CHAPTER

5 Solutions

Chapter Highlights
Type of solutions, Various terms, Vapour pressure, Raoult’s law, Ideal and non-ideal solutions, Osmotic pressure, Elevation
in boiling point, Depression in freezing point, Abnormal molar mass, Colligative properties and van’t Hoff factor and various
levels of multiple-choice questions.

SOLUTIONS AND COLLIGATIVE PROPERTIES

SOLUTION Solutions of Solids in Liquids

Solution is a homogeneous mixture of two or more chemi­
cally non­reacting substances whose composition can be
varied within certain limits. A solution is regarded as a
single phase having more than one components.
A solution which contains only two components is called
a binary solution.
The component which is present in smaller amount is
called the solute and the other present in larger amount is
called the solvent.
The following table shows the list of solutions and their
examples.
• Saturated solution is a solution which remains in
contact with excess of solute.
• The amount of solute dissolved per 100 g of sol­
vent in a saturated solution at a specific temperature
represents the solubility of the solute.
• For exothermic substances such as KOH, CaO,
Ca(OH)2, M2CO3, M2SO4 etc., solubility is inversely
proportional to temperature. (M = Alkali metals)
• For endothermic substances such as NaCl, KNO3,
NaNO2, glucose etc., solubility is directly propor­
tional to temperature.

Solubility of Gases
Table 5.1 Types of Solutions
Solute Solvent Examples • Solubility of gases is mostly expressed in terms of
absorption coefficient, that is, the volume of the gas
Solid Solid Alloys, stones
(at NTP), dissolved by unit volume of solvent, at 1
Solid Liquid Sugar, salt in water
atm pressure and a specific temperature.
Solid Gas Iodine vapours in air
• The solubility of a gas in a liquid depends upon:
Liquid Solid Mercury in metal amalgams
1. Temperature Solubility is inversely proportional
Liquid Liquid Alcohol in water
to temperature as dissolution of a gas is exo­
Liquid Gas Moist air thermic in most cases.
Occluded hydrogen on Pd, Pt, 2. Nature of gas Gases having a higher value of van
Gas Solid
Ni etc. der Waals force of attraction, that is, gases that are
Gas Liquid Aerated water more easily liquefied are more soluble. For exam­
Gas Gas Air ple, SO2 and CO2 are more soluble in water than
O2, N2 and H2.
5.2 Chapter 5

3. Nature of solvent Gases which can ionize in one litre of the solution and it is denoted by M.
aqueous solution are more soluble in water as
compared to the other solvents. • When molarity of a solution is one, it is called a
molar solution.
4. Pressure of the gas (Henry’s law) According to Weight of solute in gram
M = _____________________
this law, “At constant temperature, the solubility Molar mass × Volume in litre
of a gas in a given volume of liquid is directly M1 V1 = M2 V2 = M3 V3
proportional to the pressure of the gas over the
liquid.” M1V1 + M 2 V2
MR =
V1 + V2 or VT
m∝P
M A VA − M B VB
=
m = KP VTotal
m
__
or p = K (At constant
temperature) Molality
Here K = Henry’s constant
It is the number of moles or gram moles of solute dissolved
• Henry’s law is obeyed only when per kilogram of the solvent. It is denoted by m.
1. Pressure is not too high. Weight of solute in gram
________________________
m = Molar mass × Wt of solvent in kg
2. Temperature is not too low.
3. Gas does not dissociate.
• If molality of a solution is one, it is called molal
4. Gas is not highly soluble in the solvent. solution.
5. Gas does not chemically react with the solvent. • Concentration of one molal solution is less than that
of one molar solution.
FA C T TO R E M E M B E R • Molality is used preferrably over molarity in
experimental calculations as molality is tempera­
The volume of the dissolved gas does not depend upon
pressure at a particular temperature. ture independent while molarity is affected by
temperature.
Expression of Concentration of Solution Normality
Concentration
It is the number of ram equivalents of solute present in
It is the amount of solute present in one litre of solution. It one litre of the solution and it is denoted by N.
is denoted by C or S. Weight of solute in gram
Weight of solute in gram W N = ________________________
Equivalent mass × Volume in litre
C or S = = g/L
Volume in litre V • Relation between normality and molarity.
C=N×E N × Eq. wt = Molarity × Molar mass
N = Molarity × Valency
Concentration in parts per million (ppm) N = Molarity × Number of H+ or OH ion.
The parts of a component (A) per million parts (106) of
Formality
the solution.
Mass of A
ppm (A) = __________________
Total mass of the solution × 10
6 It is the number of gram formula present in one litre of
solution. It is denoted by F.
Concentration in parts per billion (ppb) Weight of solute in gram
F = _____________________
Formula wt × Volume in litre
The parts of a component (A) per billion parts (109) of the
• It is applicable in case of ionic solids like NaCl.
solution.
Mass of A
ppb (A) = __________________
Total mass of the solution × 10
9
Mole fraction
Molarity It is the ratio of moles of one component to the total
It is the number of gram equivalents of solute present in number of moles present in the solution. It is expressed
 Solutions 5.3

• The variation of vapour pressure with temperature

by X, for example, for a binary solution two component A
can be given by Clausius­Clapeyron equation as
and B,
follows:
nA ∆ Hvap
xA = ______
n +n
A B
P2 ______
log10 __
P = 2.303 R
1
T2 – T1
______
T T ( 1 2
)
nB
xB = ______
nA + nB
Vapour Pressure of a Solution
 w • When a miscible solute is added to a pure solvent, it
Weight per cent   results in the formation of solution. As some molecules
 W
of solute replace the molecules of the solvent from
It is weight of solute present in 100 g of solution. the surface, the escaping tendency of solvent mole­
cules decreases. This causes a lowering of the vapour
 v pressure.
Volume per cent  
 V • The vapour pressure of a solution is less than that of
It is volume of solute present in 100 mL of solution. pure solvent.
• If the vapour pressure of a solvent is p° and that
Moles of solute
Mole per cent = ______________________
Total moles present in solution × 100
of solution is ps then, lowering of vapour pressure
= p° – ps
Mass fraction Mass fraction of any component in the • The vapour pressure of a solution decreases as the sur
solution is the mass of that component divided by the total face area occupied by the solvent molecules decreases
mass of the solution. For a solution containing wA g of A and density increases.
and wB g of B, RAOULT’S LAW
WA
Mass fraction of A (XA) = _______
WA + WB Raoult’s Law for Volatile Solutes
WB Raoult’s law states that in a solution, the vapour pressure
Mass fraction of B (XB) = _______
WA + WB of a component at a given temperature is equal to the mole
So, xA + xB = 1 fraction of that component in the solution multiplied by the
vapour pressure of that component in the pure state.
The total vapour pressure P of a solution containing
FA C T TO R E M E M B E R two components A and B is
When one mole of a solute is present in one litre of solution pA = p0A × xA
at 0°C it is called one demal solution. pb = p0b × xB
1 Molar > 1 Molal P = pA + pB = p0A xA + p0B xB
As we know that
VAPOUR PRESSURE xA + xB = 1
Vapour Pressure of a Liquid xA = (1 – xB)
P = (1 – xB)p0A + p0B xB
• Vapour pressure is the pressure exerted by vapours
when they are in equilibrium with the liquid phase at P = (p0B – p0A) xB + p0A
a given temperature. It depends on the nature of the 0

liquid and temperature. +P B PB

PT = PA
0
• Vapour pressure of pure liquid is always greater than PA
the vapour pressure of its solution. 0
. XB
Vapour Pressure

• Vapour pressure of a liquid helps us to have an idea =P B

P B
of forces of attraction between the molecules of a PA =
PA 0
liquid. More the force of attraction, lower is the .X
A
vapour pressure and vice versa.
• Vapour pressure of a liquid increases with increase
in temperature due to increase in kinetic energy of
XA = 1 Mole Fraction XA = 0
molecules. XB = 1
XB = 0

Figure 5.1 Vapour Pressure Diagram for Ideal Solution

5.4 Chapter 5

Raoult’s Law for Non-volatile Solutes Types of non-ideal solutions

Raoult’s law states that the relative lowering of
vapour pressure of a solution containing a non­volatile (a) Non-ideal solutions showing positive deviations
solute is equal to the mole fraction of the solute in the Positive deviation occurs when total vapour pressure for
solution. any mole fraction is more than what is expected according
P0 – Ps n2
to Raoult’s law. This happens when the new interactions
_____
P0
= _____
n1 + n2 = x2 are weaker than the interaction in the pure component
(A – B < A – A or B – B interactions).
Here, x2= Mole fraction of solute
• ∆H = +ve, ∆V = +ve
n1 = Moles of solvent
• (V.P)obs > (V.P)exp
n2 = Moles of solute
ps = Vapour pressure of the solution • PT > PA0 X A + PB0 X B
p0 = Vapour pressure of pure solvent • It forms minimum boiling azeotrops, for example,
C2H5OH + cyclohexane. The H­bonding present in
pure C2H5OH are cut off on adding cyclohexane. For
Ideal Solutions
such solution, ∆V and ∆H are positive.
Ideal solutions are the solutions in which solute­solute
and solvent­solvent interactions are almost similar to Examples:
solute­solvent interactions (A – B = A – A or B – B 1. Acetone + carbon disulphide,
interactions) and such solutions satisfy the following 2. Acetone + benzene
requirements: 3. Carbon tetrachloride + chloroform or Toluene
1. They obey Raoult’s law for all ranges of concen­ 4. Methylalcohol + water
trations and temperature. 5. Acetone + C2H5OH
2. ∆H (mix) = 0
+P B
3. ∆V(mix) = 0 PT > PA 0
PB
4. (V.P)obs = (V.P)exp.
(B.P)obs = (B.P)exp. 0
PA PB
5. No dissociation or association takes place here.
Vapour Pressure

6. No chemical reaction between solute and solvent.

7. It does not form azeotrope mixture.
P
Examples: A

1. Benzene + toluene
2. Hexane + heptane
XA = 1 Mole Fraction XA = 0
3. Ethyl bromide + ethyl iodide XB = 0 XB = 1
4. Chlorobenzene + bromobenzene
Figure 5.2 Positive Deviations
5. CCl4 + SiCl4
6. All dilute solutions (b) Non-ideal solutions showing negative deviations
Negative deviation is seen when total vapour pressure for
Non-Ideal Solutions any mole fraction is less than that expected from Raoult’s
Non­ideal solutions are the solutions in which solute­ law. This happens when the new interactions are stronger
solvent interactions are different from solute­solute and than the interactions in the pure components (A – B >A – A
solvent­solvent interactions. These solution do not obey or B – B interactions).
Raoult’s law for all concentrations and • ∆H = –ve, ∆V = –ve
1. ∆H (mix) ≠ 0 • (V.P)obs. < (V.P)exp.

2. ∆V (mix) ≠ 0 • PT < PA0 X A + PB0 X B

 Solutions 5.5

• It forms maximum boiling azeotrope, for example, (a) This is formed by that composition of a non­ideal
CHCl3 + CH3COCH3. For such solutions ∆V and ∆H solution showing positive deviation for which the
are negative. vapour pressure is maximum.

Examples: These comprise non­ideal solutions which

show positive deviation from Raoult’s law and
1. Chloroform + benzene for which, the vapour pressure is maximum.
2. Acetone + aniline For example, ethanol (95.5%) + water (4.5%)
3. Nitric acid + water mixture boils at 351.5 K.
4. Acetic acid + pyridine (B.P. of ethanol = 78.1° C, B.P. of water = 100° C)

(b) Such mixtures on distillation will give first frac­

0
PB tion upto point M in pure state. After this, the tem­
0 perature will rise and the second component will
PA PT < PA+PB
pass over. Hence in such solutions also complete
separation is not possible.
Vapour Pressure

PB (c) The figure shows maximum vapour pressure at

point M and therefore solution has lowest boiling
point.
PA

XA = 1 Mole Fraction XA = 0
XB = 0 XB = 1
o ur M Vapo
Figure 5.3 Negative Deviations Vap ur
PA0 id
L iqu Liquid
Azeotropic Mixture
Vapour Pressure

PB0

An azeotropic mixture is a mixture of two liquids having

the same boiling point. These two liquids cannot be sepa­
rated by simple distillation because of similar boiling point XA = 1 XA = 0
of the liquids. These mixtures are thus called constant­boil­ XB = 0 XB = 1
ing mixtures. These are formed by non­ideal solutions.
Mole Fraction

Azeotropic Mixture and Composition Curves: Figure 5.4

• These are the mixture of two liquids which boils at one

particular temperature likea pure liquid and distils over
2. Azeotropic Mixtures with Maximum Boiling Point:
in the samecomposition, i.e., these are constant boiling
mixtures. These are formed by non­ideal solutions.
• The study of the vapour pressure curves of such mis­
cible liquids is of great help inseparating the constit­
uents of the liquid mixtures by distillation.
• The separation by fractional distillation is possible
only when the vapour phase has a composition dif­
ferent from that of the boiling liquid mixture.
Types of azeotropic mixtures
These are of the following two types:
1. Azeotropic Mixtures with Minimum Boiling
Point: The mixture of two liquids whose boiling point
is less than either of the two pure components.
The mixtures of two liquids whose boiling point is more
than either of the two pure components.
(a) This is formed by that composition of a non­ideal
solution showing negative deviation for which the
vapour pressure is minimum.
e.g.,– HNO3 (68%) + water (32%) mixture boils at
393.5 K.
e.g., an aqueous solution of hydrochloric acid
when subjected to distillation gives initially pure
water and later forms a constant boiling mixture at
100°C which contains 20.24 % acid.
(b) In a mixture of two volatile liquids A and B, if A
is more volatile and present in excess, then during
distillation the vapours will be rich of component
5.6 Chapter 5

A and the liquid part will be richer in component
B. Finally we reach the point N where vapour
pressure is minimum and the boiling point is
maximum as shown in the figure.
(c) At this stage, the mixture distills unchanged in
composition i.e., complete separation of compo­
nents from this type of solution into pure state is
impossible.
PA0 Vapo
u r
o
Vapour Pressure
Solubility of Partially Miscible Liquids
Conjugate solutions
Many liquids are partially miscible and form two liquid
layers at a particular temperature. Such liquid solutions in
which different compositions of components coexist are
called conjugate solutions, for example, phenol and water.
Critical temperature
The miscibility of liquids varies with temperature. At a
certain temperature the two layers become completely
miscible. This temperature is called critical temperature or
consolute temperature.
ur

