 g mol–1
It is isotonic with a 5% solution of a non-volatile solute.
(d) 2.56×104 g mol–1 The molecular weight (in g/mol) of the solute will be
 (Lakshya JEE Chemistry M-1 (a) 348.9 (b) 34.89
(c) 3489 (d) 861.2
OSMOTIC PRESSURE  (Lakshya JEE Chemistry M-1
32. The concentration in gms per litre of a solution of cane sugar
39. Osmotic pressure of 0.1 M solution of NaCl and Na2SO4
(M = 342) which is isotonic with a solution containing 6
will be
gms of urea (M = 60) per litre is
(a) Same
(a) 3.42 (b) 34.2
(b) Osmotic pressure of NaCl solution will be more than
(c) 5.7 (d) 19 Na2SO4 solution.
 (Lakshya JEE Chemistry M-1 (c) Osmotic pressure of Na2SO4 solution will be more than
33. Osmotic pressure is 0.0821 atm at temperature of 300 K. NaCl.
Find concentration in mole/litre (d) Osmotic pressure of Na2SO4 will be less than that of
(a) 0.033 (b) 0.066 NaCl solution.
(c) 0.33 × 10–2 (d) 0.3  (Lakshya JEE Chemistry M-1
 (Lakshya JEE Chemistry M-1
VAN’T HOFF FACTOR
34. A 5 % solution of cane sugar (mol. wt. = 342) is isotonic
with 1 % solution of a substance X. The molecular weight 40. Which of the following will have the highest freezing point
at 1 atm pressure?
(in g/mol) of X is
(a) 0.1 M NaCl (b) 0.1 Na2SO4
(a) 34.2 (b) 171.2
(c) 0.1 M BaCl2 (d) 0.1 M glucose
(c) 68.4 (d) 136.8
 (Lakshya JEE Chemistry M-1
 (Lakshya JEE Chemistry M-1
41. Which of the following aqueous solutions containing 10 gm
35. Which statement is wrong regarding osmotic pressure (p), of solute in each case has highest B.P.?
volume (V) and temperature (T)?
(a) NaCl solution (b) KCl solution
1 (c) Sugar solution (d) Glucose solution
(a) p µ , if T is constant
V  (Lakshya JEE Chemistry M-1
(b) p ∝ T, if V is constant 42. The freezing points of equimolar solutions of glucose,
(c) p ∝ V, if T is constant KNO3 and AlCl3 are in the order of
(d) pV is constant, if T is constant (a) AlCl3 < KNO3 < Glucose
 (Lakshya JEE Chemistry M-1 (b) Glucose < KNO3 < AlCl3
36. The value of osmotic pressure of a 0.2 M aqueous solution (c) Glucose < AlCl3 < KNO3
at 293 K is (d) AlCl3 <Glucose < KNO3
(a) 8.4 atm (b) 0.48 atm  (Lakshya JEE Chemistry M-1
(c) 4.8 atm (d) 4.0 atm 43. Which of the following salt has the same value of Van’t
 (Lakshya JEE Chemistry M-1 Hoff factor (i) as that of K4 [Fe(CN)6]?

29 JEE (XII) Module-1 CHEMISTRY PW

 (a) Al2(SO4)3 (b) NaCl 45. The molecular weight of benzoic acid in benzene as determined
(c) Na2SO4 (d) Al(NO3)3 by depression in freezing point method corresponds to
(Lakshya JEE Chemistry M-1 (a) Ionization of benzoic acid

44. One mole of a solute A is dissolved in a given volume of a (b) Dimerization of benzoic acid
solvent. The association of the solute take place according (c) Trimerization of benzoic acid
to nA  An. (d) Solvation of benzoic acid
If x is the degree of association of A, then Van’t Hoff factor  (Lakshya JEE Chemistry M-1
(i) is expressed as 46. What is the freezing point of a solution containing 8.1 g
x HBr in 100 g water assuming the acid to be 90 % ionised?
(a) i =1 – x (b) i = 1 + (Kf for water = 1.86 K mole–1)
n
x (a) 0.85°C (b) – 3.53°C (c) 0°C (d) – 0.35°C
1- x +
n  (Lakshya JEE Chemistry M-1
(c) i = (d) i = 1
1
 (Lakshya JEE Chemistry M-1

Prabal (JEE Main Level)

1. Mole fraction of C3H5(OH)3 (glycerine) in a solution of pressure (in Torr) P = 254 –119 XA where XA is mole
36 g of water and 46 g of glycerine is fraction of A in mixture. Hence, PAO and PBO are (in Torr)
(a) 0.46 (b) 0.36 (a) 254, 119 (b) 119, 254
(c) 0.20 (d) 0.40 (c) 135, 254 (d) 119, 373
 (Lakshya JEE Chemistry M-1 (Lakshya JEE Chemistry M-1)
2. An aqueous solution of urea containing 18 g urea in 7. What is ratio of mole fraction of benzene (PºB = 150 torr)
1500 cm3 of solution has a density of 1.052 g/cm3. and toluene (PºT = 50 torr) in vapour phase if the given
If the molecular weight of urea is 60, then the molality of solution has a vapour pressure of 120 torr?
solution is (a) 7 : 1 (b) 7 : 3
(a) 0.2 (b) 0.192 (c) 8 : 1 (d) 7 : 8
(c) 0.064 (d) 1.2 (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1
3. What is the molarity of H2SO4 solution that has a density of 8. At 300 K. the vapour pressure of an ideal solution
containing 3 mole of A and 2 mole of B is 600 torr.
1.84 g/cc at 35°C and contains 98% by weight?
At the same temperature, if 1.5 mole of A and 0.5 mole of C
(a) 4.18 M (b) 8.14 M (non-volatile) are added to this solution, the vapour pressure
(c) 18.4 M (d) 18 M of solution increases by 30 torr. What is the value of ?
 (Lakshya JEE Chemistry M-1 (a) 940 torr (b) 405 torr
4. When 5.0 gram of BaCl2 is dissolved in water to have 106 (c) 90 torr (d) None of these
gram of solution. The concentration of solution is (Lakshya JEE Chemistry M-1)
(a) 2.5 ppm (b) 5 ppm 9. At a constant temperature, ∆S will be maximum for which
(c) 5 M (d) 5 gm L–1 of the following processes?
 (Lakshya JEE Chemistry M-1 (a) Vaporisation of a pure solvent
(b) Vaporisation of solvent from a solution containing
5. A mixture contains 1 mole of volatile liquid A non-volatile and non electrolyte solute in it.
(PAO = 100 Hg ) and 3 moles of volatile liquid B (c) Vaporisation of solvent from a solution containing
non-volatile but electrolyte solute in it.
(P O
B= 80 mm Hg ). If solution behaves ideally, the total
vapour pressure of the distillate is (d) Entropy change will be same in all the above cases.
(a) 80 mm Hg (b) 85.88 mm Hg 
(c) 90 mm Hg (d) 92 mm Hg 10. Which of the following is less than zero for ideal solutions?
 (Lakshya JEE Chemistry M-1 (a) ∆Hmix (b) ∆Gmix (c) ∆Vmix (d) ∆Smix
 (Lakshya JEE Chemistry M-1)
6. Mixture of volatile components A and B has total vapour

30 JEE (XII) Module-1 CHEMISTRY PW

11. The vapour pressures of pure liquids ‘A’ and ‘B’ are 300 (Lakshya JEE Chemistry M-1)
and 800 torr respectively at 25°C. When these two liquids 19. The vapour pressure of water at room temperature is lowered
are mixed at this temperature to form a solution in which
by 5% by dissolving a solute in it, then the approximate
mole percentage of “B” is 92, then the total vapour pressure
molality of solution is
is observed to be 0.95 atm. Which of the following is true
for this solution? (a) 2 (b) 1 (c) 4 (d) 3
(a) ∆Vmix > 0 (b) ∆Hmix < 0 (Lakshya JEE Chemistry M-1)
(c) ∆Vmix = 0 (d) ∆Hmix = 0 20. The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is 2.74.
(Lakshya JEE Chemistry M-1) The degree of dissociation is
(a) 91.3% (b) 87% (c) 100% (d) 74%
12. Consider a binary mixture of volatile liquids. If at
XA = 0.4, the vapour pressure of solution is 580 torr then the (Lakshya JEE Chemistry M-1)
O O
mixture could be [ PA = 300 torr, PB = 800 torr] 21. The vapour pressure of pure liquid A is 10 torr and at the
same temperature when 1 g of B solid is dissolved in 20 g of
(a) H2O – HNO3 (b) C6H5Cl – C6H5Br
A, its vapour pressure is reduced to 9.0 torr. If the molecular
(c) C6H6 – C6H5CH3 (d) nC6H14 – nC7H16 mass of A is 200 amu, then the molecular mass of B is
 (Lakshya JEE Chemistry M-1) (a) 100 amu (b) 90 amu
13. Which of the following mixture of liquids will form an (c) 75 amu (d) 120 amu
ideal solution?
(Lakshya JEE Chemistry M-1)
(a) C2H5OH and water
22. The vapour pressure of a solution of a non-volatile solute
(b) HNO3 and water
B in a solvent A is 95% of the vapour pressure of the pure
(c) CHCl3 and CH3COCH3
solvent at the same temperature. If the molecular weight of
(d) C6H6 and C6H5CH3 the solvent is 0.3 times the molecular weight of the solute,
 (Lakshya JEE Chemistry M-1) what is the ratio of weight of solvent to solute?
14. Which of the following mixture shows negative deviation (a) 0.15 (b) 5.7
from Raoult’s law? (c) 0.2 (d) None of these
(a) CHCl3 and acetone
(Lakshya JEE Chemistry M-1)
(b) CHCl3 and C2H5OH
(c) C6H5CH3 and C6H6 23. The vapour pressure of a dilute aqueous solution of glucose is
750 mm of mercury at 373 K. The mole fraction of solute is
(d) C6H6 and CCl4
(Lakshya JEE Chemistry M-1) 1 1
 (a) (b)
10 7.6
15. Assuming each salt to be completely dissociated, which of
the following will have the highest osmotic pressure? 1 1
(c) (d)
(a) Decimolar Al2(SO4)3 35 76
(b) Decimolar BaCl2 (Lakshya JEE Chemistry M-1)
(c) Decimolar Na2SO4
(d) A solution obtained by mixing equal volumes of 24. 1 mol each of following solutes are taken in 5 mol water.
(b) and (c) and filtering (A) NaCl (B) K2SO4
(Lakshya JEE Chemistry M-1) (C) Na3PO4 (D) Glucose
16. A complex containing K+, Pt(IV) and Cl– is 100% ionised Assuming 100% ionisation of each electrolyte, vapour
giving i = 3. Thus, complex is pressure of solutions will be in the order
(a) K2 [PtCl4] (b) K2[PtCl6] (a) D < A < B < C (b) D < C < B < A
(c) K3[PtCl5] (d) K[PtCl3] (c) C < B < A < D (d) Equal for all
(Lakshya JEE Chemistry M-1) (Lakshya JEE Chemistry M-1)
17. pH of 1 M HA (weak acid) is 2. Hence, van’t Hoff factor of 25. The vapour pressure of a solvent is decreased by 10 mm
HA is of Hgwhen a non-volatile solute was added to the pure
(a) 1.2 (b) 1.02 solvent. The mole fraction of solute in solution is 0.2, what
(c) 1.1 (d) 1.01 would be mole fraction of the solvent if decrease in vapour
pressure is 20 mm of Hg?
(Lakshya JEE Chemistry M-1)
(a) 0.2 (b) 0.4 (c) 0.6 (d) 0.8
18. In which case, van’t Hoff factor is maximum?
(Lakshya JEE Chemistry M-1)
(a) KCl, 50% ionised (b) K2SO4 40% ionised
26. The vapour pressure of a saturated solution of sparingly
(c) FeCl3 30% ionised (d) SnCl4 20% ionised
soluble salt (XCl3) was 17.20 mm Hg at 27°C. If the vapour
31 JEE (XII) Module-1 CHEMISTRY PW
 pressure of pure H2O is 17.25 mm Hg at 300 K. What is the (Kb = 0.52°C mol–1 kg)
solubility of sparingly soluble salt XCl3 in mole/Litre? (a) K3[Fe(CN)6]
(a) 4.04 × 10–2 (b) 8.08 × 10–2 (b) Fe(CN)2
(c) 2.02 × 10 –2 (d) 4.04 × 10–3
(c) K4[Fe(CN)6]
 (Lakshya JEE Chemistry M-1)
(d) Fe(CN)4
27. 0.5 M, 100 mL A and 0.2 M, 500 mL B are mixed at 27°C.
(Lakshya JEE Chemistry M-1)
Vapour pressure of pure A and pure B is 200 mm Hg and 

