Solutions Dinesh

Solutions
T TABLE 3.1 Types of Solutions
Solutions
SOLUTE
Solvent
.............................. ................................................ .......................
Example
GAS
GAS
AIR (MIXTURE OF MANY GASES)
GAS
LIQUID
AERATED DRINKS
We
know
that
substances
exist
in three phases I.E. solid, liquid and gaseous phases. We are also familiar
GAS
SOLID
GASES ADSORBED OVER METAL SURFACE (OCCLUSION). GASES DISSOLVED
with the general characteristics ofIN these
phases.
Let us study as to what will happen if the substances
MINERALS
.
belonging
to
the
same
or
different
phases
are
mixed
LIQUID
GAS
HUMIDITY IN AIR together. In broad terms, the mixture is called solution.
Now in the mixture, the different constituents may be present either in the same phase or in more than one
LIQUID
LIQUID
* MIXTURE OF MISCIBLE LIQUIDS (ALCOHOL IN WATER)
phase I.E. the solution may be homogeneous or heterogeneous. For example, a mixture of oil and water is
L
IQUID
S
OLID
M
ERCURY IN AN AMALGAM, HYDRATED SALTS
heterogeneous while that of salt and water is normally homogeneous. Homogeneous mixture of two or more
SOLID
IODINE
VAPOURS
IN AIR The different constituents present in a true solution
substances
is knownGasAStrue solution
cr simply
a solution.
SALTS DISSOLVED
orSOLID
solution lose theirLIQUID
physical identities
and cannotINbeWATER
separated from each other by available methods like
filtration,
settling
or
centrifugation
etc.
However,
they
must
not chemically
with .each other. Thus, a true
SOLID
SOLID
ALLOYS OF METALS E.G. INTERSTITIAL
SOLIDreact
SOLUTION
solution may be defined as :
a homogeneous mixture of two or more pure non-reacting substances whose composition can
be varied within certain limits.
In the present unit, we shall focus our attention on the units of expressing the concentration of the
solution, the vapour pressure of the solution and also certain properties known as colligative properties
which depend upon the number and nature of the particles in a solution and are independent of their other
physical and chemical characteristics.
3.1. COMPONENTS OF A SOLUTION
A solution may contain two or more substances also called components or constituents. A solution
which has two components is known as binary solution ( E.G. a solution of NaCl in water) while a solution
with three components is called ternary solution (E.G. absolution of NaCl and KC1 in water). Similarly even
more than three components may also be present. However, we shall concentrate only on the binary solutions
in which the component or constituent present in smaller proportion or amount is called solute while the one
present in excess is known as solvent. For example, in a binary solution of sugar in water, sugar acts as the
solute while water is the solvent. It may be noted that out of the three states of a substance any one can act as
the solute or solvent resulting in different types of solutions which are listed in Table 3.1.
As pointed above, all of them are of binary nature in which component present in excess is the solvent
while the one present in smaller proportion is the solute. %
Note : (i) A mixture of non-reacting gases is always homogeneous i.e. it represents a solution.
(II) A solution in which a gas acts as the solvent is known as a gaseous solution. Similarly, solution in
which a liquid or solid is the solvent is called a liquid or solid solution respectively. In the
present unit, we shall focus mainly on liquid solutions.
3.2. METHODS OF EXPRESSING CONCENTRATION OF SOLUTIONS (UNITS OF
CONCENTRATION*)
Concentration ol a solution implies the amount of the solute present in a given quantity of the solution
or the solvent. Thus, while expressing the concentration of a solution, only the relative amounts of the
components are considered. The concentration of a binary solution can be expressed in a number of ways.
Strength.
Strength of a solution may be defined as :

amount of the solute in grams present in one litre (or dm3) of the solution.
Mathematically. Strength = ---------------------Mass of the solute in grams
Volume of solution in litres (or dm3)
The units of concentration are gL"1 or g dm'3.