Vap PB0
Liq COLLIGATIVE PROPERTIES
uid id
N u
Liq
Colligative properties are properties of a solution which
depend only on the number of particles like ions or mol­
XA = 1 XA = 0
XB = 0 XB = 1 ecules of the solute in a definite amount of the solvent but
not on the nature of the solute. These are properties of a
Mole Fraction dilute solution. These are as follows:
Figure 5.5 1. Relative lowering of vapour pressure
2. Osmotic pressure
3. Elevation in boiling point
3. Mixture Showing Ideal Behaviour or Zeotropic
Mixture: Those liquid mixtures which distill with a 4. Depression in freezing point
change in composition are called zeotropic mixture.
Relative Lowering of Vapour Pressure
(a) For this type of containing liquids A and B, vapour
pressure composition curve is a straight line. On When a non­volatile solute is added in a volatile solvent,
distillation, A being more volatile, will collect as the V.P of solution becomes less than the V.P of pure sol­
distillate. vent. It is due to increase in density which decreases rate
(b) The remaining fraction will be poorer in A and  1 
of evaporation.  r ∝ 
richer in B. By repeating the process of distillation  d
again and again, we can get both the components
in pure state, e.g., methanol­water mixture. If p0 = vapour pressure of pure solvent
p = vapour pressure of solvent in solution
• The lowering of vapour pressure
Vap
∆p = (p0 – p)
our o
fA • The relative lowering of vapour pressure is defined
P0 as the ratio between lowering of vapour pressure and
A
the vapour pressure of pure solvent.
Vapour Pressure

Liqu
id o
fB P0 Dp p0 - p
B
= = Realtive lowering of vapour pressure
p0 p0
XA = 1 XA = 0 • When a solution is prepared by mixing the non­vola­
XB = 0 XB = 1 tile solute B and solvent A
xA + xB = 1
Mole Fraction
xB = 1 – xA
Figure 5.6
 Solutions 5.7

Here, xB is the mole fraction of solute. • It is denoted by P or π.

pA
___ • It is measured by Pfeffer’s method, Berkely­Hartley’s
As = xA
p0A method, Townsend’s method.
PA
___
1– = 1 – xA = xB 1 – xA = xB Van’t Hoff equation of osmotic pressure
p0A
p0A – pA ∆p _____ π = CST
______ ___ n
= xB = 0 = n + N Here, π = Osmotic pressure
p0A pA
Here, n = Number of moles of the solute C = Concentration of solution in mol/L
N = Number of moles of the solvent S or R = Solution constant
(≈ 0.0821 Latm/degmol)
• In a dilute solution, N is far greater than n, and hence,
n
__ w/m
____ wM
____ T = Absolute temperature in K
xB = N = W/m = Wm
So, π α C (At constant temperature)
Here, w = Weight of solute
n
π = __
V ST (C = n/V)
W = Weight of solvent π V = nST
m = Molecular weight of solute Here, n = Numbers of moles the solute,
M = Molecular weight of solvent V = Volume of solution
w
PA0 − PA ∆P wM m × M πV = __
M RT
So, = 0 = =
PA0 P Wm 1000 As n = w/M
M = Molar mass of solute
m = molality
w = Gram weight of solute
• The molecular weight of a solute can be determined
with the help of the relative lowering of vapour pres Determination of molecular weight from osmotic
sure method. pressure
ST
M ___
__
W= π
FA C T TO R E M E M B E R WST
M = ____
π
R.L.V.P. is measured by ostwald walker method. • When solute is dissolved in V litre then
p − ps Loss in mass of solvent bulbs πV = nST (n = W/M)
=
p Gain in CaCl2 tube W
πV = __
M ST
W × ST
______
M = π×V
Osmosis
In osmosis, there is a net flow of solvent molecules from • Accurate molecular weight is obtained under follow
ing conditions
the solvent to the solution or from a less concentrated
solution to a more concentrated solution across a semi­ 1. Solution must be very dilute.
permeable membrane (membranes of animal origin, 2. Solute must be non­volatile.
membranes made from Cu2[Fe(CN)6], Ca3(PO4)2 etc.) 3. Solute should not undergo dissociation or asso­
Osmosis was first observed by Abbe Nollet in 1748. ciation in the solution.
• When height is involved then,
Osmotic Pressure π = hdg
Isotonic solution Solutions having equal molar con­
• Osmotic pressure is the equilibrium hydrostatic pres­ centrations or equal osmotic pressures are called isotonic
sure of the column set up as a result of osmosis. solutions. For example, 0.91 % solution of pure aqueous
It is the minimum pressure that must be applied on NaCl is isotonic with human RBC.
the solution to prevent the entry of the solvent into P1= P2 or π1 = π2
the solution through the semi­permeable membrane.
w1
_____ w2
_____
It is the minimum pressure needed to apply on a M1 V 1 = M2 V 2
solution to make its vapour pressure equal to vapour
• In an isotonic solution net osmosis is zero.
pressure of the solvent.
5.8 Chapter 5

Elevation in Boiling Point pressure of the solution, solid form of a solution separates
out at a lower temperature.
Boiling point is the temperature of a liquid at which
its vapour pressure becomes equal to the atmospheric Solvent
pressure. Solution
Solvent

Vapour Pressure
ΔTf
Vapour Pressure

ΔTb
TSolution T
Temperature
Figure 5.8 Depression in Freezing Point
T TSolution
Temperature
Figure 5.7 Elevation in Boiling Point • It is the decrease in freezing point of a solvent due to
the addition of a non volatile solute.
• Elevation in the boiling point is also termed as
• This is also termed as cryoscopy.
ebul-lioscopy.
• Depression in freezing point (∆Tf) = Freezing point
• It is the increase in boiling point of a solvent due to of pure solvent – Freezing point of solution
the addition of non­volatile solute in it. It is denoted • It is measured by Beckmann’s thermometer method
by ∆Tb. and Rast’s method.
• It is measured by Lands Berger’s method and • ∆Tf α m or ∆Tf = Kf ⋅ m
Koltrell’s method.
w 1000
• ∆Tf = Kf ___ ____
mw × W
• The elevation in boiling point is given as
Kf × w × 1000
___________
∆ Tb α m or ∆ Tb = Kb . m • mw = ∆ Tf × W
w 1000
∆ Tb = Kb × ___ ____
Mw × W mw = mol. wt
k b × 1000 Here w = Weight of solute
Molecular weight of solute, mw
∆Tb × W W = Weight of solvent
Kf = Molal depression constant or cryo­
Here w = Weight of solute scopic constant
W = Weight of solvent • If molality of the solution is one, then

Kb = Molal elevation constant ∆Tf = Kf

2
RT
______
or ebullioscopic constant. • Kf = 1000 L
f
If molality of the solution is one, then Here Lf = Latent heat of fusion.
∆ Tb = K b • If molar depression in freezing point constant (K) is
RT2
Kb = ______
1000 Lv
to be calculated, then replace 1000 with 100 in the
above mentioned formula, that is, K = 10 Kf
Here Lv = Latent heat of vaporization.
• If molar elevation in boiling point constant (K) is Van’t Hoff Factor
to be calculated, then replace 1000 with 100 in the
• Certain solutes which undergo dissociation or
above mentioned formula, that is, K = 10 Kb.
association in solution, are found to show abnormal
Depression in Freezing Point molecular mass. Due to this, the colligative property
becomes abnormal which can be explained by van’t
Freezing point is the temperature at which the liquid and
Hoff factor.
the solid form of the same substance are in an equilibrium
Normal molar mass
and have the same vapour pressure. Due to lower vapour i = _______________
Observed molar mass
 Solutions 5.9

Observed colligative property

i = _____________________
Normal colligative property
SOLVED EXAMPLES
Actual number of particles or species
i = ____________________________
Expected number of particles or species Concentration Terms
• For solutes showing dissociation, the van’t Hoff fac­ 1. Determine the molarity of a 40% solution of HCl
tor i > l.
which has a density of 1.2 g mL–1.
i = 2 for MX, MNO3, MSO4 Solution
i = 3 for MX2, M2O, M(NO3)2 Molarity
% strength _______
i = 4 for MX3, K3 Fe(CN)6 = Sp. gravity × ________
100 × mol1wt
40
i = 5 for M2X3, M2(SO4)3 M3(PO4)2, K4 Fe(CN)6 = 1.2 × ___ 1
_____
100 × 0.0365 = 13.15 M
2. 8.0575 × 10–2 kg of Glauber salt is dissolved in water
For example, FeCl3 Fe3+ + 3C1– for i = 4. to obtain 1 dm3 of a solution of density 1077.2 kg m–3
Calculate the molarity, molality and mole fraction of
• For solutes showing association, the van’t Hoff factor Na2SO4 in the solution.
i < 1. For example, dimerization of acids like benzoic
Solution
acid in benzene.
Volume of solution = 1 dm3
• For solutes showing neither dissociation nor associa­
tion, the van’t Hoff factor i is 1, for example, urea, Density = 1077.2 kg m–3
glucose, sucrose. Mass of Na2SO4 = 1077.2 – 1000
i–1
____ = 77.2 g in 1 litre of solution
• Degree of dissociation, α = n – 1
77.2
Here n = Number of species formed after dissociation Moles of Na2SO4 = ____
142 = 0.5436
Molarity = 0.5436 M
n (1 − i ) i −1
• Degree of association, α = = Molality = 0.5436 m
n −1 1 0.5436
−1 Mole fraction = ___________
0.5436 + 55.55 = 0.0096
n
3. Calculate the molality of one litre solution of 93%
Here n = Number of species formed after association. H2SO4 (weight/volume). The density of solution is
1.84 g/mL.
FA C T TO R E M E M B E R Solution

1. ∆Tb = i.Kb M 3. π = iCRT 93% H2SO4 solution (weight/volume) means that

P_____
– Ps n
_____ 100 mL solution contains = 93 g of H2SO4
2. ∆Tf = i. Kf M 4. P =i n+N Hence, 1000 mL solution contains = 930 g of H2SO4
Weight = Volume × Density
1000 × 1.84 = 1840 g solution contains
Measuring Molecular Mass of Polymers = 930 g of H2SO4
In this solution, weight of solvent = 1840 – 930
Molecular mass of polymers is best determined by
osmotic pressure method; firstly, because the values = 9l0g = 0.910 kg
given by other colligative properties are so low that they Molality of H2SO4
cannot be measured accurately, and secondly, osmotic
Wt. of H 2SO 4 \ Mol. wt. of H 2SO 4
pressure measurements can be made at room tempera­ =
ture and do not require heating which may change the Wt. of solvent in kg
nature of the polymer. 930/98
= _____
0.910 = 10.428
4. Calculate (i) molarity and (ii) molality of a sulphuric
• When dissociation occurs, colligative properties acid solution of specific gravity 1.198 containing 27%
gain a higher value while on association the reverse H2SO4 by weight.
occurs.
5.10 Chapter 5

Solution Solution
(i) 27% H2SO4 by weight means that 100 g of p = 17.54 mm of Hg
p – ps = 0.30 mm of Hg
solution contains = 27 g of H2SO4
Weight
________ 100
____ w = 20 g
Volume = Sp. gravity = 1.198 = 83.47 mL W= 100 g
M = 18 for water
As 83.47 mL solution contains = 27g of H2SO4 m=?
So 1000 mL solution contains According to Raoult’s law (for dilute solution)
27 × 1000g
= ________
83.47 of H2SO4 p – ps _____
_____ w×M
p = m×W
= 323.47 g of H2SO4 0.30 ______
____ 20 × 18
Strength in g/litre 1754 = 100 × m
Motlarity of solution = _____________ 20 × 18 × 17.54
Mol. wt of H2SO4
m = ____________
100 × 0.30 = 210.48
323.47
= _____
98 = 3.30 M 7. The vapour pressure of benzene at a certain tempera­
(ii) 100 g solution contains = 27 g of H2SO4 ture is 640 mm of Hg. A non­volatile and non­
electrolyte solid weighing 2.175 g is added to 39.09
So, the weight of solvent = 100 – 27 = 73 g
g of benzene. The vapour pressure of the solution is
= 0.073 kg 600 mm of Hg. What is the molecular weight of solid
Molality of solution substance?
Wt. of H 2SO 4 \ Mol. wt. of H 2SO 4 Solution
=
Wt. of solvent in kg p for benzene = 640 mm of Hg
27
__ ps for solution = 600 mm of Hg
_____
98
= 0.073 = 3.77 m Weight of non­volatile and non­electrolyte solute
5. A 6.90 M solution of KOH in water contains (w) = 2.175 g
30% by weight of KOH. What is the density of the Weight of solvent (benzene) = 39.0 g
solution? Mol. wt of benzene (M) = 72 + 6 = 78
Mol. wt of non­volatile and non­electrolyte solute
Solution (m) = ?
Molarity of KOH solution = 6.90 M p - ps w M
=
Mol. wt of KOH = 39 + 16 + 1 = 56 p m W
Weight of KOH in one litre solution 640 - 600 2.175 78
= Molarity × Mol. wt =
640 m 39
= 6.90 × 56 = 386.4 g m = 69.60
Since the solution of KOH is 30% it means that 30 g 8. The vapour pressure of an aqueous solution of
of KOH are present in glucose is 750 mm of Hg at 373 K. Calculate the
100
___ molality and mole fraction of the solute.
30 × 386.4 g of solution
= 1288 g of solution Solution
Weight in g 1288 g
Density = __________ _______
Volume in mL = 1000 mL At 373 K vapour pressure of water = 760 mm of Hg
= 1.288 g mL –1 p - ps w M
=
p m W
Raoult’s Law
p - ps 1000
= Molality
6. The vapour pressure of water at 20°C is 17.54 mm. of p M
Hg When 20 g of a non­ionic substance is dissolved 760 – 750 ____
_______ 1000
× 18 = Molality of solution
in 100 g of water, the vapour pressure is lowered by 760
0.30 mm of Hg. What is the molecular weight of the Molality of solution = 0.73 m
substance?
 Solutions 5.11

p - ps n If p0A = 100, then pA = 80 mm of Hg

p n+N W = 22 g, m = 128 g mole–1
p - ps M = 114 g
Mole fraction of solute = w × 114
100 – 80 ________
_______
p 80 = 128 × 228
760 – 750 10
= _______
760 = ___
760 = 0.0131 w = 64 g.
9. The vapour pressure of pure benzene at 25°C is 639.7 12. The vapour pressure of pure benzene at a certain
mm of Hg and vapour pressure of a solution of a solute temperature is 640 mm of Hg. A non­volatile non­
in C6H6 at the same temperature is 631.9 mm of Hg. electrolyte solid weighting 2.175 g is added to 39.0 g
Find the molality of solution. of benzene. The vapour pressure of the solution is 600
mm of Hg. What is the molecular mass of the solid
Solution
substance?
p = 639.7 mm of Hg
ps = 631.9 mm of Hg Solution
M for benzene = 78 According to Raoult’s law,
p - ps 1000 w × M ______
_____ pA0
Molality of solution = MB = × 0
p M W p A – pA
639.7 – 631.9 1000
= __________
639.7 × ____
78
w = 2.175 g, W = 39.0 g
7.8 1000
= _____ ____
639.7 × 78 = 0.156 m
M = 78, m = ?