50 mm Hg respectively at 27°C. The ratio of partial pressures 34. A solution of x moles of sucrose in 100 grams of water
of A and B (in vapour phase) after mixing is freezes at –0.2°C. As ice separates, the freezing point goes
(a) 2 : 1 (b) 1 : 2 (c) 2 : 3 (d) 4 : 1 down to –0.25°C. How many grams of ice would have
(Lakshya JEE Chemistry M-1) separated?
28. Which of the solutions have equal elevation in boiling point? (a) 18 grams (b) 20 grams
A. 0.1 M Na2SO4 (c) 25 grams (d) 23 grams
B. 0.1 M MgCl2 (Lakshya JEE Chemistry M-1)
C. 0.1 M C6H12O6 (glucose) 35. Elevation of boiling point of 1 molar aqueous glucose
D. 0.1 M Al(NO3)3 solution (density = 1.2 g/mL) is
(a) A and B (b) B and C (a) Kb (b) 1.20 Kb
(c) C and D (d) None of these (c) 1.02 Kb (d) 0.98 Kb
(Lakshya JEE Chemistry M-1)  (Lakshya JEE Chemistry M-1)
29. Aluminium phosphate is 100% ionised in 0.01 molal aqueous 36. Osmotic pressure of blood is 7.40 atm at 27°C. Number of
solution. Hence, ∆Tb/Kb is mol of glucose to be used per L for an intravenous injection
(a) 0.01 (b) 0.015 that is to have the same osmotic pressure as blood, is
(c) 0.0175 (d) 0.02 (a) 0.3 (b) 0.2
(Lakshya JEE Chemistry M-1) (c) 0.1 (d) 0.4
30. A 0.001 molal solution of a complex MA8 in water has the (Lakshya JEE Chemistry M-1)
freezing point of – 0.0054°C. Assuming 100% ionization of
37. A solution of glucose (C6H12O6) is isotonic with 4 g of urea
the complex salt and Kr for H2O = 1.86 K m–1, what is the
(NH2–CO–NH2) per liter of solution. The concentration of
correct representation for the complex?
glucose is
(a) [MA5] (b) [MA7]A
(a) 4 g/l (b) 8 g/l
(c) [MA6]A2 (d) [MA5]A3
(c) 12 g/l (d) 14 g/l
 (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1)
31. Which of the following option has been arranged in the order
of decreasing freezing point? 38. A solution of a substance containing 1.05 g per 100 mL was
(a) 0.05 M KNO3 > 0.04 M BaCl2 > 0.140 M sucrose > found to be isotonic with 3% by mass of glucose solution.
0.075 M CuSO4 The molecular mass (in g/mol) of the substance is
(b) 0.04 M BaCl2 > 0.140 M sucrose > 0.075 M CuSO4 > (a) 31.5 (b) 6.3
0.05 M KNO3 (c) 630 (d) 63
(c) 0.075 M CuSO4 > 0.140 M sucrose > 0.04 M BaCl2 > (Lakshya JEE Chemistry M-1)
0.05 M KNO3
39. The relationship between osmotic pressure at 273 K when
(d) 0.075 M CuSO4 > 0.05 M KNO3 > 0.140 M sucrose > 10 g glucose (P1), 10 g urea (P2) and 10 g sucrose (P3) are
0.04 M BaCl2
dissolved in 250 mL of water is
(Lakshya JEE Chemistry M-1)
 (a) P1 > P2 > P3 (b) P3 > P1 > P2
32. A 0.2 molal aqueous solution of a weak acid (HX) (c) P2 > P1 > P3 (d) P2 > P3 > P1
is 20% ionised. The freezing point of this solution is
(Lakshya JEE Chemistry M-1)
(Given: Kf = 1.86°C kg mol–1 for water) 
40. Which one of the following pairs of solution can we expect
(a) – 0.45°C (b) – 0.90°C
to be isotonic at the same temperature?
(c) – 0.31°C (d) – 0.53°C
(a) 0.1 M urea and 0.1 M NaCl
(Lakshya JEE Chemistry M-1)
(b) 0.1 M urea and 0.2 M MgCl2
33. A complex of iron and cyanide ions is 100% ionised at 1 m (c) 0.1 M NaCl and 0.1 M Na2SO4
(molal). If its elevation in b.p. is 2.08, then the complex is

32 JEE (XII) Module-1 CHEMISTRY PW

 (d) 0.1 M Ca(NO3)2 and 0.1 M Na2SO4 (c) 0.0558 K (d) 0.0744 K
 (Lakshya JEE Chemistry M-1) (Lakshya JEE Chemistry M-1)
41. FeCl3 on reaction with K4[Fe(CN6)] in aqueous solution 46. The vapour pressure of acetone at 20° C is 185 torr. When
gives blue colour. These two solutions are separated by a 1.2 g of non-volatile substance was dissolved in 100 g of
semipermeable membrane AB as shown. Due to osmosis, acetone at 20° C, its vapour pressure was 183 torr. The molar
there is mass (g mol– 1) of the substance is
0.01 M 0.01 M (a) 128 (b) 448
K4Fe(CN)6 FeCl3 (c) 32 (d) 64
(Lakshya JEE Chemistry M-1)
47. For 1 molal aqueous solution of the following compounds,
which one will show the highest freezing point?
Side X Side Y
(a) [Co(H2O)5Cl]Cl2·H2O (b) [Co(H2O)4Cl2]Cl·2H2O
(c) [Co(H2O)3Cl3]·3H2O (d) [Co(H2O)6]Cl3
SPM
(Lakshya JEE Chemistry M-1)
(a) Blue colour formation on side X 
48. A solution at 20°C is composed of 1.5 mol of benzene and
(b) Blue colour formation on side Y
3.5 mol of toluene. If the vapour pressure of pure benzene
(c) Blue colour formation on both sides of X and Y and pure toluene at this temperature are 74.7 torr and
(d) No blue colour formation 22.3 torr, respectively, then the total vapour pressure of
(Lakshya JEE Chemistry M-1) the solution and the benzene mole fraction in equilibrium
(in vapor phase) with it will be, respectively
42. The partial pressure of ethane over a solution containing
(a) 38.0 torr and 0.589 (b) 30.5 torr and 0.389
6.56 × 10–2 g of ethane is 1 bar. If the solution contains
5.00 × 10–2 g ethane, then partial pressure is ______ (c) 35.8 torr and 0.280 (d) 35.0 torr and 0.480
(Lakshya JEE Chemistry M-1)
(a) 1.312 bar (b) 1.0 bar
(c) 0.762 bar (d) 0.912 bar INTEGER TYPE QUESTION
(Lakshya JEE Chemistry M-1) 49. At 10°C, the osmotic pressure of urea solution is 500 mm
43. Two elements A and B form compounds AB2 and AB4 (both of Hg. The solution is diluted and the temperature is
are non-volatile and non-electrolyte). When dissolved in raised to 25°C, when the osmotic pressure is found to be
20.0 g of benzene, 1 g of AB2 lowers the freezing point of 105.3 mm of Hg. Determine the extent of dilution done
with original solution.
benzene by 2.3 K, whereas 1 .0 g of AB4 lowers it by 1 .3 K
[Kf (benzene) = 5.52 K mol–1 kg]. Thus, atomic masses of  (Lakshya JEE Chemistry M-1)
A and B respectively, are 50. Three particles of a solute ‘A’ associate in benzene to
(a) 120, 212 (b) 96, 28 form species (A)3. Calculate the freezing point (in °C) of
(c) 212, 120 (d) 28, 46 0.25 molal solution. The degree of association of solute
‘A’ is found to be 0.80. The freezing point of benzene is
(Lakshya JEE Chemistry M-1) 5.5°C and its cryoscopic constant is 5.12 K m–1.
44. Liquids A and B form an ideal solution. At 30° C, the total  (Lakshya JEE Chemistry M-1)
vapour pressure of a solution containing 1 mol of A and
51. Two liquids A and B have PA0 : PB0 = 1 : 3 at a certain
2 moles of B is 250 mm Hg. The total vapour pressure temperature. If the mole fraction ratio of XA : XB = 1:3,
becomes 300 mm Hg when 1 more mol of A is added to the the mole percentage of A in vapour in equilibrium with
first solution. The vapour pressures (in mm Hg) of pure A the solution at a given temperature is _________.
and B at the same temperature are
 (Lakshya JEE Chemistry M-1)
(a) 450, 150 (b) 250, 300
52. 500 mL of 6% (w/V) urea solution is mixed with 500 mL of
(c) 125, 150 (d) 150, 450 18 % (w/V) glucose solution and final volume of mixture
(Lakshya JEE Chemistry M-1) becomes 2 L after addition of water. The osmotic pressure
45. If sodium sulphate is considered to be completely dissociated of final 2 L solution at 27°C is 5yR. The value of y is
into cations and anions in aqueous solution, the change in [R → universal gas constant]
freezing point of water(∆ Tf),when 0.01 mol of sodium sulphate  (Lakshya JEE Chemistry M-1)
is dissolved in 1 kg of water, is (Kf = 1.86 K kg mol – 1) 53. The molal freezing point depression constant of benzene
(a) 0.0186 K (b) 0.0372 K (C6H6) is 4.90 K kg mol–1. Selenium exists as a polymer
of the type SeX. When 3.26 g of selenium is dissolved in
33 JEE (XII) Module-1 CHEMISTRY PW
 226 g of benzene, the observed freezing point is 0.112°C 16 atm and density of 1.2 gm/ml. What is depression of
lower than that of pure benzene. What is the value of X. freezing point (in °C) of this solution? [Kf of water = 1.8
(Atomic mass of Se = 78.8 mol– 1). K Kg mol–1, R = 0.08 atm litre / mole - K] (multiply final
 (Lakshya JEE Chemistry M-1) answer by 100)