For example, if 4 grams of a solute are dissolved in 250 mL of the solution, then
(4g)
Strength = (250mL)
(4g)
16 g L>
Mass Percent.
Mass percent of a solution may be defined as :

the number of parts by mass of one component (solute or solvent) per 100 parts by mass of the
solution.
While expressing the concentration of any solution, the temperature is supposed to remain constant as the
concentration usually changes with the temperature.
3.3
Solutions
If A and B are the two components of a binary solution,

Mass percent of A =
WA
X 100
WA + WB
Mass percent of B =-------Wb, * 100
W A + wb
Volume Percent.
Volume percent of a solution may be defined as :

the number of parts by volume of one component (solute or solvent) per 100 parts by volume of
the solution.
Mathematically, Volume percent of A
Volume percent of B
_________
VA + VB
V
VB
+ VB
100
x 100
Remember
Both mass percent and volume percent are simply ratios and have no units.
Concentrations can also be expressed in terms of weight/volume (i.e. WA/).

For example, 10% solution KCI (W/V) means that 10 g of the salt are dissolved
__________________ in 100 ml (or 0-1 L) of the solution.
Parts per Million (ppm).
For a dilute solution in which a very small amount of the solute is dissolved in large excess of the
solvent, the values of both mass percent and volume percent will be very small. In order to magnify the
same, the concentrations are expressed as parts per million (or as ppm). It may be defined as :
the number of parts by mass (or by volume) of one component per million parts by mass (or by volume)
or the solution.
For example, if A and B are the two components of the solution.
Mass of A ^
PPmA 'Mass of solution
or
Volume of A
Volume of solution X ^
Note : The degree of hardness of water is normally expressed as ppm. For example, if the hardness of
water due to the presence of Ca(HCC>3)2 is 16-7 ppm, this means that 16-7 parts of Ca(HC03>2 are present
in 106 parts of the solution of hard water.
Similarly, the concentration of the poisonous gases in air is also expressed as ppm. For example, 100
ppm for oxides of nitrogen (NO) implies that 100 parts by volume of the gas are present in 10 6 parts by
volume of air.
3.4
Solutions
Molarity (M)
Molarity of a solution may be defined as :

the number of gram moles of the solute dissolved per litre (or dm3) of the solution
Mathematically, Molarity (M)
Gram moles of the solute

Volume of solution in litres
Mass of solute in grams / molar mass

Volume of solution in mL/1000
UNITS OF MOLARITY : Gram moles/Litre or Moles/Utre
For example, the molarity of solution containing 4-9 grams of H2S04 dissolved in 250 mL of the
solution can be calculated as :
Molarity (M)
4 -9g / 98g mol'1

250 mL /1000
(0-05 mol)
(0 25 L)
= 0-2 mol L'1 (OR 0-2 M)

MOLARITY OF SOLUTION ON MIXING TWO SOLUTIONS. When volume V! of a solution of molarity Mj
is mixed with volume V2 of another solution of molarity M 2, then the molarity M3 of the resulting solution
(volume = V( + V2) is given by the equation :
MiV, + M2V2 = M3 (Vj + V2)
Concept of Formality
It may be noted that crystalline ionic compounds such NaCl, KC1, CuS0 4 etc. donot exist as
molecules but as formula units and their molar masses are expressed as gram formula masses and not as
gram moles. Therefore, it is not fair to express their concentrations in terms of molarity. These are rather
expressed as FORMALITY (F). The formality of a solution may be defined as :
the number of gram formula mass of the solute dissolved per litre of the solution.
Mathematically, Formality (F) =
Gram formula mass of solute

UNITS of FORMALITY : Gram formula mass/Litre.