10. A solution of a non­volatile solute in water freezes at p0A = 640 mm of Hg

–0.30°C. The vapour pressure of pure water at 298 K is pA = 600 mm of Hg
23.51 mm of Hg and Kf for water is 1.86 degree/ molal. 2.175 × 78 600
Calculate the vapour pressure of this solution at 298 K. m = ________
39.0 × _______
640 – 600 = 65.25
2.175 × 78 600
Solution = ________ ___
39.00 × 40 = 65.25
∆Tf = Kf × m
According to Raoult’s law Elevation in Boiling Point and Depression
p0A – pA _____
_______ w × M w × 1000 × M in Freezing Point
pA = m × W = ___________
m × W × 1000
p0A – pA
_______ 13. Calculate the boiling point of a 5% solution of cane
PA
M
= m (molality) × ____
1000 sugar (C12H22O11). Molal elevation constant for water
p0A – pA ___
_______ ∆T is 0.52 K kg mol–1.
pA
M
= K f × ____
1000
f
Solution
p0A = 23.51 mm of Hg
w = 5 g, W = 95 g
Kf = 1.86 K/molal
m = 342, Kb = 0.52
M = 18 K × w × 1000
∆Tb = ___________
b
m×W
∆Tf = 0.3
0.52 × 5 × 1000
23.51 – pA ____
________ 0.3 18 = ____________ = 0.08 K
PA = 1.86 × ____
1000 = 23.44 mm of Hg
342 × 95
boiling point of solution, T1 = T0 + ∆Tb
11. Assuming ideal behaviour, what mass of a non­volatile
solid of molar mass 128 g mole–1 would have to be = 373 + 0.08
dissolved in 228 g octane (CgH18) to lower the vapour (As Tb = boiling point of water = 373 K)
pressure of octane by 20%?
= 373.08 K
Solution
14. Calculate the elevation in boiling point when 12.5 g of
According to Raoult’s law, urea is dissolved in 170 g of water. Molecular mass of
p0A – pA _____
______ w×M urea is 60 and molal elevation constant of water is 0.52
pA = m × W
K kg mol–1.
5.12 Chapter 5

Solution W = 161.29g
w = 12.5 g Hence amount of ice separated from 200 g water =
m = 60 200 – 161.29 = 38.71 g.

Kb = 0.52 K kg mol–1 18. The freezing point of a solution containing 50 cm3 of

ethylene glycol in 50 g of water is found to be –34°C.
∆Tb = ? Assuming ideal behaviour, calculate the density of
Kb × w × 1000 ethylene glycol (Kf for water = 1.86 K Kg mol–1).
∆Tb = ___________
m×W Solution
12.5 × 0.52 × 1000
= ______________
60 × 170 = 0.63 K Ethylene glycol = 50 cm3
15. 1.5 g of an unknown substance was dissolved in 7.5 g Kf = 1.86 K kg mol–1
of camphor and it was found that the melting point of Mass of ethylene glycol (w) = V × d = 50 × d g
camphor was depressed by 5.3°C. If Kf is 39.75, find Mass of water (W) = 50 g
the molecular mass of the solute.
∆Tf = 34°C
Solution Kf × w × 1000
__________
∆Tf = m×W
K × w × 1000
m = ___________
f
W × ∆T 1.86 × 50 × d × 1000
_______________
f 34 = 62 × 50
39.75 × 1.5 × 1000
= ______________
7.5 × 5.3 = 150 d = 1.133 g/cm3
16. Addition of 0.643 g of a compound to 50 mL of benzene
(density = 0.879 g/mL) lowers the freezing point from Osmotic Pressure
5.51°C to 5.03°C. If Kf for benzene is 5.12 K kg mol–1,
calculate the molecular weight of the compound. 19. Osmotic pressure of a solution containing 7 g of a
protein per 100 mL of solution is 25 mm of Hg at
Solution 37°C. Calculate the molecular mass of the protein. R =
Kf = 5.12 K kg mol–1 0.082 L atm mol–1 K–1.
w = 0.643 g Solution
w RT
∆Tf = T0 –T1 = 5.51 – 5.03 = 0.48 m = ____
πV
W = 43.95 (m = v × d = 50 mL × 0.879) w=7g
Kf × w × 1000
__________
m = ∆T × W R = 0.082 L atm mol–1 K–1
f
T = 37 + 273 = 310 K
5.12 × 0.643 × 1000
= ______________ 25
0.48 × 43.95 π = ___
760 atm
= 156 V = 100 mL = 0.1 L
7 × 0.082 × 310 × 760
17. Calculate the amount of ice that will separate out on cool­ m = ________________
25 × 0.1 = 54093.7
ing a solution containing 50 g of ethylene glycol in 200 g
20. Calculate osmotic pressure at 25°C of 3% solution of
water to –9.3°C. (Kf for water = 1.86 K kg mol–1).
urea (mol. wt. of urea = 60).
Solution
Solution
w = 50 g, ∆Tf = 9.3°C
T = 273 + 25 = 298 K
Kf = 1.86 K kg mol–1
3 % urea solution means 3 g of urea is present in
m = 62
100 mL of solution
W=?
Weight of solute 3
Kf × w × 1000
__________ n = ____________ __ __ 1
Mol. wt of solute = 60 = 20
∆Tf = m×W
V = 100
1.86 × 50 × d × 1000
_______________
9.3 = 62 × 50 R = 82.1 arm cc/degree × mol
 Solutions 5.13

PV = nRT 23. Calculate the boiling point of a onemolar aqueous

82.1 × 298 solution (density 1.04 g mL–1) of potassium chloride.
nRT __
P = ____ 1
V = 20 ×
________
100 = 12.2329 atm.
(Kb for water = 0.52 K kg mol–1. Atomic mass of K =
= 12.2329 atm. 39, Cl = 35.5)
21. Calculate the osmotic pressure of a solution contain­ Solution
ing 6.00 g urea and 9.00 g glucose in one litre of
solution at 27°C. Molar mass of KCl = 74.5
Solution Mole of KCl = 1
6 Mass of solution = V × d = 1000 mL × 1.04
6 g urea = __ 1
__
60 = 10 = 0.1 mol urea = 1004 g
9
9 g glucose = ___ 1
__
180 = 20 = 0.05 mol glucose Mass of solvent = Mass of sol – Mass of solute
= 1004 – 74.5 = 929.5 g
Total moles = 0.1 + 0.05 = 0.15 mol
Molality = No. of moles of solute (n) × 1000
Volume = 1 L
Weight of solvent in g (W)
Concentration = 0.15 mol/L or 0.15 M 1 × 1000
= _______
929.5 = 1.07 m
Osmotic pressure = C. R. T
∆Tb = 1 × Kb × m
= 0.15 × 0.082 × 300
= 2 × 0.52 × 1.07
= 3.69 atm. = 1.1128 K.

Van’t Hoff Factor Boiling point of solution = T0 + ∆Tb

22. A decimolar solution of potassium ferrocyanide at
300 K is 50% dissociated. Calculate the osmotic pres­
sure of the solution, R = 0.082 L atm mol–1 K–1.
24. To 500 cm3 of water, 3.0 × 103 kg acetic acid is added.
Solution
K4Fe(CN)6 4K+ + [Fe(CN)6]4–
As one molecule of potassium ferrocyanide isso­
ciates into five particles.
= 373 + 1.1128
= 374.1128 K
If 23% of acetic acid is dissociated, what will be the
depression in freezing point? Kf and density of water
are 1.86 K. kg mol–1 and 0.997 g cm–3 respectively.
Solution

So, M = 5, ∆Tf = Kf × molality × (1 + α)

Degree of dissociation a = 50 % = 0.5 for CH3COOH
For dissociation CH3COOH CH3COO– + H+
i–1
α = _____ 1 0 0
m–1
1–α α α
i–1
0.5 = ____
5–1
As α = 23 % = 0.23,
i=3
mol of CH COOH
Osmotic pressure (π) = iCRT Molality = ______________
3
mass of water in kg
i=3 3.0 × 10–3 × 1000
= _____________
60 × 500 × 0.997 = 0.10
1
C = __
10 mol L
–1

1000
R = 0.082 L atm mol–1 K–1
∆Tf = 1.86 × 0.1 × 1.23 = 0.288 K
T = 300 K
3 × 1 × 0.082 × 300
π = ______________
10 = 7.38
5.14 Chapter 5

CONCEPTS AT A GLANCE
 In a mixture of two solutions, the solution with lower
osmotic pressure is hypotonic while solution with higher
osmotic pressure is hypertonic.
 The outflow of fluid from the plant cells placed in a hyper-
tonic solution is known a plasmolysis (shrinkage of plant
cell).
 At freezing point, solid and liquid are in equilibrium so, they
have the same vapour pressure.
 When on cooling a solution to its freezing point, the crys-
tals of solvent are separated first.
 Semi-permeable membrane is required in osmosis but not
in diffusion.
 In diffusion, a substance moves from a region of its higher
concentration to regions of its lower contraction
 In reverse osmosis, flow of solvent is from higher to lower
concentration. For example, desalination of sea water.
 Copper ferrocyanide [Cu2Fe(CN)6] is a chemically prepared
semi-permeable membrane.
 Plant and trees absorb water from soil by osmosis.
 Osmotic pressure is mainly calculated by Berklay and
Hartley method.
 Townsend method is used to find the osmotic pressure
of non aqueous solution without using semi-permeable
membrane.
 6% urea solutions and 0.1 M glucose solutions are isotonic.
 The mole fraction of the more volatile component is always
greater in vapour phase than in solution phase (Konowaloff
rule).

TOOL BOX AND SUMMARY OF IMPORTANT RELATIONS

Relation Between Normality and Molarity  Relation between Molarity (M), Molality (m) and Density
(d) of the solution
N × Eq. wt = molarity × molar mass
M
___________
N = molarity × valency m = 1000 d – MM × 1000
2

N = molarity × number of H+ or OH– ion.  Relation between Molality (m) and Mole Fraction of a
solute (x2)
Mole Fraction m M1
_______
x2 = 1 + mM
nA
______ 1
xA = n + n
A B
Raoult’s Law
nB
______
xB = n + n  Raoult’s law for volatiles solutes
A B

P = pA + pB = p0A xA + p0B x B
x A + xB = 1
P = (1 – xA) p0A + p0B x B
Mole Per cent P = (p0B – p0A) xB + p0A
Moles of solute  Raoult’s law for non-volatile solutes
= × 100
Total moles present in solution P 0 − Ps n2
= = x2
Mass Fraction P 0 n1 +n2
Mass fraction of A (xA) = wA/wA + wB ∆p
___
0
p_____
–p
p0
= p0 = Relative lowering of vapour pressure
wB
______
Mass fraction of B (xB) = w + w
A B  When a solution is prepared by mixing the non volatile solute
So, xA+ xB = l B and solvent A.
xA + xB = 1
 Relation between Mole Fraction of Solute (x2), Molarity
(M) and Molality (m) xB = 1 – xA
m M1
____________ PA0 − PA ∆P n
x2 = M (M – M ) + d = xB = =
1 2
PA0 PA0 n +N
Here M1 and M2 are molecular weight of solvent and solute
Here n = number of moles of solute
respectively
N = solvent
 Solutions 5.15

 In dilute solution N > > n and hence If molality of the solution is one, then
n
__ w/m
____ wM
____
xB = = = ∆Tb = Kb
N W/M Wm
RT2
______
0
PA − PA ∆P wM m×M Kb =
1000 Lv
So, = xB = = =
PA0 P
0 Wm 1000 Here Lv = Latent heat of vaporization.

Van’t Hoff Equation of Osmotic Pressure Depression in Freezing Point

π = CST w
___ 1000
____
 ∆Tf = Kf m × W
n
__ w
π = V ST (C = n/V)
k f × w × 1000
πV = nST  mw =
w
__ ∆Tf × W
πV = M RT
 If molality of the solution is one, then
As n = w/M
∆Tf = Kf
Determination of Molecular Weight from RT2
______
 Kf =
Osmotic Pressure 1000 Lf
M
__ ST
___ Here Lf = Latent heat of fusion.
W = π
WST
____
M= π Van’t Hoff Factor
 When solute is not dissolved in one litre or it is dissolved in Normal molar mass
V litre then i=
Observed molar mass
πV = nST (n = W/M)
W
__ Observed molar mass
πV = M ST i=
Normal molar mass
W × ST
______
M= π×V
Degree of Dissociation
 When height is involved then
i−i
π = hdg Degree of dissociation, α =
n−i
Isotonic Solution Degree of Association
w1 w2 n (1− i) i −1
= α= =
M1V1 M2 V2 n −1 1
−1
n
Elevation of Boiling Point Here n = Number of species formed after association.
w
___ 1000
____
∆Tb = Kb × m × W P − Ps n
w
=1
Molecular weight of solute, P n+N
k b × w × 1000 Henry’s Law
mw = mw =
∆Tb × W M = KP
M
__
or, P = K (At constant temperature)
5.16 Chapter 5

EXERCISES

Single Option Correct Type

1. Which of the following colligative properties can 6. In liquid CCl4 which of the following has maximum
provide molar mass of proteins (or polymers or col solubility?
loids) with greatest precision? (a) I2 (b) Br2
(a) osmotic pressure (c) NaCl (d) Cl2
(b) elevation of boiling point
7. During osmosis, flow of water through a semi­
(c) depression of freezing point
permeable membrane is
(d) relative lowing of vapour pressure
(a) from both sides of semi­permeable membrane
2. The beans are cooked sooner in a pressure cooker, with unequal flow rates
because (b) from solution having lower concentration only
(a) boiling point increase with increasing pressure (c) from solution having higher concentration only
(b) boiling point decrease with increasing pressure (d) from both sides of semi­permeable membrane
(c) extra pressure of pressure cooker, softens the beans with equal flow rates
(d) internal energy is not lost while cooking in pres­
8. A solution of acetone in ethanol
sure cooker.
(a) behaves like a near ideal solution
3. When a saturated solution of sodium chloride is (b) obeys Raoult’s law
heated, it (c) shows a negative deviation from Raoult’s law
(a) becomes remains saturated (d) shows a positive deviation from Raoult’s law
(b) becomes unsaturated
9. Which of the following represents a metastable
(c) becomes supersaturated
system?
(d) achieves equilibrium state
(a) an unsaturated solution
4. Which of these curves represents Henry Law? (b) a dilute solution
(c) a saturated solution
(d) a supersaturated solution
logM log M 10. According to Raoult’s law, relative lowering of vapour
pressure for a solution is equal to
(a) mole fraction of the solute
(a) logP
(b) log P (b) mole fraction of a solvent
(c) moles of a solute
(d) moles of a solvent
log M log M 11. When non­zero volatile solute is dissolved in a solvent,
the relative lowering of vapour pressure is equal to
(a) molar fraction of solute
log P log P (b) molar fraction of solvent
(c) (d)
(c) concentration of the solute in grams per liter
5. A solution containing components A and B follows (d) concentration of the solute in gram per 100 mL.
Raoult’s law
12. Van’t Hoff factor is
(a) A – B attraction force is greater than A – A and B – B
(a) more than one in case of association
(b) A – B attraction force is less than A – A and B–B
(b) less than one in case of dissociation
(c) A – B attraction force remains same as A – A and
normal molecular mass
B–B (c) equal to __________________
observed molecular mass
(d) volume of solution is different from sum of vol­
observed molecular mass
ume of solute and solvent. (d) equal to __________________
normal molecular mass
 Solutions 5.17