54. A radiator was filled with 10L of water to which 2.5 L of  (Lakshya JEE Chemistry M-1)
methanol (density = 0.8g.ml–1) were added. The vehicle 58. Calculate solubility (in moles/litre) of a saturated aqueous
is parked outdoors where the temperature is 0°C. The solution of Ag3PO4 if the vapour pressure of the solution
temperature is decreasing at a uniform rate of 0.50C/min. becomes 750 torr at 373 K. (multiply final answer by 54)
Upto what time (in min) will there be no danger to the  (Lakshya JEE Chemistry M-1)
radiator of the car? Kf(water) = 1.86 kg.mol–1.K. Assume
methanol to be non-volatile. Multiply final answer
by four.
 (Lakshya JEE Chemistry M-1)
55. 24.6 litre dry N2 gas is slowly passed over a liquid at 27°C
and 1 atm. The pressure of gaseous sample coming out
increases due to saturation of gas with vapours of the liquid.
If the mass ratio of N2 gas and the liquid vapour in the
gaseous sample coming out is 25 : 4 and the vapour pressure
of the liquid at 27°C is 0.04 atm, the molar mass (gm/mol)
of liquid is.
 (Lakshya JEE Chemistry M-1)
56. H2S, a toxic gas with rotten egg like smell, is used for the
quantitative analysis. If the solubility of H2S in water at STP
is 0.2m, Henry’s law constant (in bar) for H2S in water at
273K is ___
 (Lakshya JEE Chemistry M-1)
57. A CaCl2 aqueous solution at 27°C has an osmotic pressure

Parikshit (JEE Advanced Level)

SINGLE CORRECT TYPE QUESTIONS Temperature Vapour pressure Vapour pressure

1. A very small amount of non-volatile solute (that does not (0°C) of benzene (torr) of chlorobenzene
dissociate) is dissolved is 56.8 cm3 of benzene (density (torr)
0.889 g cm–3). At room temperature, vapour pressure of this 80 750 120
solution is 100 mm Hg while that of benzene is 102 mm Hg. 90 1000 200
If the freezing temperature of this solution is 1.3 degree
lower than that of benzene, then what is the value of molal 100 1350 300
freezing point depression constant of benzene? 110 1800 400
(a) 5.07 deg/molal (b) 1.3 deg/molal 120 2200 540
(c) 3.9 deg/molal (d) 4.97 deg/molal
(a) 120 °C (b) 110 °C
 (Lakshya JEE Chemistry M-1)
(c) 100 °C (d) 90 °C
2. Using the following information determine the boiling  (Lakshya JEE Chemistry M-1)
point of a mixture containing 1560 gm benzene and 1125 gm
chlorobenzene, when the external pressure is 1000 torr. 3. Pressure over ideal binary liquid mixture containing 10 moles
Assume the solution is ideal. each of liquid A and B is gradually decreased isothermally.
Given: Molar mass of benzene = 78 If PA° = 200 mm Hg and PB° = 100 mm Hg, find the pressure
Molar mass of chlorobenzene = 112.5 at which half of the liquid is converted into vapour.
(a) 150 mm Hg (b) 166.5 mm Hg

34 JEE (XII) Module-1 CHEMISTRY PW

 (c) 133 mm Hg (d) 141.4 mm Hg (a) 0.372°C to 0.558°C (b) 0.186°C to 0.93°C
 (Lakshya JEE Chemistry M-1) (c) 0.558°C to 0.93°C (d) 0.372°C to 0.93°C
4. The vapour pressure of benzene, toluene and xylene are 80
torr, 20 torr and 10 torr respectively at 25°C. Then which of the MULTIPLE CORRECT TYPE QUESTIONS
following is possible value of vapour pressure of equimolar 10. Blood cells in the human body have semipermeable
binary/ternery solution of these at same temperature? membrane and depending upon the concentration of
Assuming all forming an ideal solution with each other. solution inside blood cells and outside (in the body), ‘Lysis’
110 (expansion of blood cells) and ‘Crenation’ (contraction
(a) torr (b) 50 torr of blood cells) may occur. Kidneys are responsible for
3
keeping the solution inside blood cells and blood at the same
(c) 45 torr (d) All are possible concentration. Identify the correct information.
 (Lakshya JEE Chemistry M-1) (a) Lysis will occur when blood cells are kept in a solution
which is isotonic with blood.
5. Calculate solubility of a saturated solution of Ag2CrO4 if
(b) Crenation will occur when blood cells are kept in a
boiling point of its saturated solution is 373K at a pressure
solution which is hypertonic with blood.
of 760 mm of Hg. (c) Blood cells will have normal shape when placed in an
(1 + 1.35 ´ 10- 5 ) isotonic solution with blood.
(a) 2.5 × 10–4 M (b) 7.5 × 10–4 M (d) Lysis will occur when blood cells are kept in a solution
(c) 5.4 × 10–7 M (d) 1.8 × 10–7 M which is hypertonic with blood.
 (Lakshya JEE Chemistry M-1)  (Lakshya JEE Chemistry M-1)
6. The immiscible liquid system containing aniline-water boils 11. The example of negative deviation from Raoult's law is/are
at 98oC under a pressure of 760 mm Hg. At this temperature, (a) HCl and H2O
the vapour pressure of water is 700 mm Hg. If aniline is (b) C2H5OH and H2O
distilled in steam at 98oC, then what percent of total weight (c) CHCl3 and CH3COCH3
of the distillate will be aniline? (d) C6H6 and C6H5CH3
(a) 7.89 (b) 8.57  (Lakshya JEE Chemistry M-1)
(c) 30.5 (d) 44.3 12. Acetone and carbon disulphide form binary liquid solution
 (Lakshya JEE Chemistry M-1) showing positive deviation from Raoult’s law. The normal
7. The amino acid alanine has two isomers, such as α-alanine boiling point (Tb) of pure acetone is less than that of
and β-alanine. When equal masses of these two compounds pure CS2. Pick out the incorrect statements among the
are dissolved in equal mass of a solvent, the solution of following.
α-alanine freezes at relatively lower temperature. Which (a) Boiling temperature of mixture is always less than
forms of α-alanine or β-alanine, has the larger equilibrium boiling temperature of acetone.
constant for ionization? (b) Boiling temperature of mixture is always less than
(a) α-alanine (b) β -alanine boiling temperature of pure CS2.
(c) Same for both (d) Unpredictable (c) When a small amount of CS2 (less volatile component)
is added to excess of acetone, boiling point of resulting
 (Lakshya JEE Chemistry M-1) mixture increases.
8. The vapour pressure of a substance of low volatility can be (d) A mixture of CS2 and CH3COCH3 can be completely
measured by passing an unreactive gas over a sample of the separated by simple fractional distillation.
substance and analysing the composition of the resulting  (Lakshya JEE Chemistry M-1)
gas mixture. When di-nitrogen was passed over mercury at
13. In which of the following pairs of solutions will the values
23° C, the mixture was analysed to 0.8 mg of Hg, 50.4 g of
of the van't Hoff factor be the same?
di-nitrogen at total pressure of 720 torr. The vapour pressure
(a) 0.05 M K4 [Fe(CN)6] and 0.10 M FeSO4
of mercury at this temperature is (Hg = 200)
(b) 0.10 M K4[Fe(CN)6] and 0.05 M FeSO4.(NH4)2SO4
(a) 8 × 10–4 torr (b) 1.6 × 10–3 torr
–3 (c) 0.20 M NaCl and 0.10 M BaCl2
(c) 3.2 × 10 torr (d) 1.6 × 10–4 torr
(d) 0.05 M FeSO4.(NH4)2 SO4 . 6H2O and 0.02 M KC1.
 (Lakshya JEE Chemistry M-1) MgCl2 . 6H2O
9. ‘x’ moles of KCl and ‘y’ mole of BaCl2 are dissolved in 1  (Lakshya JEE Chemistry M-1)
kg of water. If (x + y) = 0.1, then the observed range of DTf 14. In which of the given cases, van’t Hoff factor are equal?
is (Kf of water = 1.86 K-Kg mol–1)
(a) KCl, 50% ionised (b) K2SO4, 40% ionised

35 JEE (XII) Module-1 CHEMISTRY PW

 (c) FeCl3, 30% ionised (d) SnCl4, 20% ionised 19. The diagram given below represents boiling point
 (Lakshya JEE Chemistry M-1) composition diagram of solution of component A and B,
which is/are incorrect among the following?
15. When CuSO4(s) is dissolved in NH4OH solution, then the
correct statement is/are °
TA

(a) Freezing point of solution is raised TB°

(b) Boiling point of solution is lowered T (K)
(c) Freezing point of solution is lowered
(d) Boiling point of solution is raised
 (Lakshya JEE Chemistry M-1) XB
(a) The solution shows negative deviation.
16. Which of the following statements is/are true about an
azeotropic mixture? (b) A-B-interactions are stronger than A-A and B-B.
(a) An azeotropic mixture boils at constant temperature. (c) The solution is an ideal solution.
(b) The composition of an azeotropic mixture changes on (d) The solution shows positive deviation.
distillation.  (Lakshya JEE Chemistry M-1)
(c) An azeotropic solution of two liquids has a boiling 20. For the given electrolyte AxBy, the degree of dissociation
point lower than that of either of them when it shows ‘α’ can be given as
positive deviation from Raoult’s law.
i -1
(d) An azeotropic solution of two liquids has a boiling (a) a = (b) i = (1 – α) + xα + yα
point higher than that of either of them if it shows
(x + y - 1)
positive deviation from Raoult’s law. 1- i
(c) a = (d) None of these
 (Lakshya JEE Chemistry M-1) (1 - x - y )
17. A substance ‘A’ has the following variation of vapour
 (Lakshya JEE Chemistry M-1)
pressure with temperature for its solid state and liquid state.
Identify the options which is/are correct?
21. A liquid mixture having composition corresponding to
2000 point Z in the figure shown is subjected to distillation at
Data: For solid A: log10 P = 4 - ;
T constant pressure.
1500
For liquid A: log10 P = 3.48 -
T
Where P is in mm of Hg and T in K.
(a) Enthalpy of vapourisation and enthalpy of fusion will
be temperature independent.
(b) ∆Hsub. will be approximately 9.212 kcal/mol.
(c) ∆Hfusion will be approximately 2.303 kcal/mol.
(d) ∆Hvap. will be approximately 6.909 kcal/mol.
 (Lakshya JEE Chemistry M-1) Which of the following statement is/are correct about the
process regarding point Z?
18. Consider the following vapour pressure composition graph.
Hence (a) The composition of distillate differs from the mixture.
X (b) The boiling point goes on changing.
Ps (c) The mixture has lowest vapour pressure than that for
V.P.
PA Y V.P. any other composition.