For example, the formality (F) of a solution containing 2-02 g of KN03 (Formula mass = 101)
dissolved in 500 mL of the solution may be calculated as follows :
Formality (F)=
(2-02g)/101g(formulamass)
500mL/1000
0 04 Formula mass L"1 or 0-04 F
It may be noted that in most of the cases, the concentrations of the ionic solutes are expressed
in terms of molarity and not formality. Therefore, the latter is merely a formality.
Solutions
3.5
Molality (m)
Molality of a solution may be defined as :

the number of gram moles of the solute dissolved in 1000 g (or kg) of the solvent.
Gram moles of the solute = Mass of solute in grams/molar mass
Mass of solvent in grams /1000
Mass of solvent in kg
Units of molality : Gram moles/kg or Moles/kg
For example, the molality of a solution containing 5-3 g of anhydrous Na2C03 in 200 g of water can be
calculated as follows :
Mathematically, Molality (M) =
5-3g/106gmol 1
(0 05 mol)
Molality (M) =------------------------- ~ ,n ,
= 0-25 mol/kg or (0-25 m)
200g/1000
(0-2 kg)
Difference between Molarity and Molality
In molarity, the volume of the solution is considered while in molality, the mass of the solvent
is taken into account.
The volume of the solution changes with the temperature while the mass of the solvent does
not change. Thus, molality is considered better for expressing the concentration of the solution
as compared to molarity.
Normality (N)
Normality of a solution may be defined as :
the number of gram equivalents of the solute dissolved per litre of the solution.
Mathematically, Normality (N) =
Gram equivalents of the solute

Mass of solute in gram / equivalent mass

Volume of solution in mL/1000
Units of normality : Gram equivalents/litre or Equivalents/litre
EQUIVALENT MASSES OF DIFFERENT SUBSTANCES
Equivalent mass of acid
Molar mass of acid

Basicity (No of replaceable H+ions present)
Equivalent mass of base
____________Molar mass of base____________

Acidity (No. of replaceable OH- ions present)
Equivalent mass of salt

Equivalent mass of element
______Molar mass of salt

Total positive charge on cation
Atomic mass of the element
Valency of the element
Formula mass of the ion
Equivalent mass of ion
Charge on the ion
Solutions
3.7
0Solutions
3.6
For
example,
the normality
of a solution containing 0-74 g of Ca(OH)2 dissolved in 200 mL
^ Tools
for
Numerical
Problems
of the solution can be calculated as follows :

'
_ .,
Molar mass 74
C R.
Mass of component= 37 = 37g equiv -i
Equivalent mass ot Ca(UH)2 =
x 100
Acidity
Mass Percent ~
Mass of solution
1
g / 37 of
g equiv
_
Normality of solution (N) = 0-74
011 equiv./L (OR 0-1 N)
Volume
component
200
mL
/1000
x
100
Volume Percent
Volume of solution
NORMALITY OF SOLUTION ON MIXING TWO SOLUTIONS. When volume V! of a solution of normality
Parts
of component
^
6
Nj is mixed with the volume V2 of another
solution
of normality
N
2 then the normality N3 of the resulting
Parts
million
(ppm)
Parts of solution
solution (volume
= V[per
+V
2) is given by the equation.
N,V, + N2V2 = N3 (Vi +Gram
V2) moles of solute____
Molarity (M) Volume of solution in Litres
Mole Fraction (x)
Mole
fraction
be defined
as (m)
: Mass of solvent ip Kg
Gram
molesmay
of solute
Molality
the ratio of the number of moles of one component to the total number of moles of all
Relation between Molarity and Molality
the components present in the solution.
Molarity _ Mass of solvent in kg _ Mass of solution - Mass of solute Molality
For a binary solution made up of components A and B.
Volume of solution in litres Volume of solution in litres
Mole fraction
of A
JCa) =
Density
of(solution
x Volume of solution - Moles of solute x molar mass of solute
"A + B
Mole fraction of B (xB) =
"B
AGram
+ "B equivalents of solute
Normality (N) =
Volume
n A of solution'Bin Litres
Sum of mole fractions (xA + xB) =
=1
+
,,
NoAof+ moles
of
component
B
A
+
B
Mole Fraction =-------;--- - -- --- - Moles in the solution
Remember
Mass of component
Mass
Mole Fraction
fraction being
a ratio has no units.
=
Mass of
of different
solution components in a solution is always
Sum of the mole fractions
Relation between molarity
equal toand
1.___________________________________________________________
density
_ % Strength x Density x 10
Mass Fraction
Molarity (M) Molar mass of solute
Mass fraction may be defined as :
Relationthe
between
normality
ratio of
the massand
of density
one component to the total mass of all the components present in the
solution.
% Strength x Density x 10
For a binary solution
containing
components A and B
Normality
(N) twoEquivelent
mass of solute
W4
Mass fraction of A =Normality of Acid = Molarity x Basicity