13. The solubility of a gas in a liquid increases with 21. The vant Hoff factor ‘i’ accounts for
(a) increase of temperature (a) the extent of dissociation of solute
(b) amount of liquid taken (b) the extent of dissolution of solute
(c) decrease in temperature (c) the degree of decomposition of solution
(d) reduction of gas pressure (d) degree of solubilization of solute
14. Which of the following solution would exhibit abnormal 22. The azeotropic mixture of water and ethonal boils at
colligative properties? 78.15°C. When this mixture is distilled, it is possible
(a) 1 M glucose to obtain
(b) 0.1 M NaCl (a) pure H2O
(c) 0.1 M sucrose (b) pure C2H5OH
(d) 10 gram glass powder in water (c) pure H2O as well as pure C2H5OH
15. Which one of the statements given below concerning (d) neither H2O nor C2H5OH in their pure state
properties of solutions, describe a colligative effect?
23. The solution of sugar in water contains
(a) boiling point of pure water decreases by the
addition of ethanol (a) free ions
(b) vapour pressure of pure water decreases by the (b) free atoms
addition of nitric acid (c) free molecules
(c) vapour pressure of pure benzene decreases by the (d) free atoms and molecules
addition of naphthalene 24. Which of the following changes with change in
(d) boiling point of pure benzene increases by the temperature?
addition of toluene (a) mole fraction (b) formality
16. V litres of a solution contains m2 g of non­volatile sol­ (c) % (w/W) (d) molality
ute of molecular mass M2. Which of the following can 25. When the solute is present in trace quantities the
be used to calculate the molecular mass of solute in following expression is used
terms of osmotic pressure?
(a) gram per million (b) nanogram per cent
M2 ___
M2 M m (c) microgram per cent (d) parts per million
(a) ___
V = π VRT
2
(b) ____ ___2
V = π RT
26. The vapour pressure of a solution (P) and the vapour
M2 m2 ___
(c) M2 = ___ (d) M2 = ___
π pressure of the solvent (P0) are related to each other as
V πRT V RT
(a) P = P0x2 (b) P = P0x1
17. The number of moles of sodium hydroxide present in 0
(c) P = Px2 (d) P0 = Px1
2.5 L and 0.5 M aqueous solution will be
(a) 1.25 (b) 0.5 27. Increasing the temperature of an aqueous solution will
(c) 12.5 (d) 5 cause
(a) decrease in molality
18. Highest boiling point is found in
(b) decrease in molarity
(a) 0.1 M Sucrose (b) 0.1 M BaCl2 (c) decrease in mole fraction
(c) 0.1 M NaCl (d) 0.1 M KCl (d) decrease in % (w/w)
19. Maximum freezing point will be for 1 molal solution 28. During depression in freezing point in a solution, the
of, assuming equal ionization in each case: following are in equilibrium
(a) [Fe(H2O)6] Cl3 (a) liquid solvent, solid solvent
(b) [Fe(H2O)5Cl] Cl2.H2O (b) liquid solvent, solid solute
(c) [Fe(H2O)4Cl2]Cl.2H2O (c) liquid solute, solid solute
(d) [Fe(H2O)3Cl3].3H2O (d) liquid solute, solid solvent
20. The solution which has the lowest freezing point is 29. When attraction between A – B is more than that of
(a) 0.1 M potassium nitrate A – A and B – B, the solution will show deviation from
(b) 0.1 M aluminium sulphate Raoult’s law
(c) 0.1 M potassium chloride (a) positive (b) negative
(d) 0.1 M potassium sulphate (c) no (d) cannot be predicted
5.18 Chapter 5

30. People add sodium chloride to water while boiling 36. Which of the following is correct for a solution show­
eggs. This is to ing positive deviations from Raoult’s law?
(a) decrease the boiling point of water (a) ∆V = +ve, ∆H = +ve
(b) increase the boiling point of water (b) ∆V = –ve, ∆H = +ve
(c) prevent breaking of eggs (c) ∆V = +ve, ∆H = –ve
(d) make eggs tasty (d) ∆V = –ve, ∆H = –ve
31. FeCl3 reacts with K4Fe(CN)6 in aqueous solution to 37. Which one of the following solution has least vapour
give blue colour if these two are separated by a semi­ pressure?
permeable membrance (as shown in the figure), then
(a) 0.01 M CaCl2
due to osmosis
(b) 0.01 M glucose
(c) 0.01 M Na2SO4
(d) 0.01 M Na3PO4
0.1M 0.02M 38. Which is true about enthalpy of solution containing
K4Fe(CN)6 FeCI3 benzene and toluene?
solution solution (a) ∆Hsol < 0
(b) ∆Hsol = 0
Side A Semi-permeable Side B
membrance (c) ∆Hsol > 0
(d) ∆Hsol may be zero or greater than zero

(a) blue colour is formed towards side A 39. A 5% solution of sugarcane (Mol wt = 342) is isotonic
(b) blue colour is formed towards side B with 1% solution of X under similar conditions. The
(c) blue colour is formed on both the sides side mol. Wt of X is:
(d) no blue colouration (a) 136.2 (b) 68.4
(c) 34.2 (d) 171.2
32. Which pair of the following will not form an ideal
solution? 40. Which of the following statement is true about ideal
(a) C2H5Br + C2H5I (b) H2O + C4H9OH solutions?
(c) CCl4 + SiCl4 (d) C6H14 + C7H16 (a) the volume of mixing is zero
(b) the enthalpy of mixing is zero
33. A molal solution is one that contains one mole of a
(c) both A and B
solute in
(d) none of these
(a) 1000 g of the solvent
(b) one litre of solvent 41. The relationship between osmotic pressure at 273
(c) one litre of solution K when 10 g glucose (P1) 10 g urea (P2) and 10 g
(d) 22.4 litre of the solution sucrose (P3) are dissolved in 250 mL of water is
34. A liquid is in equilibrium with its vapour at its boiling (a) P1 > P2 > P3
point. On the average, the molecules in the two phase (b) P3 > P2 > P1
have equal (c) P2 > P1 > P3
(a) intermolecular forces (d) P2 > P3 > P1
(b) potential energy 42. Which of the following salt will have the
(c) temperature same volume of vant Hoff factor ‘i’as that of
(d) kinetic energy K4[Fe (CN)6]?
35. The molecular weight of benzoic acid in benzene as (a) Al2(SO4)3 (b) NaCl
determined by depression in freezing point method (c) Al(NO3)3 (d) Na2SO4
corresponds to
43. Which of the following 0.1 M aqueous solutions will
(a) ionization of benzoic acid have the lowest freezing point?
(b) dimerization of benzoic acid
(c) trimerization of benzoic acid (a) K2SO4 (b) NaCl
(d) solvation of benzoic acid (c) urea (d) glucose
 Solutions 5.19

44. Consider this figure and select the correct statement. 51. The vapours pressure of water at 23°C is 19.8 mm.
of Hg. 0.1 mole of glucose is dissolved in 178.2 g of
water. What is the vapour pressure (in mm of Hg) of
0.1M 0.05M the resultant solution?
KCI BaCI2 (a) 19.0 (b) 19.602
solution solution (c) 19.402 (d) 19.202
Semi-permeable membrance 52. A molal solution of sodium chloride has a density of
(a) BaCl2 flows towards the KCl solution 1.21 g mL–1. The molarity of this solution is
(b) KCl flows towards the BaCl2 solution (a) 3.15 (b) 1.143
(c) there will be no movement of any solution (c) 2.95 (d) 4.15
(d) first KCl flows towards BaCl2 then reverse 53. 0.5 M of H2SO4 is diluted from 1 litre to 10 litre,
process takes place normaliy of the resulting solution is
45. Camphor is used as a solvent to determine molecular (a) 1 N (b) 10 N
weight of non­volatile solute by Rast method because (c) 11 N (d) 0.1 N
for camphor
54. Which of the following solutions are isotonic with
(a) its molal depression constant is high respect to one another?
(b) being very cheap
1. 0.15 M urea 2. 0.05 M CaCl2
(c) high melting point
3. 0.1 M MgSO4 4. 0.15 M glucose
(d) all of these
Select the correct answer using the codes given below:
46. 3.65 grams of HCl is dissolved in 16.2 grams of water
The mole fraction of HCl in the resulting solution is (a) 1 and 4 (b) 1, 2 and 4
(c) 2 and 3 (d) 2, 3 and 4
(a) 0.4 (b) 0.3
(c) 0.2 (d) 0.1 55. At room temperature, the mole fraction of a solute is
0.25 and the vapour pressure of a solvent is 0.80 atm.
47. By dissolving 5g substance in 50g of water, the
The lowering of vapour pressure is
decrease in freezing point is 1.2°C. The molal
depression constant is 1.85° kg mol–1. The molecular (a) 0.60 (b) 0.75
weight of substance is (c) 0.20 (d) 0.80.
(a) 105.4 (b) 118.2 56. 50 mL of 10 N H2SO4, 25 mL of 12 N HCl and 40 mL
(c) 137.2 (d) 154.2 of 5N HNO3 are mixed and the volume of the mixture
48. If the molarity of 20% solution of sulphuric is made 1000 mL by adding water. The normality of
acid is 2.55M. The density of the solution resulting solution will be
will be (a) 9 N (b) 4 N
(a) 2.55 gem–3 (b) 1.25 g cm–3 (c) 1 N (d) 2 N
–1
(c) 0.125 g L (d) 3.25 g L–1 57. Equal volumes of ethylene glycol (molar mass = 62)
49. If the boiling point of ethanol (mol. wt = 46) is and water (molar mass = 18) are mixed. The depres­
78°C, what is the boiling point of diethyl ether sion in freezing point of water is (given Kf of water =
(mol. wt =74)? 1.86 K mor–1 kg and specific gravity of ethylene glycol
(a) 100°C (b) 78°C is 1.11)
(c) 86°C (d) 34°C (a) 0.0033 (b) 0.033
(c) 0.33 (d) 33.3
50. ‘x’ grams of water is mixed in 69 grams of ethanol
Mole fraction of ethanol in the resultant solution is 58. The elevation in boiling point for 13.44g of CuCl2
0.6. what is the value of ‘x’ in grams? dissolved in 1 kg of water as solvent will be
(a) 54 (b) 36 (Kb = 0.52 kg/J, molar mass of CuCl2 = 134.4 g/mol)
(c) 180 (d) 18 (a) 0.05 (b) 0.10
(c) 0.16 (d) 0.20.
5.20 Chapter 5

59. The temperature at which 10% aqueous solution of 67. KBr is 80% dissociated in aqueous solution of 0.5 M
glucose will show the osmotic pressure of 14 atm is concentration. (Given Kf for water = 1.86 K kg mol–1).
(a) 34 K (b) 307.3°C The solution freezes at
(c) 307.3 K (d) 34°C (a) 271.326 K (b) 272 K
(c) 270.5 K (d) 268.5 K
60. The mass of glucose that should be dissolved in
50 g of water in order to produce the same lowering 68. If at certain temperature the vapour pressure of
of vapour pressure as is produced by dissolving 1 g of pure water is 25 mm of Hg and that of a very dilute
urea in the same quantity of water is aqueous urea solution is 24.5 mm of Hg, the molality
(a) 1 g (b) 3 g of the solution is
(c) 6 g (d) 18 g (a) 0.02 (b) 1.2
(c) 1.11 (d) 0.08
61. Osmotic pressure observed when benzoic acid is
dissolved in benzene is less than that expected from 69. Benzoic acid undergoes dimerization in benzene
theoretical considerations. This is because solution, the van’t Hoff factor ‘i’ is related to the degree
of association ‘x’ of to the acid as
(a) benzoic acid is an organic solute
(b) benzoic acid has higher molar mass than benzene (a) i = (1 + x) (b) i = (1 – x)
(c) benzoic acid gets associated in benzene (c) i = (1 – x/2) (d) i = (1 + x/2)
(d) benzoic acid gets dissociated in benzene 70. The vapour pressure of water at 300 K in a closed
container is 0.4 atm. If the volume of the container is
62. The rise in the boiling point of a solution containing
doubled, its vapour pressure at 300 K will be
1.8 g of glucose in 100 g of solvent is 0.1°C. The molal
elevation constant of the liquid is (a) 0.8 atm (b) 0.2 atm
(c) 0.4 atm (d) 0.6 atm
(a) 1 K/m (b) 0.1 K/m
(c) 0.01 K/m (d) 10 K/m 71. A solution is obtained by dissolving 6 g of urea
(mol. wt = 60) in a litre solution, another solution
63. Which of the following solutions will exhibit highest
is prepared by dissolving 34.2 g of cane sugar (mol.
boiling point?
wt = 342) in a litre of solution at the same temperature
(a) 0.01 M Na2SO4 (aq) The lowering of vapour pressure in the first solution is
(b) 0.01 M KNO3 (aq)
(a) same as that of second solution
(c) 0.015 M urea (aq) (b) double that of second solution
(d) 0.015 M glucose (aq) (c) half that of second solution
64. At same temperature, which pair of the following (d) nearly one fifth of the second solution
solutions are isotonic solutions? 72. The aqueous solution that has the lowest vapour
(a) 0.2 M BaCl2 and 0.2 M urea pressure at a given temperature is
(b) 0.1 M urea and 0.1 MNaCl (a) 0.1 molal sodium phosphate
(c) 0.1 M NaCl and 0.1 M K2SO4 (b) 0.1 molal barium chloride
(d) 0.1 M Ba(NO3)2 and 0.1 M Na2SO4 (c) 0.1 molal sodium chloride
65. At certain temperature, a 5.12% solution of cane sugar (d) 0.1 molal glucose
is isotonic with a 0.9% solution of an unknown solute. 73. Van’t Hoff factor for a dilute solution of sodium
The molar mass of solute is argento cyanide is
(a) 60 (b) 46.17 (a) 2 (b) 0.25
(c) 120 (d) 90 (c) 3.0 (d) 0.50
66. The freezing point of 0.1 M solution of glucose is 74. What is the density (in g L–1) of CO2 at 400 K and
–1.86°C. If an equal volume of 0.3 M glucose solution exerting a pressure of 0.0821 atm?(R = 0.0821 L atm
is added, the freezing point of the mixture will be mol–1 K–1)
(a) –5.58°C (b) –7.44°C (a) 0.01 (b) 0.11
(c) –3.72°C (d) –2.79°C (c) 2.5 (d) 44
 Solutions 5.21