PB Z (d) Composition of an azeotrope alters on changing the

external pressure.
XAA == 01
X S XX
A A= 0
=1  (Lakshya JEE Chemistry M-1)
22. Two solutions S1 and S2 containing 0.1 M NaCl(aq.) and
(a) V.P. of A = SZ
0.08 M BaCl2(aq.) are separated by a semipermeable
(b) V.P. of B = ZY membrane. Which among the following statements is/are
(c) V.P. of B = SY correct?
(d) V.P. of solution at X = SZ + SY (a) S1 and S2 are isotonic.
 (Lakshya JEE Chemistry M-1) (b) S1 is hypertonic and S2 is hypotonic.

36 JEE (XII) Module-1 CHEMISTRY PW

 (c) S1 is hypotonic and S2 is hypertonic. Comprehension (Q. 27 to 29): Colligative properties i.e., the
(d) Osmosis will take place from S1 to S2. properties of solution which depend upon the number of particles
present in solution are osmotic pressure, depression in freezing
 (Lakshya JEE Chemistry M-1)
point, elevation in boiling point and lowering in vapour pressure.
23. 1 mole of a non-volatile solid is dissolved in 200 moles Experimental values of colligative properties for electrolytes
of water. The solution is taken to a temperature TK are always higher than those obtained theoretically because
(lower than the freezing point of solution) to cause ice electrolytes dissociate to furnish more ions in solution. On the
formation. After removal of ice, the remaining solution is other hand, experimentally obtained values of colligative properties
taken to 373 K where vapour pressure is observed to be 740 for associating nature of solute are lower than those obtained
theoretically. The ratio of experimental colligative properties value to
mm of Hg. Identify the correct option.
theoretical colligative properties value is called as van't Hoff factor.
[Given data: Kf (H2O) = 2 K kg mol–1 and normal boiling
point of H2O = 373 K.]  (Lakshya JEE Chemistry M-1)
(a) 163 moles of ice will be formed. 27. A weak monoprotic acid (molar mass 180) aqueous
2000 solution of 0.18% w/v at 300 K has observed osmotic
(b) F.P. of final solution = 273 – K. pressure 0.369 atm. What should be its Van't Hoff
37 ´ 18
factor (i)? (R = 0.082 L-atm/K mole)
(c) Freezing point of original solution should be - 10 °C.
18 (a) 1.2 (b) 1.5 (c) 1 (d) 0.5
(d) Relative lowering of vapour pressure of final solution  (Lakshya JEE Chemistry M-1)
1 28. What is observed molar mass (in g/mol) of weak monoprotic
will be . acid in solution in above question?
201
(a) 270 (b) 180 (c) 120 (d) 90
(Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1)
29. If equal volume of 0.01 M NaOH is added in the solution
COMPREHENSION BASED QUESTIONS of above weak acid solution, then what will be new
Comprehension (Q. 24 to 26): Vapour pressure of a solvent is observed osmotic pressure at same temperature? Neglect
the pressure exerted by vapours when they are in equilibrium the hydrolysis, dissociation of water and any volume
with its solvent at that temperature. The vapour pressure of a contraction or expansion. Assume 100% dissociation of the
solvent is dependent on nature of solvent, temperature, addition salt formed.
of a non-volatile solute as well as nature of solute that dissociates (a) 0.246 atm (b) 0.369 atm
or associates. The vapour pressure of a mixture obtained by (c) 0.123 atm (d) 0.492 atm
mixing two volatile liquids is given by PM = P°A. XA + P°B. XB (Lakshya JEE Chemistry M-1)
where P°A and P°B are vapour pressures of pure components A
and B and XA and XB are their mole fraction in liquid mixture. Comprehension (Q. 30 to 31): The composition of vapour over
For solute-solvent system, the relation becomes PM = P°A. XA a binary ideal solution is determined by the composition of the
where B is a non-volatile solute. liquid. XA and YA are the mole fractions of ‘A’ in the liquid and
vapour at equilibrium, respectively.
 (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1)
24. The vapour pressure of benzene and its solution with a non-
electrolyte solute are 640 and 600 mm respectively. The 30. The value of XA for which (YA – XA) is maximum is
molality of the solution is PAo .PBo – PBo
PAo .PBo – PAo
(a) 0.80 (b) 0.85 (c) 0.90 (d) 0.95 (a) (b)
PAo – PBo PAo – PBo
 (Lakshya JEE Chemistry M-1)
25. A mixture of two volatile liquids A and B for 1 and 3 moles PAo .PBo – PBo PAo .PBo – PAo
(c) (d)
respectively has a V.P. of 300 mm at 27°C. If one mole PAo PBo
of A is further added to this solution, the vapour pressure  (Lakshya JEE Chemistry M-1)
becomes 290 mm at 27°C. The vapour pressure of pure A is
(a) 250 mm (b) 316 mm 31. The vapour pressure of solution at this composition is
(c) 220 mm (d) 270 mm (a) PAo . PBo (b) (PAo – PBo )
 (Lakshya JEE Chemistry M-1)
(c) (PAo + PBo ) (d) 0.5(PAo + PBo )
26. The amount of solute (mol. wt. 60 g/mol) required to
(Lakshya JEE Chemistry M-1)
dissolve in 180 g of water to reduce the vapour pressure to
4/5th of the vapour pressure of pure water, is Comprehension (Q. 32 to 34): The experimental values of
(a) 120 g (b) 150 g (c) 200 g (d) 60 g colligative properties of many solutes in solution resembles

37 JEE (XII) Module-1 CHEMISTRY PW

calculated values of colligative properties. B. 10 mL of 0.1 M NaOH q. Vapour pressure
However in same cases, the experimental value of colligative aqueous solution is added to of solution
property differ widely than those obtained by calculation. Such 10 mL of 0.1 M CH3COOH increases
experimental values of colligative properties are known as aqueous solution
Abnormal values of colligative property. Cause for abnormal
values of colligative properties are: C. 10 mL of 0.1 M HCl r. Boiling point of
(i) Dissociation of solute: It increases the value of colligative aqueous solution is added solution decreases
properties. e.g.: Dissociation of KCl, NaCl etc. in H2O. to 10 mL of 0.1 M NH3
(ii) Association of solute: It decreases the value of aqueous solution
colligative properties. e.g.: Dimerisation of acetic acid D. 10 mL of 0.1 M HCl s. Freezing point of
in benzene aqueous solution is added solution increases
 (Lakshya JEE Chemistry M-1) to 10 mL of 0.1 M KOH
32. If degree of dissociation of an electrolyte A2B3 is 25% in a aqueous solution
solvent, then
(a) A→ q, r, s; B→ p, q, r, s; C→ p, q, r; D→ p, r, s
(a) Normal boiling point = Experimental boiling point
(b) A→ p, q; B→ q, r, s; C→ p, r, s; D→ p, q, r, s
(b) Normal freezing point < Experimental freezing point
(c) A→ p, q, r, s; B→ p, q, r, s; C→ p, q, r, s; D→ p, q, r, s
(c) Normal osmotic pressure = (1/2) Experimental osmotic
pressure (d) A→ p, q, r; B→ p, q, s; C→ p, q, r, s; D→ p, q,
(d) Normal molecular weight = Experimental molecular 36.
weight
Column-I Column-II
 (Lakshya JEE Chemistry M-1)
33. 4 different 100 mL solutions are prepared by mixing 1 gram A. Acetone + CHCl3 p. ∆Smix. > 0
each of NaCl, (NH2)2CO, Na2SO4 and K4[Fe(CN)6] at B. Ethanol + Water q. ∆Vmix. > 0
temperature T. Correct order of osmotic pressure is
C. C2H5Br + C2H5l r. ∆Hmix. < 0
(a) (NH2)2CO solution > NaCl solution > Na2SO4 solution
> K4[Fe(CN)6] solution D. Acetone + Benzene s. Maximum boiling azeotrope
(b) NaCl solution > Na2SO4 solution > (NH2)2CO solution
> K4 [Fe(CN)6] solution t. Minimum boiling azeotrope
(c) K4[Fe(CN)6] solution > Na2SO4 solution > NaCl
solution (NH2)2CO solution (a) A→ p ; B→ p, q, t; C→ p; D→ q, t
(d) Na2SO4 solution > (NH2)2CO solution > NaCl (b) A→ p, s,; B→ q, t; C→ p; D→ p, q,
solution > K4 [Fe(CN)6] solution (c) A→ p, r; B→ q, t; C→ p; D→ p, q, t
 (Lakshya JEE Chemistry M-1) (d) A→ p, s, r; B→ p, q, t; C→ p; D→ p, q, t
(Lakshya JEE Chemistry M-1)
34. One mole l2 (solid) is added in 1 M, 1 litre Kl solution.
Then 37.
(a) Osmotic pressure of solution increases
Column-I Column-II
(b) Freezing point of solution increases (Solute, degree of (van't Hoff
(c) Relative lowering in vapour pressure decreases ionisation) factor)
(d) No change in boiling point of solution
A. K2SO4 ; α = 0.85 p. 3.7
 (Lakshya JEE Chemistry M-1)
B. SnCl2 ; α = 0.7 q. 4.0
MATCH THE COLUMN TYPE QUESTIONS C. Al(NO3)3 ; α = 0.9 r. 2.7

 (LAKSHYA JEE CHEMISTRY M-1) D. Fe2(SO4)3 ; α = 0.75 s. 2.4

35. Assuming all the solutes are non-volatile and all solutions (a) A→ r; B→ s; C→ p; D→ q
are ideal and neglect the hydrolysis of cation and anion. (b) A→ p; B→ s; C→ r; D→ q
(c) A→ s; B→ r; C→ p; D→ q
Column-I Column-II
(d) A→ q; B→ r; C→ p; D→ s
A. 10 mL of 0.1 M NaOH p. Osmotic pressure (Lakshya JEE Chemistry M-1)
aqueous solution is mixed of solution
38.
with 10 mL of 0.1 M HCl decreases
aqueous solution Column-I Column-II