WA + W B
Normality of Base = Normality x Acidity
WB
Mass fraction
of B =on mixing solutions : M]V, + M2V2 = M3 '(Vj + V2)
Molarity
wA + w B
Normality on mixing solutions : N]Vj + N2V2 = N3 (V[ + V2)

NOTE : Mass fraction like mole fraction has no units. Mass fraction can be converted to mass percent on
multiplying with 100.
Mass percent = Mass fraction x 100
Solutions
3.8
GJ Problems on Mass Percent/Volume Percent/ppm
ÊXAMPLE 3.1. A solution has been prepared by dissolving 5g of urea in 95g of water. What is
the mass percent of urea in the solution ?
Mass of solute
Solution. Mass percent (Mass
Mass of solution
x 100
Mass of urea = 5g, Mass of water = 95g

(5g)
Mass percent of urea = Y5gT~95g7 * 100 = 5%
3 Example 3.2. Calculate the masses of cane sugar and water required to prepare 250 g of 25%
solution of cane sugar.
Solution.
Mass of solute , m
Mass percent = 77---------~~x !UU
Mass of solution
Mass percent = 25, Mass of solution = 250 g
25 _ Mass of cane sugar ^ ^
(250g)
25 x (250g)
Mass of cane sugar =---------------- = 62-5 g
Mass of water = 250 - 62-5 = 187-5 G

3Example 3.3. The density of 85% sulphuric acid is 1-7 g cm~3. What is the volume of the
solution which contains 17 g of sulphuric acid ?
Solution. 85 g of H2SO4 are present in the solution = 100 g
100 ,-7
17 g of H2SO4 are present in the solution = ~r x 17 = 20 g
OJ
Thus, mass of solution = 20 g ; Density of solution T7 g cm"3
Volume of solution
Mass
Density
(20g)
^5T = 11-8 cm3
(l-7gcm )
3 EXAMPLE 3.4. One litre of sea water weighs 1050 grams and contains 6 X 10~3 g of dissolved oxygen
gas. Calculate the concentration of the dissolved oxygen in ppm.
Solution. Mass of oxygen (O2) = 6 X 10"3 g
Mass of sea water = 1050 g
Mass of oxygen . n6
ppm of oxygen ~ -------------------- x
Mass of sea water
(6x 10~3g) .. 1f)6 " (lOSOgT =
5'71 ppm
3.9
Solutions
Problems on Molarity/Molalrty/Mole Fraction
01 XAMPLE 3.5. Calculate the molarity of a solution containing 4g of NaOH dissolved in 200 mL of the
solution.
(Haryana Board 2004)
SOLUTION.
Mass of NaOH / Molar mass of NaOH

Volume of solution in Litres
Mass of NaOH = 4g. Molar mass of NaOH 40 g mol-1,
Molarity (M) =
200
Volume of solution = 200 mL =
1000
= 0-2L
4g/(40gmol ')
,
Molarity (M) = & (Q *--------------- = 0-5 mol L"1 = 0-5 M
O EXAMPLE 3.6. The density of 10% by mass of KCl solution is 106 g cm'3. Calculate the molarity of
the solution.
(Pb. Board 2000)
Solution. Step L Calculation of volume of solution.
Mass of solution = 100 g Density
of solution = L06 g cm"3
... f
Mass of solution = (lOOg)
Volume of solution =---------- -;------Density
(i - uo g cm )
=94-34 cm3
STEP II. Calculation of molarity of solution