75. The vapour pressure of two liquids ‘P’ and ‘Q’ are 80 83. If P0 and P are the vapour pressure of solvent and
and 60 torr respectively. The total vapour pressure of solution and n1 and n2 are the moles of solute and
solution obtained by mixing 3 mole of P and 2 mol of solvent respectively
Q would be
(a) 20 torr (b) 72 torr  n1 
0
(c) 68 torr (d) 140 torr (a) P = P  
 n1 + n 2 
76. A solution containing 10 g per dm3 of urea (molecular
mass = 60 g mol–1) is isotonic with a 5% solution of 0  n2 
a nonvolatile solute. The molecular mass of this non (b) P = P  
 n1 + n 2 
volatile solute is
(a) 350 g mol–1 (b) 200 g mol–1 0 n2 
(c) 250 g mol –1
(d) 300 g mol–1 (c) P = P  
 1 + n2 
n
77. 1.00 g of a non­electrolyte solute (molar mass (d) P0 = P × n1
250 g mol–1) was dissolved in 51.2 g of benzene. If
the freezing point depression constant, Kf of benzene 84. Two liquids having vapour pressures P10 and P20 in
is 5.12 K kg mol–1, the freezing point of benzene will pure state in the ratio of 2 : 1 are mixed in a molar ratio
be lowered by of 1 : 2. The ratio of their moles in the vapour state can
(a) 0.5 K (b) 0.2 K be
(c) 0.4 K (d) 0.3 K (a) 2 : 1 (b) 1 : 2
78. If 0.44 g of substance dissolved in 22.2 g of benzene (c) 1 : 1 (d) 3 : 3
lowers the freezing point of benzene by 0.567°C, then
85. The molal elevation constant of water is 0.51. The
the molecular mass of substance is, (the molal depres­
boiling point of 0.1 molal aqueous NaCl solution is
sion constant = 5.12°C mol–1 kg)
nearly
(a) 128.4 (b) 156.6
(a) 100.05°C (b) 100.1°C
(c) 178.9 (d) 232.4
(c) 100.2°C (d) 101.0°C
79. The osmotic pressure at 17°C of an aqueous solution
containing 1.75 g of sucrose per 150 mL solution is 86. An aqueous solution containing 1 g of urea boils at
100.25°C. The aqueous solution containing 3 g of
(a) 0.08 atm (b) 8.1 atm
glucose in the same volume will boil at
(c) 0.81 (d) 9. l atm
(a) 100.75°C (b) 100.5°C
80. Two solutions containing 0.75 g of urea (molecular
(c) 100°C (d) 100.25°C
weight 60) and 1.5 g of compound A in 100 g water,
freeze at the same temperature. The molecular weight 87. Equal volumes of 0.1 M AgNO3 and 0.2 M NaCl are
of A is mixed. The concentration of nitrate ions in the mixture
(a) 60 (b) 30 will be
(c) 120 (d) 240 (a) 0.1M (b) 0.05M
81. By dissolving 10 g of a non­volatile solute in 100 g of (c) 0.2M (d) 0.15M
benzene, the boiling point rises by 1°C. The molecular 88. A solution obtained by dissolving 0.2 g of solute in
mass of solute is [Kb for benzene = 2.53 K m–1] 100 cm3 of solution in benzene at 21°C develops a rise
(a) 235 g (b) 352 g of 2.4 mm Hg osmotic equilibrium. Find molarity and
(c) 250 g (d) 253 g molality in the solution. (If density of solution is 0.88
82. Among the following aqueous solutions, the correct g/cm3)
order of increasing boiling point can be given as (a) 8.3 × 10–3 mol/L (b) 4.15 × 10–6 mol/L
(i) 10 −4 M KCl (ii) 10 −3 M urea (c) 8.3 × 10–4 (d) none

(iii) 10 −3 M CaCl 2 (iv) 10–3 M KCl 89. In a depression in freezing point experiment, it is
(a) I < IV < II< III (b) I < II < IV < III found that
(c) IV < II < I < III (d) I < II < III < IV (1) the vapour pressure of the solution is less than
that of pure solvent
5.22 Chapter 5

(2) the vapour pressure of the solution is more than 97. Osmotic pressure of a solution is 0.0821 atm at a tem­
that of pure solvent perature of 300 K. The concentration in moles/litre
(3) only solute molecules solidify at the freezing point will be
(4) only solvent molecules solidify at the freezing (a) 0.33 (b) 0.066
point (c) 0.3 × l0–2 (d) 3
(a) 1, 2 (b) 2, 3
(c) 1, 4 (d) 1, 3 98. Lowering of vapour pressure, ∆p; elevation in
boiling point ∆Tb; and depression freezing point
90. On mixing 3 g of non­volatile solute in 200 mL of ∆Tf of a solvent for the same molar concentration
water its boiling point (100°C) becomes 100.52°C. If of each of the three solutes: (a) sugar, (b) NaCl and
Kb for water is 0.6 K/m then molecular weight of the (c) BaCl2 following the sequence
solute is (a) ∆Tb:C > B > A (b) ∆Tf : A < B < C
(a) 10.5 g mol–1 (b) 12.6 g mol–1 (c) ∆p : A < B < C (d) all the above
–1
(c) 15.7 g mol (d) 17.3 g mol–1
99. A 1.02% solution of glycerine is isotopic with 2%
91. 20 g of a substance were dissolved in 500 mL of water solution of glucose. What will be the molecular mass
and the osmotic pressure of the solution was found to of glycerine?
be 600 mm of mercury at 15°C. The molecular weight (a) 91.8 (b) 93.0
of substance is (c) 90.2 (d) 96.4
(a) 998 (b) 1028
(c) 1098 (d) 1198 100. The osmotic pressure of a solution containing 4.0
g of solute (molar mass 246) per litre at 27°C is
92. The freezing point of equimolal aqueous solution will (R = 0.082 L atm K–1 mol–1).
be highest for (a) 0.l atm (b) 0.3 atm
(a) C6H5N+ H3Cl– (aniline hydrochloride) (c) 0.4 atm (d) 0.9 atm
(b) Ca(NO3)2
(c) La(NO3)3 101. A solution of urea (mol. mass 56 g mol–1) boils at
(d) C6H12O6 (glucose) 100.18°C at atmospheric pressure. If Kf and Kb for
water are 1.86 and 0.512 K kg mol–1 respectively, the
93. A sugar syrup weighing 214.2 g, contains 34.2 g of above solution will freeze at
water. The molal concentration is (a) 6.54°C (b) –6.54°C
(a) 0.55 (b) 5.5 (c) –0.654°C (d) 0.654°C
(c) 55 (d) 0.1
102. An aqueous solution of sucrose C12H22O11, containing
94. When mercuric iodide is added to the aqueous solution 34.2 g/L, has an osmotic pressure of 2.38 atmospheres
of potassium iodide, the at 17°C. For an aqueous solution of glucose C6H12O6 to
(a) freezing point is raised be isotonic with this solution, it would have
(b) freezing point does not change (a) 18.0 g/L (b) 16.2 g/L
(c) freezing point is lowered (c) 36.6 g/L of glucose (d) 14.0 g/L
(d) boiling point does not change
103. A 5% solution (by mass) of cane sugar in water has
95. The relative lowering of vapour pressure of an aqueous a freezing point of 271 K and freezing point of pure
solution containing non­volatile solute is 0.0125. The water is 273.15 K. The freezing point of a 5% solution
molarity of the solution is (by mass) of glucose in water is
(a) 0.70 (b) 0.45 (a) 271 IK (b) 273.15 K.
(c) 0.34 (d) 0.50 (c) 269.07 K (d) 277.23 K
96. The depression in freezing point of 0.01 M aque­ 104. A decimolar solution of potassium ferrocyanide is
ous solution of urea, sodium chloride and sodium 50% dissociated at 300 K. Calculate the osmotic pres­
sulphate is in the ratio sure of the solution. (R = 8.314 JK–1 mol–1)
(a) 1 : 1 : 1 (b) 1 : 2 : 3 (a) 0.07389 atm (b) 7.389 atm
(c) 1 : 2 :4 (d) 2 : 2 : 3 (c) 738.89 atm (d) 73.89 atm
 Solutions 5.23

105. The volume strength of 1.5 N H2O2 solution is 114. The van’t Hoff factor for 0.1 M Ba(NO3)2 solution is
(a) 4.8 (b) 5.2 2.74. The degree of dissociation is
(c) 8.8 (d) 8.4 (a) 91.4% (b) 87%
(c) 100% (d) 75%
106. pH of 0.1 M monobasic acid solution is found to be 2.
Thus its osmotic pressure at T. K. is 115. A 0.2 molal aqueous solution of a weak acid (HX)
(a) 11.11 ST (b) 0.11 ST is 20% ionized. The freezing point of this solution is
(Given Kf = 1.86°C kg mol–1 for water)
(c) 0.011 ST (d) 1.11 ST
(a) –0.45°C (b) –0.90°C
107. The elevation in boiling point for 13.44 g of CuCl2 dis­ (c) –0.21°C (d) –0.43°C
solved in 1 kg of water as solvent will be (Kb = 0.52
kg/J, molar mass of CuCl2 = 134.4 g/mol) 116. How many moles of Fe2+ ions are formed when excess
iron is treated with 500 mL of 0.4 N HCl under inert
(a) 0.05 (b) 0.10 atmosphere? Assume no change in volume.
(c) 0.16 (d) 0.20.
(a) 0.4 (b) 0.1
108. A 0.004 M solution of Na2SO4 is isotonic with a 0.010 (c) 0.2 (d) 0.8
M solution of glucose at same temperature. The appar­
117. The osmotic pressure of urea solution is 500 mm of
ent degree of dissociation of Na2SO4 is Hg at 10°C. If the solution is diluted and temperature
(a) 25% (b) 50% is raised to 25°C, the osmotic pressure decreases to
(c) 75% (d) 85% 105.3 mm of Hg, what is the extent of dilution?
109. What is the freezing point of one litre of an aqueous (a) 10 times (b) 2.5 times
solution of a non­electrolyte having an osmotic pres­ (c) 5 times (d) 7.5 times
sure of 2 atm at 300 K.
118. The molality of a 15% (w/v) solution of H2SO4 of den­
(a) 273.349 K (b) 263.159 K sity 1.1 g/cm3 is nearly
(c) 215.569 K (d) 272.849 K
(a) 1.3 (b) 1.6
110. The molality of 1 litre solution of 93% H2SO4 (w/v) (c) 1.46 (d) 1.86
having density 1.84 g/mL is 119. The vapour pressure of a solution of 5 g of non elec­
(a) 10.43 (b) 1.043 trolyte in 100 g of water at a particular temperature is
(c) 0.1043 (d) 100.43 2985 Nm–2. The vapour pressure of pure water at that
temperature is 3000 Nm–2. The molecular weight of
111. The vapour pressure of pure benzene and toluene are
the solute is
160 and 60 torr respectively. The mole fraction of tolu­
ene in vapour phase in contact with equimolar solution (a) 180 (b) 90
of benzene and toluene is (c) 270 (d) 360
(a) 0.6 (b) 0.50 120. A current of dry air was bubbled through a bulb con­
(c) 0.27 (d) 0.74 taining 26 g of an organic substance in 200 g of water,
then through a bulb at the same temperature, contain­
112. An aqueous solution of 6.3 g oxalic acid dihydrate ing pure water and finally through a tube containing
is made up to 250 mL. The volume of 0.1 N NaOH fused CaCl2. The loss of weight of water bulb is 0.013
required to completely neutralize 10 mL of this solu­ g and the gain of the weight of CaCl2 tube is 4 g. The
tion is molecular weight of organic substance is
(a) 40 mL (b) 20 mL (a) 820 (b) 740
(c) 10 mL (d) 4 mL (c) 720 (d) 840
113. To 500 cm3 of water, 3.0 × 10–3 kg of acetic acid is 121. Organic liquids A and B have vapour pressures po1 and
added. If 23% of acetic acid is dissociated, what will p°2 as pure liquids at 80°C. A mixture of the two liquids
be the depression in freezing point? Kf and density of behaving ideally and boiling at 80°C has mole fraction
water at 1.86 K kg–1 and 0.0997 g cm–3 respectively. of A = 0.16. If (p°2 – p°1 ) = 472 mm of Hg, what is the
(a) 0.186 K (b) 0.228 K value of p01 (in mm Hg)?
(c) 0.371 K (d) 0.555 K (a) 263.6 mm (b) 463.5 mm
(c) 663.3 mm (d) 363.5 mm
5.24 Chapter 5
More than One Option Correct Type
122. When 2 moles each of Hexane and heptane are mixed
and if P°Hexane and P°Heptane are 50mm Hg and 60mm Hg
respectively than?
(a) PTotal = 55mm Hg
(b) PHexane = 25mm Hg
(c) PHeptane = 30mm Hg
(d) None­Ideal solution
123. The freezing point of a solution prepared by dissolv­
ing 20.5 g of a non­ volatile non­ electrolyte with
empricial formula (C3H2) in 400 g of benzene is
4.33oC. The benzene used to prepare the solution
freezes at 5.48oC, using the same thermometer. (Given
: Kf of benzene = 5.1 kg K mol­1, Kb of benzene = 2.53
kg K mol­1 and boiling point of benzene 80.2oC).
(a) The boiling point of the solution will be 80.17oC.
(b) The boiling point of the solution will be 80.77oC
(c) The molecular formula of non electrolyte is C18H12.
(d) The molecular formula of non­ electrolyte is
C15H12.
124. In the freezing point depression experiment, it is
observed that
(a) at the freezing point the solvent begins to freeze.
(b) relative lowering of vapour pressure of solution
(X) is more than (Y).
(c) the decrease in freezing point of 0.1 M CH3COOH
(X) in C6H6 is lower than that of 0.1 M CH3COOH
(Y) in water.
(d) the decrease in freezing point in the two solutions
is same.
125. 1mole benzene (pobenzene=42 mm) and 2 mole toluene
(pobenzene = 36 mm) will have:
(a) Mole fraction of benzene in vapour phase above
liq. Mixture is 1/3.
(b) Mole fraction of toluene in vapour phase above
liq. Mixture is 8/19
(c) Total vapour pressure of solution is 38 mm
(d) Mole fraction of benzene in vapour phase above
liquid mixture is 7/19
126. An aqueous solution of a solute which neither associ­
ates nor dissociates has a freezing point depression of
XoC. An equimolar solution of a second has a freezing
point depression of 4XoC. The second solution could
be a salt of formula (assuming 100 % dissociation )
(a) AB2 (b) A2B2
(c) A3B (d) AB3
127. A solution containing 0.1 mole of naphthalene and
0.9 mole of benzene is cooled out until some benzene
freezes out. The solution is then decanted off from
the solid and warmed upto 353 K where its vapour
pressure was found to be 670 torr. The freezing point
and boiling point of benzene are 278.5 K and 353 K
respectively and its enthalpy of fusion is 10.67 kJ mol­1.
Which of the following statement (s) is /are correct?
(a) Temperature to which solution is frozen is 269.7 K
(b) Weight of naphthalene that freezes is 0.025 g.
(c) Weight of benzene frozen out is 12.13 g
(d) The depression in freezing point is 8.92 g
128. The amount of dissolved oxygen in 1 litre water in
equilibrium with air at 1 atm pressure at 25oC will be
(assume that air contains 20 mole % oxygen, Henry’s
constant (kH) for oxygen is 3.04 × 107 mm Hg and
density of H2O at 25oC is 1 g/ cc)
(a) the mole fraction of O2 in solution is 5 × 10­6
(b) the mole fraction of O2 in solution is 5 × 10­7
(c) the molarity of O2 in solution is 2.77 × 10­5 M
(d) the molarity of O2 in solution is 2.77 × 10­4 M
129. Which of the following can form minimum boiling
point azeotropic mixture?
(a) Ethyl alcohol + water
(b) Carbon tetrachloride + chloroform
(c) Ethyl alcohol + water
(d) Acetone + chloroform
130. Correct mathematical equations for the Raoult’s law
are O
P − PS
(a) = mole fraction of solvent
PS
P O − PS
(b) PO = mole fraction of a nonvolatile solute
(c) PS ∝ mole fraction of solvent
(d) PS ∝ mole fraction of a non volatile solute
131. For the binary ideal solution having 1 mole of A and 2
moles of B at 298 K which one is correct?
(a) ∆Smix = −R∑xi ln xi
(b) ∆Hmix = 0
(c) ∆Gmix = RT ∑xi ln xi
(d) ∆Hmix = (+)ve
 Solutions 5.25