38 JEE (XII) Module-1 CHEMISTRY PW

 42. A solution comprising 0.1 mol of naphthalene and 0.6 mol
A. Ideal solutions p. Solute-solvent
of benzene is cooled until some solid benzene freezes out.
interactions are weaker
The solution is then decanted off from solid and warmed to
than either solute-solute 353 K, where its vapour pressure is found to be 608 torr. The
or solvent-solvent freezing and normal boiling points of benzene are 278.5 K
interactions and 353 K respectively. The amount of benzene that freezes
B. Solutions showing q. Solute-solvent out due to cooling is x g. The value of 5x is _________ .
positive deviations interactions are similar  (Lakshya JEE Chemistry M-1)
to solute-solute 43. A solution containing compound 'X' in water and a solution
and solvent-solvent containing glucose in water were put in a closed system.
interactions By doing this, some water vapour was removed from one
C. Solutions showing r. Solute-solvent solution and got condensed in the other. It is found that when
both the solutions were at equilibrium vapour pressure, one
negative deviations interactions are stronger
solution contains 10% (w/w) of 'X' and the other 5% (w/w)
than both solute-solute
glucose. The molar mass (in g/mol) of 'X' is
and solvent-solvent
 (Lakshya JEE Chemistry M-1)
interactions
44. Safrole is contained in oil of sassafras and was once used to
(a) A→ p; B→ r; C→ q
flavour root beer. A 2.4 mg sample of safrole was dissolved
(b) A→ r; B→ p; C→ q in 100.0 mg of diphenyl ether. The solution has a freezing
(c) A→ p; B→ q; C→ r of 25.64oC. The freezing point of pure diphenyl ether is
(d) A→ q; B→ p; C→ r 26.84oC and the freezing-point-depression constant Kf, is
(Lakshya JEE Chemistry M-1) 8.00oC/m. The molecular mass (in g/mol) of safrole is
 (Lakshya JEE Chemistry M-1)
INTEGER TYPE QUESTIONS
45. 1.22 g of benzoic acid is dissolved in 100 g of acetone and
 (LAKSHYA JEE CHEMISTRY M-1) 100 g of benzene separately. Boiling point of the solution
in acetone increases by 0.17 °C while in benzene increases
39. At 20°C, the vapour pressure of 0.1 molal aqueous solution
by 0.13°C. Kb for acetone and benzene are 1.7 K kg mol–1
of urea is 0.03 mm less than that of water and the vapour
and 2.6 K kg mol–1. If x and y are the molecular weight
pressure of 0.1 molal solution of KCl is 0.0594 mm less
of benzoic acid in acetone and benzene respectively, then
than that of water. The apparent percentage dissociation of
the value of (x + y) is:
KCI in water at the given temperature is (Neglect the mole
of solute particles in comparison to the mole of water in both  (Lakshya JEE Chemistry M-1)
solutions.) 46. Vapour pressure of an equimolar mixture of benzene and
 (Lakshya JEE Chemistry M-1) toluene at a given temperature was found to be 80 mm Hg.
40. Equimolar mixture of A and B form an ideal solution If vapour above the liquid phase is condensed in a beaker,
at 300 K. The vapour of this solution is condensed vapour pressure of this condensate at the same temperature
in 2nd container and temperature is maintained at was found to be 100 mm Hg. If the pure sate vapour pressure
300 K. The vapour of 2nd container is condensed into 3rd of benzene and toluene is respectively x and y. Then
container and temperature is maintained at 300 K. If total x + 2y
determine the value of .
vapour pressure of solution in 3rd container is x mm Hg, 50
 (Lakshya JEE Chemistry M-1)
x
the value of is [P°A, and P°B at 300 K are 100 mm Hg
9 47. In 10 3 Litre sample of hard water CaSO 4 and MgSO 4
and 200 mm Hg respectively.] is present. If elevation in Boiling point is 0.000052°C.
 (Lakshya JEE Chemistry M-1) Calculate the degree of Hardness (in ppm) of hard water.
(Kb for H2O = 0.52 K.kg/mol)
41. A non-volatile solute P is present in 500 mL solution and
molarity is found to be 1 M. A sample of 5 mL of this  (Lakshya JEE Chemistry M-1)
solution is taken in another container and further 0.4 g of
P is added and volume is increased by adding water such 48. The vapour pressure of fluorobenzene at t°C is given by the
that final volume becomes 10 L. If molarity of diluted equation
solution is 10–3 M, the molar mass of solute P (in g/mol) 1250
is _________ .
log p (mm Hg) = 7.0 -
t + 220
 (Lakshya JEE Chemistry M-1) Calculate the boiling point of the liquid in °C if the external
39 JEE (XII) Module-1 CHEMISTRY PW
 (applied) pressure is 5.26% more than required for normal 54. Calculate the density of glycol solution whose 2.976 litre on
boiling point. (log 2 = 0.3) addition to 5 litres of water produces an antifreeze solution
which protects automobile radiator down to –20°C.
(Lakshya JEE Chemistry M-1) Kb and Kf for water = 1.86 and 0.52 (K kg/mol).
 (Lakshya JEE Chemistry M-1)
NUMERICAL TYPE QUESTIONS 55. 1 g of monobasic acid when dissolved in 100 g of water
(UPTO TWO DECIMAL PLACE) lower the freezing point by 0.168°C. 0.2 gm of the same
acid when dissolved and titrated required 15.1 ml of N/10
alkali. Calculate degree of dissociation of the acid. (kf for
 (LAKSHYA JEE CHEMISTRY M-1) water is 1.86 K kg/mol).
 (Lakshya JEE Chemistry M-1)
 (LAKSHYA JEE CHEMISTRY M-1)
49. A binary solution of A and B is ideal. If total vapour
pressure of this solution is represented as
PS (in mm Hg) = 100 – 50 XB
Here, PS ⇒ Total vapour pressure
XB ⇒ Mole fraction of B in liquid state
This solution is passed through different distillation stages
and at a particular stage, it is found that the mole fraction
4
of A in vapour phase is . The total vapour pressure of
7
solution at this stage of distillation is ______ (in mm Hg).
 (Lakshya JEE Chemistry M-1)
50. The mole fraction, x of a solute in an ideal saturated
- DH æ 1 1 ö
solution in a solvent is given by log10x = ´ç - ÷
2.303R è T T0 ø
where DHf and T0 are the molar heat of fusion and the
freezing point of the solute. The melting point of
phenanthrene is 100°C and the latent heat of fusion is
24.3 cal g –1 . Calculate x, (the ideal solubility) of
phenanthrene (C14H10) in benzene at 25°C.
 (Lakshya JEE Chemistry M-1)
51. Mixture of two liquids A and B is placed in cylinder
containing piston. Piston is pulled out isothermally so that
volume of liquid decreases but that of vapour increases.
When negligibly small amount of liquid was remaining,
the mole fraction of A in vapour is 0.4. Given PA° = 0.4 atm
and P B° = 1.2 atm at the experimental temperature.
Calculate the total pressure (in atm) at which the liquid
has almost evaporated. (Assume ideal behaviour).
 (Lakshya JEE Chemistry M-1)
52. The Ksp(25°C) of sparingly soluble salt XY2(s) is
3.56 × 10– 5 (mol lit–1)3 and at 30°C, the vapour pressure of
its saturated solution in water is 31.78 mm of Hg. Calculate
the enthalpy change (in kJ/mol) of the reaction.
 X+2 (aq) + 2Y–(aq)
XY2(s) 
Given : Vapour pressure of pure water = 31.82 mm of Hg
 (Lakshya JEE Chemistry M-1)
53. What is Van’t Hoff factor when benzene vapour pressure
falls from 165 mm Hg to 162 mm Hg on addition of 6 g
of CH3COOH to 3 moles of benzene?
 (Lakshya JEE Chemistry M-1)

40 JEE (XII) Module-1 CHEMISTRY PW

 PYQ’s (Past Year Questions)

EXPRESSING CONCENTRATIONS 9. The density of 'x' M solution ('x' molar) of NaOH is 1.12 g
mL–1. while in molality, the concentration of the solution is
OF SOLUTIONS 3 m (3 molal). Then x is [06 April, 2024 (Shift-I)]
1. The quantity which changes with temperature is: (Given: Molar mass of NaOH is 40 g/mol)
 [27 Jan, 2024 (Shift-II)] (a) 3.5 (b) 3.0
(a) Molarity (b) Mass percentage (c) 3.8 (d) 2.8
(c) Molality (d) Mole fraction  (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1) 10. Molality (m) of 3M aqueous solution of NaCl is: (Given:
2. Volume of 3M NaOH (formula weight 40 g mol–1) which Density of solution = 1.25 g mL–1, Molar mass in g mol–1 :
can be prepared from 84 g of NaOH is _____ × 10–1 dm3. Na-23,Cl-35.5) [06 April, 2024 (Shift-II)]
 [27 Jan, 2024 (Shift-II)] (a) 2.90 m (b) 2.79 m
 (Lakshya JEE Chemistry M-1) (c) 1.90 m (d) 3.85 m
3. A solution of H2SO4 is 31.4% H2SO4 by mass and has a  (Lakshya JEE Chemistry M-1)
density of 1.25g/mL.The molarity of the H2SO4 solution 11. Molality of an aqueous solution of urea is 4.44 m. Mole
is____M (nearest integer) fraction of urea in solution is x × 10–3.
[Given molar mass of H2SO4 = 98g mol–1] Value of x is _______. (integer answer)
 [29 Jan, 2024 (Shift-I)]  [08 April, 2024 (Shift-II)]
 (Lakshya JEE Chemistry M-1)  (Lakshya JEE Chemistry M-1)
4. Molality of 0.8 M H2SO4 solution (density 1.06 g cm–3)
is 12. A solution is prepared by adding 1 mole ethyl alcohol in 9
______ × 10–3 m. [29 Jan, 2024 (Shift-II)] mole water. The mass percent of solute in the solution is
_______ (Integer Answer)
 (Lakshya JEE Chemistry M-1)
(Given: Molar mass in g mol–1 Ethyl alcohol: 46, water: 18)
5. The mass of sodium acetate (CH3COONa) required to  [08 April, 2024 (Shift-II)]
prepare 250 mL of 0.35 M aqueous solution is _____ g.  (Lakshya JEE Chemistry M-1)
(Molar mass of CH3COONa is 82.02 g mol–1)
13. Given below are two statements: one is labelled as Assertion
 [30 Jan, 2024 (Shift-I)]
(A) and the other is labelled as Reason (R).
 (Lakshya JEE Chemistry M-1) Assertion (A): 3.1500g of hydrated oxalic acid dissolved in

6. If a substance 'A' dissolves in solution of a mixture of 'B' and water to make 250.0 mL solution will result in 0.1 M oxalic
'C' with their respective number of moles as nA, nB and nC, acid solution.
mole fraction of C in the solution is:
Reason (R): Molar mass of hydrated oxalic acid is