. . . .
,..
.... Mass of KCl / Molar mass of KCl
Molarity of solution (M) =----------------------------------------Volume of solution in dmr
Mass of KCl = 10 g ; Molar mass of KCl = 39 + 35-5 = 74-5 g mol"1
94.34
Volume of solution -- 94-34 cm3 =
= 0-0943 dm3
lUUU
Molarity (M) -
lOg / (74 5g mol-1)

(0-0943 dm3)- - - = 142 mo1 dm 3 = l'42 M
Molarity of solution can also be obtained by applying the formula :

% Strength of solution x Density of solution x 10
Molarity =------------------------------- -----------------------
Molar mass of KCl
10 x 1-06 x 10
Molarity =--------------------- = 1-42 M
O EXAMPLE 3.7. What is molarity of the resulting solution obtained by mixing 2-5 L of 0 5 M urea
solution and 500 mL of 2M urea solution ?
Solution. Molarity of solution on mixing :
M,^ + M2V2
M 3
(V1 + V2)
Solutions
3.10
According to available data :

M( = 0-5 M, Vj 2-5 L ; M2 = 2M ; V2 = 500 mL = 0-5 L _ (0-5 M
x 2-5 L) + (2M x Q-5L)
(2-25ML) _
"
(2-5 L + 0-5 L)
(3-0 L) 75 M
OEXAMPLC 3.8 Calculate the molality of 1 litre solution of 93% H2S04 (weight/volume). The density of
solution is 1-84 g mL'1.
(I.I.T. 1990. Pb. Board 2003)
Mj
Solution. STEP L. Calculation of the mass of solvent (water)

Volume of solution = 1L = 1000 mL
Density of solution = 1-84 g mL-1
Mass of solution = V x D = (1000 mL) x (1-84 mL-1) = 1840 g
Mass of H2S04/L of solution = ------------ - - x (1000 mL) = 930 g
(100 mL)
Mass of solvent (water) = 1840 - 930 = 910 g
Step r. Calculation of the molality of solution.
Molality (M)
Mass of H2S04
_ Mass of H2S04/MolarmassofH2S04
Mass of water in kg
= 930 g ; Molar mass of H2S04 = 98 g mol'1
Mass of water =
& = 0-91 kg
1000
Molality (M) = (930g/(98gmol *) = 10.43 mo, kg-i = 10.43 m (0-91 kg)
O EXAMPLE 3.9. The solubility of Ba(OH)2.8H20 in water at 298 K is 5-6 g per 100 g of water. What is
the molality of the hydroxide ions in a saturated solution of barium hydroxide at 298 K ? (Atomic mass of Ba
~ 137, O = 16)
(A.I.S.B. 1997)
SOLUTION. STEP 1. Calculation of molality of solution.
Massof solute / Molar massof
solute
Massof solvent in kg
Mass of solute, Ba(0H)2.8H20 = 5-6 g
Molar mass of solute, Ba(0H)28H20 = 137 + 2 x (16 + 1) + 8 x 18 = 315 g mol'1 Mass of
solvent (water) = 100 g = 0 -1 kg
(5-6g)/(315gmol_l)
Molality (MI) =-----------~Q }
-------- =0-18 mol kg'1 = 0-18 m
Molality of solution (M)
Step 11. CALCULATION OF MOLALITY OF OH' IONS