Passage Based Questions

Passage-1 into ions in solution. It is the number of solute particles

that determine the colligative properties of a solution. The
132. The van’t Hoff factor (i), is a measure of association or electrolyte solutions, therefore show abnormal colligative
dissociation. The van’t Hoff factor for 0.1 M aqueous properties. To account for this effect we define a quantity;
sodium chloride is 1.87. In magnesium sulphate the called the van’t Hoff factor which is given by
ionic interactions [solution]
(a) Are weaker than that observed in sodium chloride. i=
(b) Are same as that observed in sodium chloride Actual number of particles in solution after dissociation
(c) Are stronger than that observed in sodium chloride. Number of formula units initally dissolved in solution
(d) Are not responsible for the (i) value.
i = 1 (for non ­ electrolytes);
133. Mercuric iodide is added to an aqueous solution of i > 1 (for electrolytes, undergoing dissociation)
potassium iodide. Identify the correct statement(s) i < 1 (for solute, undergoing association)
(a) Freezing point is raised.
135. Benzoic acid undergoes dimerisation in benzene solu­
(b) Freezing point is lowered.
tion. The van’t Hoff factor ‘i’ is related to the degree of
(c) Freezing point and boiling point does not change.
association ‘α’ of the acid as
(d) Boiling point is raised.
(a) 1 and 4 (b) 3 and 4 (a) i = 1 + α (b) i = 1 − α
(c) Only 1 (d) 2 and 4 α α
(c) i = 1 + 2 (d) i = 1 −
2
134. A protein has been isolated as a salt with the formula
136. For a solution of a non electrolyte in water, the van’t
Na20P (this notation means that there are 20 Na+ ions
Hoff factor is
associated with a negatively charged protein P20−).
The osmotic pressure of a 10.0 ml solution contain­ (a) Always equal to 2 (b) Always equal to 0
ing 0.225 g of the protein is 0.257 atm at 25oC. The (c) > 1 but < 2 (d) ≤ 1
actual molar mass of the protein from these data is 137. 0.1 M K4[Fe(CN)6] is 60 % ionized. What will be its
approximately. van’t Hoff factor ?
(a) 2.6 × 105 g mol­1 (b) 4.5 × 104 g mol­1 (a) 3.4 (b) 1.7
6 ­1
(c) 4.5 × 10 g mol (d) 2.3 × 103 g mol­1 (c) 2.4 (d) 2.2
Passage-2
The colligative properties of electrolytes require a slightly
different approach than the one used for the colligative
properties of non­ electrolytes. The electrolytes dissociate

Match the Column Type

138. Match the following (d) m­ nitrotoluene in (s) i ≠ 1

benzene
Column–I Column–II (t) (Molecular Weight)obs
(a) 0.1 m urea in water W RT >(Molecular Weight)
(p) Msolute = i solute calc
πV
(b) 0.1 m NaCl in water (q) ∆Tf = i × Kf × m
(c) 0.1 m benzoic acid in (r) ∆Tb (obs) ≠ ∆Tb (cal)
benzene
5.26 Chapter 5

Integer Type

139. A molecule Bn dissolves in water and is non­ volatile.
A solution of certain molality showed a depression of
0.93 K in freezing point. The same solution boiled at
100.26oC. When 7.9 g of Bn was dissolved in 100 g
water, the solution boiled at 100.44oC. Given Kf for
water = 1.86 K mol–1 kg and Atomic mass of B = 31.
The value of ‘n’ is ________
143. K2HgI4 is 50% ionized in aqueous solution. Find the
value of i.
144. What would be the pH of a 0.1 molal aqueous solution
of a monoprotic acid ‘HA’, that freezes at −0.2046oC?
[Kf(H2O) = 1.86o mol–1 kg; assuming molality =
molarity]

140. Assuming 100 % polymerisation of phenol in its aque­
ous solution, the number of phenol molecules under­
going polymerization containing 9.4 g of phenol per
100 g of the solution is _____. Freezing point of the
solution is 0.93oC.
141. A 0.001 molal solution of [Pt(NH3)4Cl4] in water had
a freezing point depression, 0.0056oC. Kf for water is
1.86ocm­1. The number of moles of AgNO3 required to
react with one mole of the complex in aqueous solu­
tion is ______
145. Freezing point of 0.2 M KCN solution is −0.7oC. On
adding 0.1 mole of Hg(CN)2 to one litre of the 0.2
M KCN solution, the freezing point of the solution
becomes −0.53oC due to the reaction Hg(CN)2 + mCN−
→ [Hg(CN)]m– m+2
. What is the value of m? (Assuming
molality = molarity)
146. An aqueous solution containing ionic salt having
molality equal to 0.1892 freezes at – 0.704oC. The
van’t Hoff factor of the ionic salt will be equal to ____.
(Kf = 1.86 Km­1)

142. Relationship between molarity (M) and molality (m)

M
of a solution is given as m= × 10n
(1000 × d-M × M B )
where n is ____ (Given : d­ density of the solution in g

cm­3 ; MB – molar mass of solute)

Previous Years’ Questions

147. Which of the following concentration factor is affected 150. In a 0.2 molal aqueous solution of a weak acid HX,
by change in temperature? [2002] the degree of ionization is 0.3. Taking Kf for water as
(a) molarity (b) molality 1.85 k kg melt, the freezing point of the solution will
(c) mole fraction (d) weight fraction be nearest to [2003]
(a) –0.480°C (b) –0.360°C
148. In a mixture of A and B, components show negative (c) –0.260°C (d) +0.480°C
deviation when: [2002]
(a) A – B interaction is stronger than A – A and B – B 151. A pressure cooker reduces cooking time for food
interaction because [2003]
(b) A – B interaction is weaker than A – A and B – B (a) heat is more evenly distributed in the cooking
interaction space
(c) ∆Vmix> 0, ∆Smix > 0 (b) boiling point of water involved in cooking is
(d) ∆Vmix = 0, ∆Smix > 0 increased
(c) the higher pressure inside the cooker crushes the
149. For an aqueous solution, freezing point is –0.186°C. food material
Elevation of the boiling point of the same solution is (d) cooking involves chemical changes helped by a
(Kf = 1.86° mol–1 kg and Kb = 0.512° mol–1 kg) [2002] rise in temperature
(a) 0.186° (b) 0.0512°
(c) 1.86° (d) 5.12° 152. If liquids A and B form an ideal solution, the [2003]
(a) enthalpy of mixing is zero
 Solutions 5.27

(b) entropy of mixing is zero 159. Density of a 2.05 M solution of acetic acid in water is
(c) free energy of mixing is zero 1.02 g/mL. The molality of the solution is [2006]
(d) free energy as well as the entropy of mixing are (a) 1.14 mol kg –1
(b) 3.28 mol kg–1
each zero (c) 2.28 mol kg –1
(d) 0.44 mol kg–1
153. Which one of the following aqueous solutions will
exhibit highest boiling point? [2004] 160. 18 g of glucose (C6H12O6) is added to 178.2 g of water.
(a) 0.05 M glucose (b) 0.01 M KNO3 The vapour pressure of water for this aqueous solution
(c) 0.015 M urea (d) 0.01 M Na2SO4 at 100°C is [2006]
(a) 759.00 torr (b) 7.60 torr
154. Which of the following liquid pairs shows a positive­ (c) 76.00 torr (d) 752.40 torr
deviation from Raoult’ law? [2004]
(a) water–nitric acid 161. A 5.25% solution of a substance is isotonic with a
(b) water–hydrochloric acid 1.5% solution of urea (molar mass = 60 g mol–1) in the
(c) benzene–methanol same solvent. If the densities of both the solutions are
(d) acetone–chloroform assumed to be equal to 1.0 g cm–3, molar mass of the
substance will be [2007]
155. Which one of the following statements is false?
–1
[2004] (a) 115.0 g mol (b) 105.0 g mol–1
–1
(a) two sucrose solutions of same molality prepared (c) 210.0 g mol (d) 90.0 g mol–1
in different solvents will have the same freezing
point depression 162. A mixture of ethyl alcohol and propyl alcohol has a
(b) the osmotic pressure (π) of a solution is given by vapour pressure of 290 mm at 300 K. The vapour pres­
the equation π = MRT, where M is the molarity of sure of propyl alcohol is 200 mm. If the mole fraction
the solution of ethyl alcohol is 0.6, its vapour pressure (in mm) at
(c) Raoult’s law states that the vapour pressure of a the same temperature will be [2007]
component over a solution is proportional to its (a) 300 (b) 700
mole fraction (c) 360 (c) 350
(d) the correct order of osmotic pressure for 0.01 M
aqueous solution of each compound is BaCl2 > 163. At 80°C, the vapour pressure of pure liquid ‘A’ is 520
KCl < CH3COOH > Sucrose
mm Hg and that of pure liquid ‘B’ is 1000 mm Hg. If a
156. If a is the degree of dissociation of Na2SO4 the van’t mixture solution of ‘A’ and ‘B’ boils at 80°C and 1 atm
Hoff factor (i) used for calculating the molecular mass pressure, the amount of ‘A’ in the mixture is (1 atm =
is [2005] 760 mm Hg). [2008]
(a) 1 + α (b) 1 – α (a) 52 mol per cent
(c) 1 + 2α (d) 1 – 2α (b) 34 mol per cent
(c) 48 mol per cent
157. Benzene and toluene form nearly ideal solutions. At (d) 50 mol per cent
20°C, the vapour pressure of benzene is 75 torr and
that of toluene is 22 torr. The partial vapour pressure 164. The vapour pressure of water at 20°C is 17.5 mm Hg.
of benzene at 20°C for a solution containing 78 g of If 18 g of glucose (C6H12O6) is added to 178.2 g of
benzene and 46 g of toluene in torr is [2005] water at 20°C, the vapour pressure of the resulting
(a) 25 (b) 50 solution will be [2008]
(c) 37.5 (d) 53.5 (a) 17.675 mm Hg (b) 15.750 mm Hg
(c) 16.500 mm Hg (d) 17.325 mm Hg.
158. Two solutions of a substance (non­electrolyte) are
mixed in the following manner. 480 mL of 1.5 M 165. Two liquids X and Y form an ideal solution. At 300K,
first solution +520 mL of 1.2 M second solution.
vapour pressure of the solutions containing 1 mol of
What is the molarity of the final mixture? [2005]
X and 3 mol of Y is 550 mmHg. At the same tem­
(a) 1.344 M (b) 2.70M
perature, if 1 mol of Y is further added to this solu­
(c) 1.50M (d) 1.20M
5.28 Chapter 5

tion, vapour pressure of the solution increases by 10
mmHg. Vapour pressure (in mmHg) of X and Y in
their pure states will be, respectively: [2009]
(a) 300 and 400 (b) 400 and 600
(c) 500 and 600 (d) 200 and 300
166. A binary liquid solution is prepared by mixing n­heptane
and ethanol. Which on of the following statement is cor­
rect regarding the behavior of the solution? [2009]
(a) The solution in non­ideal, showing +ve deviation
from Raoult’s Law.
(b) The solution in non­ideal, showing –ve deviation
from Raoult’s Law.
(c) n­heptane shows +ve deviation while ethanol
shows –ve deviation from Raoult’s Law.
(d) The solution formed is an ideal solution.
167. If sodium sulphate is considered to be completely
dissociated into cations and anions in aqueous solu­
tion, the change in freezing point of water (ΔTf), when
0.01 mol of sodium sulphate is dissolved in 1 Kg of
water, is (Kf = 1.86 K kg mol–1) [2010]
(a) 0.0372 K (b) 0.0558 K
(c) 0.0744 K (d) 0.0186 K
168. On mixing, heptane and octane form an ideal solution.
At 373 K, the vapour pressures of the two liquid com­
ponents (heptane and octane) are 105 kPa and 45 kPa
respectively. Vapour pressure of the solution obtained
by mixing 25.0 g of heptane and 35 g of octane will be
(molar mass of heptane = 100 g mol–1 and of octane =
114 g mol–1) [2010]
(a) 72.0 kPa (b) 36.1 kPa
(c) 96.2 kPa (d) 144.5 kPa
170. Ethylene glycol is used as antifreeze in a cold cli­
mate. Mass of ethylene glycol which should be added
to 4 kg of water to prevent it form freezing at –6°C
will be: (Kf for water = 1.86 kg mol–1, and molar mass
of ethylene glycol = 62 g mol–1) [2011]
(a) 204.11 g (b) 804.32 g
(c) 600.20 g (d) 302.40 g
171. Kf for water is 1.86 K kg mol–1. If your automobile
radiator holds 1.0 kg of water, how many grams of
ethylene glycol (C2H6O2) must you add to get the
freezing point of the solution lowered to –2.8°C?
[2012]
(a) 39 g (b) 93 g
(c) 72 g (d) 27 g
172. Consider separate solution of 0.500 M C2H5OH(aq),
0.100 M Mg3(PO4)2(aq), 0.250 M KBr(aq) and 0.125
M Na3PO4(aq) at 25° C. Which statement is true about
these solutions, assuming all salts to be strong electro­
lytes? [2014]
(a) 0.125 M Na3PO4 (aq) has the highest osmotic
pressure.
(b) 0.500 M C2H5OH (aq) has the highest osmotic
pressure.
(c) They all have the same osmotic pressure.
(d) 0.100 M Mg3(PO4)2 (aq) has the highest osmotic
pressure.
173. The vapour pressure of acetone at 20°C is 185 torr.
When 1.2 g of a non­volatile substance was dissolved
in 100 g of acetone at 20°C, its vapour pressure was
183 torr. The molar mass (g mol–1) of the substance is
[2015]
(a) 32 (b) 64
(c) 128 (d) 488