 [30 Jan, 2024 (Shift-II)]
nC nC 126 g mol–1. [10 April, 2023 (Shift-II)]
(a) (b)
nA ´ nB ´ nC nA + nB + nC In the light of the above statements, choose the correct
nB answer from the options given below:
nC
(c) (d)
nA - nB - nC nA + nB (a) Both (A) and (R) are true but (R) is NOT the correct
explanation of (A).
 (Lakshya JEE Chemistry M-1)
(b) (A) is false but (R) is true.
7. The molarity of 1L orthophosphoric acid (H3PO4) having
70% purity by weight (specific gravity 1.54 g cm–3 ) is (c) (A) is true but (R) is false.
______M. (Molar mass of H3PO4 = 98 g mol–1) (d) Both (A) and (R) are true and (R) is the correct
 [31 Jan, 2024 (Shift-II)] explanation of (A).
 (Lakshya JEE Chemistry M-1)  (Lakshya JEE Chemistry M-1)
14. The molality of a 10%(V/V) solution of di-bromine solution
8. The Molarity (M) of an aqueous solution containing 5.85 g in CCl4 (carbon tetrachloride) is 'x'. x = _________ × 10–2 M.
of NaCl in 500 mL water is: [04 April, 2024 (Shift-I)] (Nearest Integer)
(Given: Molar Mass Na : 23 and Cl : 35.5 gmol–1) [Given: molar mass of Br2 = 160 g mol–1
(a) 20 (b) 0.2 (c) 2 (d) 4 atomic mass of C = 12 g mol–1
atomic mass of Cl = 35.5 g mol–1
 (Lakshya JEE Chemistry M-1)
density of dibromine 3.2 g cm–3

41 JEE (XII) Module-1 CHEMISTRY PW

 density of CCl4 = 1.6 g cm–3] of millimoles of O2 gas that dissolve in 1 litre of water is
 [1 Feb, 2023 (Shift-II)] __________. (Nearest Integer)
 (Lakshya JEE Chemistry M-1) (Given: Henry’s Law constant for O2 at 303 K is 46.82 k bar
15. A solution of sugar is obtained by mixing 200 g of its 25% and partial pressure of O2 = 0.920 bar)
solution and 500 g of its 40% solution (both by mass). The (Assume solubility of O 2 in water is too small, nearly
mass percentage of the resulting sugar solution is. (Nearest negligible) [29 July, 2022 (Shift-II)]
Integer) [11 April, 2023 (Shift-I)]  (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1) 23. The oxygen dissolved in water exerts a partial pressure of
16. When 800 mL of 0.5 M nitric acid is heated in a beaker, 20 kPa in the vapour above water. The molar solubility of
its volume is reduced to half and 11.5 g of nitric acid is oxygen in water is ____ × 10–5 mol dm–3.
evaporated. The molarity of the remaining nitric acid (Round off to the Nearest Integer).
solution is x × 10–2M. (Nearest Integer) [Given: Henry’s law constant = KH = 8.0 × 104 kPa for O2
Density of water with dissolved oxygen = 1.0 kg dm–³]
(Molar mass of nitric acid is 63 g mol–1)
 [17 March, 2021 (Shift-I)]
[26 July, 2022 (Shift-I)]
 (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1) 24. At 35°C, the vapour pressure of CS2 is 512 mm of Hg
17. The molarity of the solution prepared by dissolving 6.3 g of and that of acetone is 344 mm of Hg. A solution of CS2 in
oxalic acid (H2C2O4 . 2H2O) in 250 mL of water in mol L–1 acetone has a total vapour pressure of 600 mm of Hg. The
is x × 10–2. The value of x is ______. (Nearest Integer) false statement among the following is
(a) CS2 and acetone are less attracted to each other than to
[Atomic mass : H : 1.0, C : 12.0, O : 16.0] themselves
 [31Aug, 2021 (Shift-I)] (b) Heat must be absorbed in order to produce the solution
at 35°C
 (Lakshya JEE Chemistry M-1)
(c) Raoult's law is not obeyed by this system
18. 100 mL of Na3PO4 solution contains 3.45 g of sodium. (d) a mixture of 100 mL CS2 and 100 mL acetone has a
The molarity of the solution is ____ × 10–2 mol L–1, (Nearest volume of < 200 mL [7 Jan, 2020 (Shift-I)]
 (Lakshya JEE Chemistry M-1)
Integer)
25. Liquids A and B form an ideal solution for all compositions
[Atomic Masses – Na : 23.0 u, O : 16.0 u, P : 31.0 u] of A and B at 25°C. Two such solutions with 0.25 and 0.50
 [26 Aug, 2021 (Shift-II)] mole fractions of A have the total vapor pressures of 0.3
and 0.4 bar, respectively. What is the vapor pressure of pure
 (Lakshya JEE Chemistry M-1) liquid B in bar? [JEE Adv 2020]
19. The mole fraction of glucose (C6H12O6) in an aqueous binary  (Lakshya JEE Chemistry M-1)
26. Liquids A and B form an ideal solution in the entire
solution is 0.1. The mass percentage of water in it, to the
composition range. At 350 K, the vapor pressures of pure
nearest Integer, is __________ . [3 Sept, 2020 (Shift-I)] A and pure B are 7 × 103 Pa and 12 × 103 Pa, respectively.
 (Lakshya JEE Chemistry M-1) The composition of the vapour in equilibrium with a solution
20. The mole fraction of urea in an aqueous urea solution containing 40 mole percent of A at this temperature is
containing 900 g of water is 0.05. If the density of the  [10 Jan, 2019 (Shift-I)]
solution is 1.2 g cm–3, the molarity of urea solution is _____. (a) XA = 0.76 ; XB = 0.24 (b) XA = 0.37 ; XB = 0.63
(Given data: Molar masses of urea and water are 60 g mol–1 (c) XA = 0.28 ; XB = 0.72 (d) XA = 0.4 ; XB = 0.6
and 18 g mol–1, respectively) [JEE Adv (2019)]  (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1) 27. At room temperature, a dilute solution of urea is prepared
by dissolving 0.60 g of urea in 360 g of water. If the vapour
SOLUBILITY AND VAPOUR PRESSURE pressure of pure water at this temperature is 35 mm Hg,
OF LIQUID SOLUTIONS lowering of vapour pressure will be: (molar mass of urea =
60 g mol–1) [10 April, 2019 (Shift-I)]
21. The vapour pressure of pure benzene and methyl benzene at (a) 0.027 mmHg (b) 0.031 mmHg
27°C is given as 80 Torr and 24 Torr, respectively. The mole (c) 0.028 mmHg (d) 0.017 mmHg
fraction of methyl benzene in vapour phase, in equilibrium  (Lakshya JEE Chemistry M-1)
with an equimolar mixture of those two liquids (ideal
solution) at the same temperature is____× 10–2 (nearest IDEAL AND NON-IDEAL SOLUTIONS
integer) [09 April, 2024 (Shift-II)] 28. A solution of two miscible liquids showing negative
 (Lakshya JEE Chemistry M-1) deviation from Raoult's law will have:
22. If O2 gas is bubbled through water at 303 K, the number  [27 Jan, 2024 (Shift-I)]

42 JEE (XII) Module-1 CHEMISTRY PW

 (a)increased vapour pressure, increased boiling point (c) iA = iB = iC (d) iA > iB > iC
(b)increased vapour pressure, decreased boiling point
 (Lakshya JEE Chemistry M-1)
(c)decreased vapour pressure, decreased boiling point
(d)decreased vapour pressure, increased boiling point 35. Mass of ethylene glycol (antifreeze) to be added to 18.6 kg
 (Lakshya JEE Chemistry M-1) of water to protect the freezing point at –24°C is________
29. Identify the mixture that shows positive deviations from kg (Molar mass in g mol–1 for ethylene glycol is 62, Kf of
Raoult’s Law [31 Jan, 2024 (Shift-I)] water = 1.86 K kg mol–1). [01 Feb, 2024 (Shift-II)]
(a) (CH3)2CO + C6H5NH2  (Lakshya JEE Chemistry M-1)
(b) CHCl3 + C6H6 36. 2.5 g of a non-volatile, non-electrolyte is dissolved in 100
(c) CHCl3 + (CH3)2CO g of water at 25°C. The solution showed a boiling point
elevation by 2°C. Assuming the solute concentration in
(d) (CH3)2CO + CS2 negligible with respect to the solvent concentration, the
 (Lakshya JEE Chemistry M-1) vapour pressure of the resulting aqueous solution is _______
30. Two open beakers one containing a solvent and the other mm of Hg (nearest integer) [04 April, 2024 (Shift-I)]
containing a mixture of that solvent with a non-volatile [Given: Molal boiling point elevation constant of water (Kb)
solute are together sealed in a container. Over time. = 0.52 K. kg mol–1, 1 atm pressure = 760 mm of Hg, molar
(a) The volume of the solution and the solvent does not change. mass of water = 18 g mol–1]
(b) The volume of the solution increases and the volume  (Lakshya JEE Chemistry M-1)
of the solvent decreases.
37. 2.7 Kg of each of water and acetic acid are mixed, The
(c) The volume of the solution does not change and the freezing point of the solution will be –x °C. Consider the
volume of the solvent decreases. acetic acid does not dimerise in water, nor dissociates in
(d) The volume of the solution decreases and the volume water x = ______ (nearest integer)
of the solvent increases. [7 Jan, 2020 (Shift-II)  [04 April, 2024 (Shift-II)]
 (Lakshya JEE Chemistry M-1)]
[Given: Molar mass of water = 18 g mol–1, acetic acid = 60
g mol–1]
COLLIGATIVE PROPERTIES AND Kf H2O: 1.86 K kg mol–1
ABNORMAL MOLAR MASS Kf acetic acid: 3.90 K kg mol–1
31. The osmotic pressure of a dilute solution is 7 × 105 Pa at 273K. freezing point: H2O = 273 K, acetic acid = 290 K]
Osmotic pressure of the same solution at 283K is____× 104  (Lakshya JEE Chemistry M-1)
Nm–2. [29 Jan, 2024 (Shift-I)]
38. An artificial cell is made by encapsulating 0.2 M glucose
 (Lakshya JEE Chemistry M-1)
solution within a semipermeable membrane. The osmotic
32. What happens to freezing point of benzene when small
pressure developed when the artificial cell is placed within
quantity of napthalene is added to benzene?
a 0.05 M solution of NaCl at 300 K is _______ × 10–1 bar.
 [30 Jan, 2024 (Shift-I)]
(Nearest Integer) [05 April, 2024 (Shift-I)]
(a) Increases
(b) Remains unchanged [Given: R = 0.083 L bar mol–1 K–1]
(c) First decreases and then increases Assume complete dissociation of NaCl
(d) Decreases  (Lakshya JEE Chemistry M-1)
 (Lakshya JEE Chemistry M-1) 39. Considering acetic acid dissociates in water, its dissociation
33. The solution from the following with highest depression in constant is 6.25 × 10–5. If 5 mL of acetic acid is dissolved in
freezing point/lowest freezing point is 1 liter water, the solution will freeze at –x × 10–2 °C, provided
 [30 Jan, 2024 (Shift-II)] pure water freezes at 0 °C. [05 April, 2024 (Shift-II)]
(a) 180 g of acetic acid dissolved in water x = _________. (Nearest integer)
(b) 180 g of acetic acid dissolved in benzene Given: (Kf )water = 1.86 K kg mol–1.
(c) 180 g of benzoic acid dissolved in benzene density of acetic acid is 1.2 g mol–1
(d) 180 g of glucose dissolved in water molar mass of water = 18 g mol–1.
 (Lakshya JEE Chemistry M-1) molar mass of acetic acid = 60 g mol–1.
34. We have three aqueous solutions of NaCl labelled as ‘A’, density of water = 1g cm–3
‘B’ and ‘C’ with concentration 0.1 M, 0.01M & 0.001 M, Acetic acid dissociates as
respectively. The value of van’t Hoff factor (i) for these CH3COOH  CH3COOΘ + H⊕
solutions will be in the order. [01 Feb, 2024 (Shift-I)]
(a) iA < iB < iC (b) iA < iC < iB  (Lakshya JEE Chemistry M-1)