169. The degree of dissociation (α) of a weak electrolyte, 174. 18 g glucose (C6H12O6) is added to 178.2 g water.
The vapour pressure of water (in torr) for this aqueous
AxBy is related to van't Hoff factor (i) by the expres­
solution is: [2016]
sion: [2011]
(a) 76.0 (b) 752.4
(c) 759.0 (d) 7.6
x + y −1 x + y +1
(a) α = (b) α =
i −1 i −1
i −1 i −1
(c) α = (d) α =
(x + y − 1) x + y +1
 Solutions 5.29

ANSWER KEYS

Single Option Correct Type

1. (a) 2. (a) 3. (b) 4. (d) 5. (c) 6. (b) 7. (a) 8. (c) 9. (d) 10. (a)
11. (a) 12. (c) 13. (c) 14. (b) 15. (c) 16. (b) 17. (a) 18. (b) 19. (d) 20. (b)
21. (a) 22. (d) 23. (c) 24. (b) 25. (d) 26. (b) 27. (b) 28. (a) 29. (b) 30. (b)
31. (d) 32. (b) 33. (a) 34. (d) 35. (b) 36. (a) 37. (d) 38. (b) 39. (b) 40. (c)
41. (c) 42. (a) 43. (a) 44. (c) 45. (a) 46. (d) 47. (d) 48. (a) 49. (d) 50. (d)
51. (b) 52. (b) 53. (d) 54. (b) 55. (c) 56. (c) 57. (d) 58. (c) 59. (c) 60. (b)
61. (c) 62. (a) 63. (a) 64. (d) 65. (a) 66. (c) 67. (a) 68. (c) 69. (c) 70. (c)
71. (a) 72. (a) 73. (a) 74. (b) 75. (b) 76. (d) 77. (c) 78. (c) 79. (c) 80. (c)
81. (d) 82. (a) 83. (a) 84. (a) 85. (a) 86. (d) 87. (b) 88. (a) 89. (c) 90. (d)
91. (d) 92. (d) 93. (a) 94. (a) 95. (a) 96. (b) 97. (c) 98. (d) 99. (a) 100. (c)
101. (c) 102. (a) 103. (c) 104. (b) 105. (d) 106. (b) 107. (c) 108. (c) 109. (d) 110. (a)
111. (c) 112. (a) 113. (b) 114. (b) 115. (a) 116. (b) 117. (c) 118. (b) 119. (a) 120. (c)
121. (d)

More than One Option Correct Type

122. (a), (b) and (c) 123. (b) and (c) 124. (a) and (c) 125. (c) and (d)
126. (b), (c) and (d) 127. (a) and (c) 128. (a) and (c) 129. (b) and (c)
130. (b) and (c) 131. (a), (b) and (c)

Passage Based Questions

132. (c) 133. (c) 134. (b) 135. (d) 136. (d) 137. (a)

Match the Column Type

138. (a) →(p) and (q); (b) →(p), (q), (r) and (s); (c) →(p), (q), (r), (s) and (t); (d) →(p) and (q);

Integer Type
139. 3 140. 2 141. 2 142. 3 143. 2 144. 2 145. 2 146. 2

Previous Years’ Questions

147. (a) 148. (a) 149. (b) 150. (a) 151. (b) 152. (a) 153. (c) 154. (c) 155. (a) 156. (c)
157. (b) 158. (a) 159. (c) 160. (d) 161. (a) 162. (d) 163. (d) 164. (d) 165. (b) 166. (a)
167. (b) 168. (a) 169. (c) 170. (b) 171. (b) 172. (b) 173. (c) 174. (b)
5.30 Chapter 5

HINTS AND SOLUTIONS

Single Option Correct Type

3. Due to increase of temperature the solubility of NaCl will 36. For non­ideal solution showing positive deviation, ∆H = +ve
increase, so it will become unsaturated. and, ∆V = +ve.
6. Br2 being a liquid is more soluble than Cl2 or I2. 37. 0.01 M Na3PO4 give more number of ions hence there is
8. The molecules of acetone and chloroform develop H­bonds. greater lowering in vapour pressure. Thus it has least vapour
9. A supersaturated solution is metastable, as on slight distur­ pressure.
bance, solid separates easily. 39. πSugarcane = πx
11. The relative lowering of vapour pressure is equal to mole Csugar = Cx
fraction of the solute.
13. Solubility of a gas in a liquid increases with decreases in 5 × 1000 1 × 1000
=
temperature 342 × 100 M × 100
as s α 1/T on solving M = 68.4
14. As here only NaCl may undergo dissociation so it can show 42. For Al2 (S04 )3, ‘i’ is five, as for K4Fe(CN)6.
abnormal colligative properties 48. As v = w/d
17. moles = molarity × volume in litre w × d × 1000
__________
So, M = W × Mol. wt
= 0.5 × 2.5 = 1.25
2.55 × 100 × 98
____________
19. As it will give least number of ions (lowest ‘i’) so it will have ... d = 20 × 1000 = 1.25 (nearly)
maximum boiling point. 52. 1 m NaCl sol = 1 mol NaCl in 1000 g water
20. As ‘i’ is maximum for Al2(SO4)3 so it has lowest F.P. = 58.5+ 1000 g solution
22. The azeotropic mixture cannot be separated into indi­ = 1058.5 g solution
vidual components as both the components boil at the same 1058.5
_____
temperature. = 1.21 ≈ 875 mL
23. As the solution of sugar in water has free molecules. 1
________
molarity = 875 × 1000 = 1.143
24. Formality is the number of formula weights present in one
litre of the solution. Formality changes with temperature 53. 0.5 M H2SO4 = 1 N H2SO4
because it involves volumes, which in­turn change with N1V1 = N2 V2
temperature. (cone.) (dil.)
25. When solute is present in trace quantities, concentration is 1N × 1L = N2 × 10L
expressed in parts per million (ppm). N2 = 1/10 N = 0.1 N
27. Molarity decreases and, volume increases with increase in p0 – ps
_____
55. p0
= x solute
temperature.
0
p –
_____s p
28. At the freezing point, liquid and solid are in equilibrium. = 0.25
0.80
When a solution of a non­volatile solute is cooled to a
temperature below the freezing point of solution, some of p0 – ps = 0.20 atm
the liquid solvent will separate out as a solid solvent. nRT
____
59. P = V
29. When A – B attractions are greater, less vapours are formed. 14 × 100 × 10–8 × 180
________________
So, T = PV/Rn = 0.082 × 10
= 307.3 K.
30. As addition of a non­volatile solute to water increases its
boiling point, so egg will cook sooner. 61. Benzoic acid associates in benzene as
31. As there is no movement of ions. 2C6H5COOH (C6H5COOH)2
32. Due to H­bonding between H2O and C4H9OH. The number of particles decreases and hence osmotic pres­
sure decreases.
33. One molal solution is one which contains one mole of a sol­
1.8/180
______
ute in 1000 g of the solvent. 62. Molality = 100 × 1000 = 0.1
34. As temperature of the two phases is same, their average K.E. ∆Tb = Kbm
is same. Kb =ATb/m = 0.1/0.1
35. Benzoic acid exists as a dimer because of hydrogen bonding. = 1 K/m
 Solutions 5.31

66. Kf = ∆T/m = 1.86/0.1 = 18.6 M = 8.3 × 10–3 mol/m3

0.1 × v + 0.3 V = M3 × 2V = 8.3 × 10–3 mol/L.
or M3 = 0.2, ∆Tf = 18.6 × 0.2 = 3.72°C 92. Except glucose, all other are electrolytes undergo­
Tf = –3.72°C ing dissociation (i > 1). Glucose is non electrolyte,
69. 2C6H5COOH (C6H5COOH)2 i = 1. So, it has least value of ∆Tf and freezing point is
maximum.
before association 1 mol 0
after association 1–x x/2 93. Weight of sugar solution = 214.2 g
x
__ x
__ Weight of sugar = 34.2 g
Total = 1 – x + 2 = 1 – 2
1 – x/2
_____ Weight of water = 214.2 – 34.2 = 180 g
i= 1 Molality = W2/M2 × 1000 × W1
x
__
as i = 1 – 2 = 34.2/342 × 1000/180 = 0.55 m
72. 0.1 m Na3PO4 = 0.4 m particles which is maximum. 94. 2KI + HgI2 K2[HgI4] 2K+ + [HgI4]–2
So, lowering of vapour pressure will be maximum. there is a decrease in the number of ions present in the sol
73. NaAg(CN)2 Na+ + Ag(CN)2– tion so ∆Tf decrease or freezing point is raised.
1 0 0 so i = 1 + α P − P5 m×M P − P5 1000
95. As = or m = ×
1­α α α so i = l + l = 2 P 1000 P M
as α = 1 for very dilute solution
1000
75. n(P) = 3, n(Q) = 2 m = 0.0125 × = 0.7m
18
p0(P) = 80 torr, p0(Q) = 60 torr
96. Number of ions formed
x(P) = 3/5, x(Q) = 2/5
Urea: NaCl: Na2SO4
p(P) = 3/5 × 80 = 48 torr
0.01 mole : 0.01 × 2 mole : 0.01 × 3 mole
p(Q) = 2/5 × 60 = 24 torr
1:2:3
p(Total) = p(P) + p(Q)= 48 + 24 = 72 torr
Thus, ∆Tf is also in the same ratio.
76. For isotonic solution
(∆Tf α i when molality is constant)
W1/M1V1 = W2/M2V2 97. π = CRT
10
_______ 5
_______ ___
π 0.0821
__________
= C = RT = 0.0821 × 300
60 × 100 M2 × 100
= 0.3 × 10–2 mol L–1.
On solving M2 = 300 g/mole
99. Since the two solution are isotonic, thus
1000 × Kf × w
___________
77. ∆T = W×m W2 W2
(glycerine) = (glucose)
1000 × 5.12 × 1
____________ M 2 .V2 M 2 .V2
So, ∆T = 250 × 51.2
= 0.4 K
1.02
_______ 2
_______
=
M2 × 0.1 180 × 0.1
85. ∆Tb = Kbm = 0.51 × 0.1 = 0.051°C
1.02 × 180 × 0.1
____________
Now, boiling point of solution = 100 + ∆Tb or M2 = 0.1 × 2
= 91.8
= 100 + 0.051 W2 . RT
______ 4 × 0.082 × 300
____________
= 100.051°C 100. π = M . V = 246 × 1
2
86. At constant volume and pressure we get π = 0.4 atm.
T1/T2 = W1 m2/W2 m1 101. ∆Tb = 100.18 – 100 = 0.18
After putting the values and solving ∆Tb ____
Kb m __
Kb
____
T2=100.25°C. = =
∆Tf Kf m Kf
87. Concentration of NO3– ions will be 0.18 _____
____ 0.512
∆Tf
= 1.86
= 0.1 M / 2 = 0.05 M.
88. Osmotic pressure 0.18 × 1.86
________
∆Tf = 0.512
= 0.654
P=hdg
= (2.4 × 10–3 m) (0.88 × 103 kg m–3) Tf = (0 – 0.654)°C = –0.654°C.
= 20.7 Pa = 2.7 Nt/m2 102. Solution of sucrose is isotonic with solution of gulucose,
thus
molarity = P/RT
P (sucrose) = P (glucose)
20.7 Nt/m2
________________ ns nG
= 8.314 J/kmol × 298 K __ __
vs RT = vG
5.32 Chapter 5

ns __
__ nG At equilibrium. C(l – α) Cα Cα
vs = vG
VS = VG = 1 L [H+] = Cα

So, ns = nG or α = [H+]/C = 10–2/0.1 = 0.1

WS WG i = 1 + α = 1 + 0.1 = 1.1
=
( mol wt ) S ( mol wt ) G Now, π = iCST
= 1.1 × 0.l × ST
34.2 x = 0.11 ST
=
342 18.0 g 108. P (Na2SO4) = i CRT = i (0.004) RT
x = 18.0 g P (glucose) = CRT = 0.010 RT
As solutions are isotonic, i (0.004) RT
DTf W m = 0.01 RT
103. Kf for water =
1000 w This gives i = 2.5
(here W = Wt of water, w = Wt of cane sugar, Na2SO4 2Na+ + SO42–
m = Molecular wt of cane sugar) 1 mole 0 0
2.15 × 100 × 342
____________ 1–α 2α α,
= 1000 × 5
= 14.7
for 5% glucose Total = 1 + 2α, that is, i = 1 2 α
2.5 – 1 ___
i – 1 _____
____ 1.5
Kf × 1000 × W´
___________ α= 2
= 2 = 2 = 0.75 = 75 %
∆ Tf = W×m´ 109. πV = nRT
14.7 × 1000 × 5
____________
= 100 × 80
= 4.08 2 × l = n × 0.0821 × 300
freezing point of glucose solution or n = 0.0821 = molality
= 273.15 – 4.08 = 269.07 K. ∆Tf = KF.m
104. K4 [Fe(CN)6] 4K+ + [Fe(CN)6]–4 = 1.86 × 0.0821 = 0.1510
freezing point of solution
Initial cone 10 0 0
= 273 – 0.1510 = 272.849 K.
At eq 1–α 4α α
110. 93% H2SO4 (w/v) means 93 g of H2SO4 is present in 100 cc
i = l – α + 4α + α = l + 4α of solution.
50
___ Since, volume of solution = 1000 mL
α= = 0.5
100
Amount of H2SO4 = 930 g per litre
i = l + 4 × 0.5 = 3
d = 1.84 g/mL
π = iCRT M
__
d = v or
= 3 × 0.1 × 0.0821 × 300 M=d×V
= 7.389 atm. = 1.84 × 1000
105. Normality (N) = 1.5 = 1840 g
Equivalent weight of H2O2 = 17 Wt. of solvent = 1840 – 930 = 910 g
930
___ 1000
____
Strength = normality × equivalent weight Molality = 98 × 910 = 10.43 m
= 1.5 × 17 = 25.5. 111. For equimolar solutions, xB = xT = 0.5 as
2H2O2 2H2O + O2 As pB = xB.p0B= 0.5 × 160 = 80 mm