43 JEE (XII) Module-1 CHEMISTRY PW

 40. Consider the dissociation of the weak acid HX as given below  (Lakshya JEE Chemistry M-1)
HX(aq)  H+(aq) + X–(aq), Ka = 1.2 × 10–5 45. Evaluate the following statements for their correctness.
[Ka: dissociation constant] (A) The elevation in boiling point temperature of water
The osmotic pressure of 0.03M aqueous solution of HX at will be same for 0.1 M NaCl and 0.1 M urea.
300 K is ______ ×10–2 bar (nearest integer). (B) Azeotropic mixtures boil without change in their
[Given: R = 0.083 L bar Mol–1 K–1] composition
 [06 April, 2024 (Shift-I)] (C) Osmosis always takes place from hypertonic to
hypotonic solution
 (Lakshya JEE Chemistry M-1)
(D) The density of 32% H2SO 4 solution having molarity
41. When 'x' × 10–2 mL methanol (molar mass = 32 g; density = 4.09 M is approximately 1.26 g mL−1
0.792 g/cm3) is added to 100 mL water (density =1 g/cm3),
(E) A negatively charged sol is obtained when KI solution
the following diagram is obtained.
is added to silver nitrate solution.
Water c Choose the correct answer from the options given below :
noli
Vapour pressurce

m M etha tion  [31 Jan, 2023 (Shift-II)]

yste sol u
en s
Froz (a) (B), (D), and (E) only
(b) (A), (B), and (D) only
270.65 273.15 (c) (A) and (C) only
Temperature/K
(d) (B) and (D) only
x = ................... (nearest integer)
(Lakshya JEE Chemistry M-1)
[Given: Molal freezing point depression constant of water
46. What weight of glucose must be dissolved in 100 g of water
at 273.15K is 1.86 K kg mol–1]
to lower the vapour pressure by 0.20 mm Hg?
 [06 April, 2024 (Shift-II)]
(Assume dilute solution is being formed)
 (Lakshya JEE Chemistry M-1) Given: Vapour pressure of pure water is 54.2 mm Hg at
42. A solution containing 10 g of an electrolyte AB2 in 100 g room temperature. Molar mass of glucose is 180 g mol–1.
of water boils at 100.52°C. The degree of ionization of the [11 April, 2023 (Shift-II)]
electrolyte (α) is ______ × 10 –1 (nearest integer).
(a) 4.69 g (b) 3.59 g (c) 2.59 g (d) 3.69 g
[Given: Molar mass of AB2 = 200 g mol–1 Kb (molal boiling
 (Lakshya JEE Chemistry M-1)
point elevation const. of water) = 0.52 K kg mol–1, boiling
47. A solution containing 2g of a non-volatile solute in 20g of
point of water = 100°C; AB2 ionises as AB2 → A2+ +2B –]
water boils at 373.52 K. The molecular mass of the solute
 [08 April, 2024 (Shift-I)] is gmol–1. (Nearest Integer)
 (Lakshya JEE Chemistry M-1) Given, water boils at 373 K, Kb for water = 0.52 K kg mol–1
43. 0.05M CuSO4 when treated with 0.01M K2Cr2O7 gives green [30 Jan, 2023 (Shift-I)]
colour solution of Cu2Cr2O7. The [SPM : Semi Permeable  (Lakshya JEE Chemistry M-1)
Membrane] [09 April, 2024 (Shift-I)] 48. When a certain amount of solid A is dissolved in 100 g of
water at 25°C to make a dilute solution, the vapour pressure
K2Cr2O7 CuSO4 of the solution is reduced to one-half of that of pure water.
SideX SPM SideY The vapour pressure of pure water is 23.76 mmHg. The
Due to osmosis: number of moles of solute A added is________. (Nearest
Integer) [27 July, 2022 (Shift-II)]
(a) Green colour formation observed on side Y.
(b) Green colour formation observed on side X.  (Lakshya JEE Chemistry M-1)
(c) Molarity of K2Cr2O7 solution is lowered. 49. The osmotic pressure exerted by a solution prepared by
(d) Molarity of CuSO4 solution is lowered. dissolving 2.0 g of protein of molar mass 60 kg mol–1 in
 (Lakshya JEE Chemistry M-1)
200 mL of water at 27°C is _____Pa. (nearest Integer)
44. Solid Lead nitrate is dissolved in 1 litre of water. The solution (Use R = 0.083 L bar mol–1 K–1) [26 June, 2022 (Shift-II)]
was found to boil at 100.15ºC. When 0.2 mol of NaCl is
added to the resulting solution, it was observed that the  (Lakshya JEE Chemistry M-1)
solution froze at –0.8ºC. The solubility product of PbCl2
formed is _____________ ×10–6 at 298 K. (Nearest Integer) 50. Which one of the following 0.06 M aqueous solutions has
Given: Kb = 0.5 K kg mol–1 and Kf = 1.8 kg mol–1. Assume lowest freezing point? [22 July, 2021 (Shift-II)]
molality to be equal to molarity in all cases. (a) Kl
[29 Jan, 2023 (Shift-I)] (b) Al2(SO4)3
44 JEE (XII) Module-1 CHEMISTRY PW
 (c) C6H12O6 diluted sample? [11 Jan, 2019 (Shift-I)]
(d) K2SO4 (a) 1 cup of water to 2 cups of pure milk
(b) 3 cups of water to 2 cups of pure milk
 (Lakshya JEE Chemistry M-1)
(c) 1 cup of water to 3 cups of pure milk
51. 40 g of glucose (Molar mass = 180) is mixed with
(d) 2 cups of water to 3 cups of pure milk
200 mL of water. The freezing point of solution is _____ K.
 (Lakshya JEE Chemistry M-1)
(Nearest Integer)
[Given: Kf =1.86 K kg mol–1; Density of water = 1.00 g
cm–3; Freezing point of water = 273.15 K]
 [27 Aug, 2021 (Shift-II)]
 (Lakshya JEE Chemistry M-1)
Question stem for Question No. (52-53)
The boiling point of water in a 0.1 molal silver nitrate solution
(solution A) is x°C. To this solution A, an equal volume of 0.1
molal aqueous barium chloride solution is added to make a new
solution B. The difference in the boiling points of water in the two
solutions A and B is y × 10–2 °C.
(Assume: Densities of the solutions A and B are the same as that
of water and the soluble salts dissociate completely.
Use: Molal elevation constant (Ebullioscopic constant).
Kb = 0.5 K kg mol–1; Boiling point of pure water as 100°C.)
52. The value of x is ______. [JEE Adv 2021]
 (Lakshya JEE Chemistry M-1)
53. The value of |y| is ______. [JEE Adv 2021]
 (Lakshya JEE Chemistry M-1)
54. On dissolving 0.5 g of a non-volatile non-ionic solute to
39 g of benzene, vapor pressure decreases from 650 mm
Hg to 640 mm Hg. The depression of freezing point of
benzene (in K) upon addition of the solute is ______.
(Given data: Molar mass and the molal freezing point
depression constant of benzene are 78 g mol–1 and
5.12 K kg mol–1, respectively) [JEE Adv (2019)]
(Lakshya JEE Chemistry M-1)
55. A set of solutions is prepared using 180 g of water as a
solvent and 10 g of different non-volatile solutes A, B and C.
The relative lowering of vapour pressure in the presence
of these solutes are in the order [Given, molar mass of
A = 100 g mol–1; B = 200 g mol–1; C = 10,000 g mol–1]
 [6 Sept, 2020 (Shift-II)]
(a) A > C > B (b) C > B >A
(c) A > B > C (d) B > C >A
 (Lakshya JEE Chemistry M-1)
56. The osmotic pressure of a solution of NaCl is 0.10 atm
and that of a glucose solution is 0.20 atm. The osmotic
pressure of a solution formed by mixing 1 L of the sodium
chloride solution with 2 L of the glucose solution is
x × 10–3 atm. x is____. (nearest Integer)
 [4 Sept, 2020 (Shift-II)]
 (Lakshya JEE Chemistry M-1)
57. The freezing point of diluted milk sample is found to be
0.2°C, while it should have been –0.5°C for pure milk.
How much water has been added to pure milk to make the

45 JEE (XII) Module-1 CHEMISTRY PW

 PW Challengers

INTEGER TYPE QUESTIONS compartment, separated by SPM. At equilibrium, the height

of liquid in the right compartment is 74.5 mm in excess of
 (LAKSHYA JEE CHEMISTRY M-1) that in the left compartment. The temperature of the system
is maintained at 298K. The number of millimoles in 320 g
1. The molecular weight of a newly synthesized organic
of haemoglobin is (Given: The density of final solution is
compound was determined by the method of isothermal
1.013 g/ml, g = 10 m/s2, R = 0.08 L-atm / K-mol)
distillation. In this procedure two solutions, each in an open
calibrated vial, are placed side by side in a closed chamber.  NUMERICAL TYPE QUESTIONS
One of the solutions contained 9.3 mg of the new compound,
the other 13.2 mg of azobenzene (MW = 182). Both were  (LAKSHYA JEE CHEMISTRY M-1)
dissolved in portions of the same solvent. During a period 5. Two solutions of non-volatile solutes A and B are prepared.
of 3 days of equilibration, solvent distilled from one vial The molar mass ratio, M A = 1 . Both are prepared as 5%
MB 3
into the other until the same partial pressure of solvent was
solutions by weight in water. If the two solutions are mixed
reached in the two vials. At this point the distillation of
to prepare two new solution S1 and S2, the mixing ratio being
solvent stopped. Neither of the solutes distilled at all. The 2 : 3 and 3 : 2 by volume for S1 and S2 respectively what
volume of the two solutions at equilibrium were then read (DTf )S1
would be the value of ?
on the calibration marks of the vials. The solution containing (DTf )S2
the new compound occupied 1.72 mL and the azobenzene  (Answer upto two decimal place)
solution occupied 1.02 mL. What is the molecular weight
 (Lakshya JEE Chemistry M-1)
(in g/mol) of the new compound? The mass of solvent in
solution may be assumed to be proportional to the volume SINGLE CHOICE TYPE QUESTIONS
of the solution.
 (LAKSHYA JEE CHEMISTRY M-1)
 (Lakshya JEE Chemistry M-1) 6. A dilute solution contains m mol of solute A in 1 kg of
a solvent with molal elevation constant K b; The solute
2. In water at 20°C, the Henry’s law constant for oxygen is
dimerises in solution as 2A  A2. What is correct
4.6 × 104 atm, and for nitrogen it is 8.2 × 104 atm, where
expression for the equilibrium constant for this dimer
the concentration are expressed as mole fractions. If we
formation? (DTb is the elevation in boiling point for the
are to prepare 90 mole % pure oxygen from air (successive
treatments by partially dissolving in water and then all the given solution)
K b (K b m + DTb ) K b (K b m + DTb )
gas is removed under vacuum the water), how many cycles
(a) K = (b) K =
would be necessary to achieve this result? (2DTb + K b m) 2 (DTb + K b m) 2
 (Lakshya JEE Chemistry M-1) K b (K b m + DTb ) K b (K b m - DTb )
(c) K = 2 (d) K =
3. When cells of the skeletal vacuole of a frog wee placed in (DTb - 2K b m) (2DTb - K b m) 2
series of NaCl solution of different concentrations at 6°C, it  (Lakshya JEE Chemistry M-1)
was observed microscopically that they remained unchanged
in x% NaCl solution, it shrank in more concentrated solution 7. The partial molar volumes of propanone (CH3COCH3)
and swells in more dilute solutions. Water freezes from the and butanone (CH3COCH2CH3 ) in a mixture in which
x% salt solution at –0.40°C. If the osmotic pressure of the mole fraction of propanone is 0.4 are 75 cm3 mol–1 and
cell cytoplasm at 6°C is ‘y’× 0.0821 atm, then the value of 80 cm3 mol–1. Thus, the total volume of solution of total
‘y’ is (Kf = 1.86 K mol–1 kg) mass 1 kg, is
(a) 1175 cm3 (b) 1000 cm3
 (Lakshya JEE Chemistry M-1) (c) 1200 cm3 (d) 972 cm3
4. Consider the following arrangements, in which a solution
containing 20 g of haemoglobin in 1 dm3 of the solution is
COMPREHENSION BASED QUESTIONS
placed in right compartment and pure water is placed in left

46 JEE (XII) Module-1 CHEMISTRY PW

 Comprehension I Comprehension III
10 mole of liquid ‘A’ and 20 mole of liquid ‘B’ is mixed in a cylindrical The solubility of iodine per unit volume is 200 times greater in
vessel containing a piston arrangement. Initially a pressure of 2 atm ether than in water at a particular temperature.
is maintained on the solution. Now, the piston is raised slowly and
isothermally. Assume ideal behaviour of solution and A and B are 13. If an aqueous solution of iodine, 30 mL in volume and
completely miscible. containing 2.0 mg of iodine, is shaken with 30 mL of ether
and the ether is allowed to separate, what quantity of iodine
PA° = 0.6 atm and PB° = 0.9 atm
(in mg) remains in the water layer?
 (Lakshya JEE Chemistry M-1)  (Answer upto three decimal place)
8. The pressure below which the evaporation of liquid solution
will start, is  (Lakshya JEE Chemistry M-1)
(a) 0.6 atm (b) 0.8 atm 14. What quantity of iodine (in mg) remains in the water layer
(c) 0.77 atm (d) 0.9 atm if only 3 mL of ether is used?
 (Lakshya JEE Chemistry M-1)  (Answer upto three decimal place)
1  (Lakshya JEE Chemistry M-1)
9. The pressure at which th of the total amount (by mol) of
3 15. How much iodine (in mg) is left in the water layer if the
liquid solution taken initially, will be present in the vapour extraction in (b) is followed by a second extraction, again
form, is
using 3 mL of ether?
(a) 0.283 (b) 0.791 (c) 0.600 (d) 0.652
 (Answer upto four decimal place)
 (Lakshya JEE Chemistry M-1)
10. The minimum pressure for the existence of liquid solution is Comprehension IV
(a) 0.6 atm (b) 0.8 atm A liquid mixture of benzene and toluene is composed of 1 mol of
(c) 0.77 atm (d) 0.9 atm benzene and 1 mol of toluene.
 (Lakshya JEE Chemistry M-1) Given: PT° = 32.05 mm Hg, PB° = 103 mm Hg
Comprehension II 16. If the pressure over the mixture at 300 K is reduced, at what
The freezing point of an aqueous saturated solution of I2 is pressure (in mm Hg) does the first vapour form?
–0.0024°C. More than this can dissolve in an KI solution because  (Answer upto two decimal place)
of the following equilibrium:
 (Lakshya JEE Chemistry M-1)
I2(aq) + I–(aq)_______ 
 _______I3–(aq)
17. What is the mole percent of benzene in the first trace of vapour
0.1 M KI solution dissolves 12.5 g/L of I2. formed. (Integer Type)
11. Identify the closest value of equilibrium constant KC for the
above equilibrium. (When concentrations are taking mole/L)  (Lakshya JEE Chemistry M-1)
(a) 512.7 (b) 707.2 18. If the pressure is reduced further, at what pressure
(c) 634.5 (d) 891.3 (in mm Hg) does the last trace of liquid disappear?
 (Lakshya JEE Chemistry M-1)  (Integer Type)

12. Calculate the freezing point (in K) of the resulting solution.  (Lakshya JEE Chemistry M-1)
Assume molarity to be equal to molality and also assume that
19. What is the mole percent of Toluene in the last trace of liquid?
conc. of I2 in all saturated solution is same.
 (Integer Type)
[Kf for water = 1.86 K kg mol– 1]
(a) 263.4 (b) 252.5  (Lakshya JEE Chemistry M-1)
(c) 272.6 (d) 265.7 20. What will be the pressure (in mm Hg) when 1 mol of the
 (Lakshya JEE Chemistry M-1) mixture has been vaporized?
(a) 72.56 (b) 67.29
(c) 63.52 (d) 57.46
 (Lakshya JEE Chemistry M-1)

“You may have to

fight a battle
more than once

47 JEE (XII) Module-1 CHEMISTRY PW

 ANSWER KEY
CONCEPT APPLICATION
1. (d) 2. (b) 3. (a) 4. (b) 5. [ PBº = 600 mm Hg , PAº = 400 mm Hg ] 6. [< 80 mL]
7. [65.25 g/mol]
8. vapour pressure of pure water = 20.22 Torr.
Mol. weight of non-volatile solute = 54 g/mol. 9. [0.33] 10. [5.08 K kg mole–1] 11. [π = 8.35 atm]
12. [34.89 g/mol.] 13. [i = 1.0753, Ka = 3.07 × 10–3]

BOARD LEVEL PROBLEMS

1. (b) 2. (b) 3. (c) 4. (d) 5. (d) 6. (b) 7. (b) 8. (c) 9. (d) 10. (a)
11. (c) 12. (a) 13. (d) 14. (a) 25. (I)-(d), (II)-(d), (III)-(a), (IV)-(c)

PRARAMBH (TOPICWISE)
1. (d) 2. (c) 3. (d) 4. (b) 5. (c) 6. (a) 7. (b) 8. (d) 9. (c) 10. (d)
11. (a) 12. (c) 13. (d) 14. (c) 15. (b) 16. (d) 17. (d) 18. (c) 19. (d) 20. (c)
21. (b) 22. (a) 23. (b) 24. (b) 25. (b) 26. (a) 27. (d) 28. (b) 29. (a) 30. (b)
31. (a) 32. (b) 33. (c) 34. (c) 35. (c) 36. (c) 37. (a) 38. (a) 39. (c) 40. (d)
41. (a) 42. (a) 43. (a) 44. (c) 45. (b) 46. (b)

PRABAL (JEE MAIN LEVEL)

1. (c) 2. (b) 3. (c) 4. (b) 5. (b) 6. (c) 7. (a) 8. (c) 9. (a) 10. (b)
11. (b) 12. (a) 13. (d) 14. (a) 15. (a) 16. (b) 17. (d) 18. (c) 19. (d) 20. (b)
21. (b) 22. (b) 23. (d) 24. (c) 25. (c) 26. (a) 27. (a) 28. (a) 29. (d) 30. (c)
31. (a) 32. (a) 33. (a) 34. (b) 35. (d) 36. (a) 37. (c) 38. (d) 39. (c) 40. (d)
41. (d) 42. (c) 43. (d) 44. (a) 45. (c) 46. (d) 47. (c) 48. (a) 49. [5] 50. [5]
51. [10] 52. [30] 53. [8] 54. [93] 55. [112] 56. [278] 57. [102] 58. [10]

PARIKSHIT (JEE ADVANCED LEVEL)

1. (a) 2. (c) 3. (d) 4. (d) 5. (a) 6. (c) 7. (a) 8. (b) 9. (a) 10. (b,c,d)
11. (a,c) 12. (a,c,d) 13. (b,d) 14. (b,d) 15. (a,b) 16. (a,c) 17. (a,b,c,d) 18. (a,c,d) 19. (a,b,c) 20. (a,b,c)
21. (c,d) 22. (c,d) 23. (a,b,c) 24. (b) 25. (a) 26. (b) 27. (b) 28. (c) 29. (a) 30. (b)
31. (a) 32. (c) 33. (b) 34. (d) 35. (c) 36. (d) 37. (a) 38. (d) 39. [98] 40. [20]
41. [80] 42. [78] 43. [380] 44. [160] 45. [366] 46. [4] 47. [5] 48. [85] 49. [71.42] 50. [0.23]
51. [0.67] 52. [52.5] 53. [0.56] 54. [1.04] 55. [0.20]

PYQ’s (PAST YEAR QUESTIONS)

1. (a) 2. [7] 3. [4] 4. [815] 5. [7] 6. (b) 7. [11] 8. (b) 9. (b) 10. (b)
11. [74] 12. [22] 13. (d) 14. [139] 15. [36] 16. [54] 17. [20] 18. [50] 19. [47]
20. [2.8-3.05] 21. [23] 22. [1] 23. [25] 24. (d) 25. [0.20] 26. (c) 27. (d) 28. (d)
29. (d) 30. (b) 31. [73] 32. (d) 33. (a) 34. (a) 35. [15] 36. [707] 37. [31] 38. [25]
39. [19] 40. [76] 41. [543] 42. [5] 43. (d) 44. [13] 45. (d) 46. (d) 47. [100] 48. [6]
49. [415] 50. (b) 51. [271] 52. [100.1] 53. [2.5] 54. [0.97 to 1.06] 55. (c) 56. [167] 57. (b)

PW CHALLENGERS
1. [76] 2. [7] 3. [60] 4. [5] 5. [0.82] 6. (d) 7. (a) 8. (b) 9. (b) 10. (c)
11. (b) 12. (c) 13. [0.010] 14. [0.095] 15. [0.0045] 16 [67.52] 17. [76] 18. [49] 19. [76] 20. (d)

48 JEE (XII) Module-1 CHEMISTRY PW