As (2 × 34 = ) 68 g of H2O2 produces 22.4 litres oxygen at As pT = xT. p0T = 0.5 × 60 = 30 mm

NTP, therefore 25.5 g of H2O2 will produce Hence, pTotal = pB + pT
22.4
____ = 80 + 30 = 110 mm
= 68 × 25.5 = 8.4 litres of oxygen.
Mole fraction of toluene in vapour phase
So, volume strength of H2O2 solution = 8.4.
= pT/pmix
106. pH = 2, [H+] = 10–2 = 30/110 = 0.27
HA H+ + A 112. Eq wt of (COOH)2.2H2O = 126/2 = 63
Initially C 0 0 Normality of oxalic acid (N)
 Solutions 5.33

W
_____
N = E × V × 1000 W2
6.3 ____
___ 1000 117. For original solution, pV1 = S.T.
= 63 × 250 = 0.4 N M2
(oxalic acid) (NaOH) 500
___ W2
___
760
× V1 = M × S × 283 (i)
N1 V1 = N2 V2 2

0.4 × 10 = 0.1 × V2 After dilution,

So, V2 = 40 mL. 105.3
_____ W2
___
76
× V2 = M × S × 298 (ii)
113. α = 0.23 2
V2 _____
__ 105.3 ___298
i = 1 + α = 1 + 0.23 = 1.23 now Now, V × 760 = 283
1
3 × 10–3 × 103
___________ V2 ___
__ 298 _____
500
n (moles of acetic acid) = 60
= 0.05 Or V = 283 × 105.3 = 5
1
Moles of acetic acid
______________
Molality = Wt. of solvent in kg Thus, the solution is diluted to five times its original volume.
118. Mass of solution = d × V= 1.1 × 1000 = 1100
0.05
__________ 15
___
= 498.5 × 1000 = 0.1 now mass of solute = 100 × 1000
∆Tf = i KF m = 1.23 × 1.86 × 0.1 = 150 g
= 0.228 K So, mass of solvent = 1100 – 150 = 950 g

114. Ba(NO3)2 Ba2+ + 2NO3– w

_____
molality = m × W × 1000
Initial 0.1 M 0 0
150 × 1000
________
= 98 × 950 = 1.6
At eq. (0.1 – α) M αM αM
(0.1 – α) + α + 2 α p0 – ps ___
_____ W2 ___
M1
_____________
i= 0.1
119. p =M ×W
2 1

W2 . M1
____________
0.1+ 2a M2 = (p0 – p /p0) . W
= = 2.74 s 1
0.1
5 × 18
___________________
On solving, = (3000 – 2985/3000) × 100
α = 0.087 On solving,
0.087
_____
So, α % = 0.1 × 100 = 87% M2=180.
__________________ p0 – ps
Loss in wt of water bulb _____ 0.013
_____
115. HX H+ + X– 120. Gain in wt of CaCl tube = p =
s 4
Initially 1 0 0 2
According to Raoult’s law,
At eq. (1–0.2)0.2 0.2 × 0.2 0.2 × 0.2
0.013 _____
_____ 26/M
0.16 M 0.04 M 0.04 M 4
= 200/18
Total moles of solution at eq. 26 × 18 × 4
_________
M = 0.013 × 200 = 720.
= 0.16 + 0.04 + 0.04
121. p1 + p2 = p0x + p20 (1 – x)
= 0.24
= p01 (0.16) + p02 (0.84) = 760 mm
∆Tf = Kfm
p02 – p01 = 472 mm of Hg
= 1.86 × 0.24
p01 = (p01 + 472) mm of Hg
= 0.45
p01(0.16) + (p01 + 472) 0.84 = 760
So, f.p. = 0 – ∆Tf = 0 – 0.45
p01 mm of Hg = 760 – (0.84 × 472)
= –0.45°C
p01 = 363.5 mmof Hg
116. Fe + 2HC1 FeCl2 + H2
2+
Moles of Fe formed
= ½ × moles of HCl used
0.4 × 500
_______
½× 1000
= 0.1
5.34 Chapter 5

More than One Option Correct Type

122. Hexane Heptane 127. 760-670 0.1
=
2 2 670 N
PT = × 50 + × 60
4 4  67 
= 25 + 30 So N =  
 90 
= 55 mm Hg
Weight of benzene that is frozen out
Hence PHexane = 25 mm Hg
PHeptane = 30 mm Hg  67 
=  0.9 −  × 78gm
 90 
PTotal = 55 mm Hg
= 12.16 g
123. ∆Tf = Kf × m
∆Tf = kf × m
20.5 1000
(5.48 - 4.33)=5.1 × × 90 1000
38n 400 = 5.12 × ×
670 72
n ≈ 6.0
Molecular formula of non­ electrolyte = (C3H2)6 = 8.81 K
= C18H12. Temperature to which it must be frozen
= 278.5 − 8.81 = 269.69 K = 269.7 K
20.5 1000
Molality of solution (m) = × 128. According to Dalton’s law,
38 × 6 400
∆Tb = Kb × m po2 = Ptotal X Ogas
2

20.5 × 5
T’b = Tb + 2.53 × = 0.20 × 760 = 152 mm Hg.
38 × 12
According to Henry’s law,
≃ 0.57
T’b = Tb + 0.57 = 80.2 + 0.57 = 80.77oC po2 = K H × X Oliq.2
Alternatively, the carbons and hydrogens in the compound 152 = 3.04 × 107 X Oliq2 .
must be in the ratio of 3 : 2, which is true in C18H12. The boil­
ing of solution will be higher than 80.2oC, so it would mean X O2 = 5 × 10−6
that (d) cannot be the right choice and calculation suggest
that the boiling point of solution is 80.77oC. no2
X O2 =
nO2 + nH 2 O
125. Ptotal = PBo X B + PTo X T
1 3 no2
= 42 × + 36 × = 38mm =
3 2 nO2 + 1000 / 18
PM YB = PoB × XBwhere YB is the mole fraction of Benzene is
vapour phase no2 no2
= ≈
nO2 + 55.56 55.56
14 7
38 × YB = 14; YB = = ;
38 19 Number of moles of O2 dissolved nO2
7 11
YA = 1 − = = 55.56 × 5 × 10­6 = 2.77 × 10­4
19 19
[O2] = 2.77 × 10­4 M
126. Solute which is not undergoing association or dissociation 130. According to Raoult's law of dilute solution.
has X = Kf.m (i)
P O − PS
Solute which is undergoing 100 % dissociation has 4X = = mole fraction of solute and PS ∝ mole fraction
PO
i.Kf.m
of solvent.
From (1) and (2), we get i = 4
i would be 4 for salts of the type A3B, AB3, A2B2.
 Solutions 5.35

Passage Based Questions

132. The colligative properties of electrolyte solutions are usually = 20[H20P] + [H20P]
smaller than anticipated because at higher concentrations, = (20 + 1) [H20P]
electrostatic forces come into play and bring about the for­ = 21[H20P]
mation of ion pairs. The presence of an ion pair reduces the
πV = nRT
number of particles in solution, causing a reduction in the
colligative properties. π = CRT
Electrolyte containing multi charged ions such as Mg2+, C is total concentration of all ions present in the solution
SO42− has a greater tendency to form ion pairs than electro­ 0.225 1000
lytes such as NaCl, which is made up of singly charged ions. [H 20 P] = ×
M 10
133. When complex ions are formed their solutions show abnor­ 0.225 1000
mally low colligative effects than expected because they C=21 × ×
M 10
contain fewer particles of solute than would otherwise be 0.225 1000
present. When a little mercuric iodide is added to potassium 0.257=21 × × × 0.0821 × 298
M 10
iodide solution the freezing point depression is smaller than 21 × 0.225 × 0.08821 × 298 × 1000
before because the simple ions have united as follows: M=
0.257 × 10
2K+ + 2I­ + HgI2 2K+ + [HgI4]2­
134. Salt of protein undergoes dissociation as follows. On solving M = 4.5 × 104 g mol­1
137. K4[Fe(CN)6] 4K+ + [Fe(CN)6]4−
Na20P 20Na+ + P20−
1 0 0
The formula of protein will be H20P
(1 ­α) 4α α
Total concentration of ions in the solution
= concentration of cations +conc. of anion 1 + 4α
i= = 1 + 4 × 0.6 = 3.4
1

Integer Type
139. ∆Tf = Kfm 0.93 = 1.86 × m M
m = 0.5 molal 142. m= × 10
103
(1000 × d-M × M B )
∆Tb = Kbm 0.26 = Kb × 0.5
Kb = 0.52 K kg mol­1 144. 0.2046 = (1 + α) × 1.86 × 0.1
1 + α = 1.1 ; α = 0.1
7.9 × 1000
Similarly 0.44 = 0.52 × [H+] = Cα = 0.1 × (0.1) = 10­2 M
31n × 100
[mol. mass = 31 n] pH = 2
n =3 145. 0.7 = 2 × Kf × 0.2
140. Let n molecules of phenol polymerise 0.7 7
∆Tf = iKfm Kf = =
0.4 4
∆Tf 0.93 × 94 × 100
i= = Hg(CN)2 + mCN–→ Hg(CN)m­ m+2
K f m 1.86 × 9.4 × 103
0.1 0.2 0
i 1
=1or (i-1) = -1, 0 (0.2 – 0.1 m) 0.1
1/n-1 n
Now, molarity of K+ = 0.2 M
i = 1/n = 1/0.5 = 2.0 Molarity of CN− = (0.2 – 0.1m) M
141. ∆Tf = i × Kf × m Molarity of complex = 0.1 M
0.0054 = i × 1.80 × 0.001 0.53 = Kf (0.2 + 0.2 – 0.1 m + 0.1)
0.0054 = Kf (0.5 – 0.1 m)
i= =3
1.8 × 0.001 7
0.53 = (0.5 − 0.1m)
i.e., the complex salt gives 3 ions during dissociation in 4
aqueous solution. 2.1 = 3.5 – 0.7 m
[Pt(NH3)4Cl4] [Pt(NH3)4Cl2]2+ + 2Cl− 0.7 m = 1.4
2 Cl− ions require 2 moles of Ag+ ions. m=2
5.36 Chapter 5

146. ΔTf = i × Kf × m 0.704

i= ≈2
0 – (−0.704) = i × 1.86 × 0.1892 1.86 × 0.1892

Previous Years’ Questions

149. ∆Tb = mKb 2.05
_________________
M = 1000 × 1.02 – 2.05 × 60 = 2.28 mol kg–1
∆Tf = mKf
p0 – ps __
_____ 18 × 18
n _________
∆Tb __
___ Kb _____
0.512 160. ps = N = 180 × 178.2 = 0.01
= = 1.86
∆Tf Kf
(p0 = 760 torr)
0.512
_____
∆Tb = 1.86 × 0.186 = 0.0512°C 760 – ps
______
ps = 0.01.
150. ∆Tf = molality × Kf × i 161. Solutions with the same osmotic pressure are called isotonic.
= 0.2 × 1.85 × 1.3 Let the molar mass of the substance be M.
= 0.481°C π1 = π2 C1RT = C2RT
Freezing point = –0.481°C So, C1 = C2
153. Boiling point As density of the solutions are same
= T0 (solvent) + ∆Tb (elevation in b.p.) 5.25
____ 15
__
So, M = 60
∆Tb = mi Kb 5.25 × 60
_______
M= 1.5
= 210.
where, m is the molality (≈ molarity m)
162. Let the vapour prepssure of pure ethyl alcohol be P,
i, the van’t Hoff factor = [1 + (y – 1) x] According to Raoult’s Law,
Kb, molal elevation constant.
290 = 200 × 0.4 + P × 0.6
Thus, ∆Tb∆ i 290 – 80
_______
P= 0.6
= 350 mm Hg.
Assume 100 % ionization
(a) mi (Na23SO4) = 0.01 [1 + (y – l)x] = 0.03 163. PT = P°A XA + P°B XB
(b) mi (KNO3) = 0.01 × 2 = 0.02 760 = 520 XA + P°B (1 – XA)
(c) mi (urea) = 0.015 On solving, we get
(d) mi (glucose) = 0.015 XA = 0.5
156. Na2SO4 2Na+ + SO42– So mole % of A = 50 %
1 0 0 P0 – P S
_____
164. PS = XSolute
1–α 2α α
17.5 – PS ___
_______ 0.1
van’t Hoff Factor (i) = 10
PS
1___________
–α+2α+α
= 1 1+2α 17.5 – PS/PS = 0.01
157. PB = P0B xB On solving, we get
P0B = 75 torr PS = 17.325 mm Hg.
78 / 78
_______________ 1
_____ 1
___ 165. As P = P0 .X + P0 .X
xB = (78 / 78) + (46 + 92) = 1 + 0.5 = 1.5 T X X Y Y
1
___
PB = 75 × 1.5 = 50 torr 1 3
500 = PX0 . + PY0 .
158. M1 V1 + M2V2 = M3V3 4 4
(1st sol) (2nd sol) (mixture)
1.5 × 480 + 1.2 × 520 = M3 (480 + 520) PX0 + 30Y = 2200 (i)
1000 M3 = 720 + 624 on adding 1 mole of Y (P) be comes 560 so
M3 = 1344/1000= 1.344 M 1 4
M
___________ 560 = PX0 . + PY0 .
159. Molality , m = 1000d – M.M × 1000 5 5
2

where M = Molarity, d = Density, PX0 + 4 PY0 = 2800

(ii)
M2 = Molecular mass From eq. (i) and (ii)
 Solutions 5.37

169. Moles at AxBy xAy+ + yBx–

PX0 = 400 mm hg
Elquilibrium 1–α xα yα
PY0 = 600 mm hg i = 1 – α + xα + yα
166. As interactions decrease so a +ve deviation is observed here (i – 1) = α(x + y – 1)
167. Na2SO4(s) → 2Na+ (aq) + SO42– (aq) i −1
α=
3 (x + y − 1)
i= =3
1
170. ∆Tf = Kf × m
∆Tf = i.Kf.m w
= 3 × 1.86 × 0.01 6 = 1.86 ×
62 × 4
= 0.0558 k 6 × 62 × 4
w= = 800 g
168. PT = ( 0
Pheptane x heptane ) (
+ 0
Poctane x octane ) 1.86
171. ∆Tf = Kf m
 25   35 
 100   114  WB 1000
PT = 105 ×  + 45 × 2.8 = 1.86 ×
35   35 
×
25 25 MB WA
 +   + 
100 114   100 114 
WB 1000
= 1.86 × ×
 0.25   0.3  62 1000
=  105 ×  +  45 × 
 0.25 + 0.3   0.25 + 0.3  = 93.3 g

 0.25   0.3 
=  105 ×  +  45 × 
 0.55 0.55 

= 47.25 + 24.75 = 72 kPa