Barium hydroxide ionises in water as follows :
Ba(OH)2
Ba2* (AQ) + 20H' (AQ)
This shows that the molality of OH ions is twice the molality of Ba(OH) 2 = 2 x 0-18 m = 0-36 M
Solutions
3.11
OEXAMPLE 3.10. Calculate the number of moles of methanol in 5 litres its 2m solution if the density of
solution is 0-981 kg L'1. (Molar mass of methanol = 32-0 g m o l ( A . / . S . B . 2002) SOLUTION. 2M
SOLUTION OF METHANOL MEANS THAT 2 MOLES OF METHANOL ARE DISSOLVED IN 1 KG (LOOOG) OF WATER.
Mass of methanol (CH3OH) in 2 moles = (2 mol) x (32 0 g mol'1) = 64-0g Mass
of water in the solution = 1 kg = 1000 g
Mass of the solution = (1000 + 64) = 1064 g = 1-064 kg
Density of the solution = 0-981 kg L'1
Volume of the solution = _Hass _ (1 064 kg) _
Density (0-981 kg LT )
Now, 1 085 L of solution contain methanol = 2 mol
(2mol)
x (5-0L) = 9-22 mol.
(1-085L)
5-0 L of solution contain methanol =

mass.
3 EXAMPLE 3.11. Calculate the mole fraction of ethanol in a sample of spirit containing 92% ethanol by
(H. P. Board 2002)
Solution.
*C2H5OH -
C2H5OH + N\I20
Mass of C2H5OH = 92 g. Molar mass of C2H5OH = 46 g mol'1,

(92 g)
C2H5OH (46gmor) = 2mo1
Mass of H20 = 8g, Molar mass of H20 = 18 g mol'1 ; "H2O (i8g mol-1) = 0-44 mo1
(8g)
_
(2 mo!)
^C2H5OH " (2 mol) +(0-44 mol) = '82
OEXAMPLE 3.12. The mole fraction of CHjOH in an aqueous solution is 0-02 and density is
994 g cm'3. Determine the molarity and molality.
SOLUTION. STEP I. Calculation of molality of solution.
Molality of CH3OH solution is number of moles of CH3OH dissolved in 1000 g of water (kg of
water)
No of moles of H20 (ri|)
(tooog)
mo
j-t ^ = 55-55 mol
Mote fraction of CH3OH (*CH30H) = 0-02

No of moles of CH3OH (n2) can be calculated as :
n
2 _ n2
(XCH3OH)
N2 -
! + /i2
55-55 +
0-02
0-02 N2 = 55-55 x 0-02 = Mil
0-98 N2 = 1 111 or N2 =
Mil
= 1*13 mol
0-98
Solutions
3.12
Molality of CH3OH solution = 1*13 molal

Calculation of the molarity of solution.
No of gram inoles of CH3OH Molarity of solution (M) volume of solution in litres
In solution, mass of H20 = 1000 g ; mass of CH3OH = (1 * 13 mol) x (32 g mol'1) = 3616 g Total
mass of solution = 1000 g + 3616g = 1036-16 g Density of solution = 0-994 g cm"3
Volume of solution . Mass of solution =
(1036-16 g) = 1042.4
Density
(0 994 g cm 3)
(1-13 mol) (1-13 x 1000 mol)
cnr
Molarity of solution (M)
3
H2S04 = 1-02 g cm-*)
SOLUTION.
f 1042-4 , 3>|
(1042-4 dm3)
dm
l-fMT
J
1000
= 1-08 mol (dm3)'1 = 108 M
Find the molarity and molality of a 15% solution w/w of H2S04 (density of
'
(A.I.S.B. 1999. D.S.B. 1999)
Calculation of molality of solution.
Weight of H2S04 in 100 g solution = 15 0 g

Weight of water in solution = 100 - 15 = 85 0 g = 0 085 kg
Molar mass of H2S04 = 98g mol'1
No of gram moles of H2SQ4 _ 15g/(98gmol *)

Mass of water in kg
(0 085kg)
= 1-8 (MOL KG"1) = 1-8 M
Calculation of molarity of solution.

Weight of solution
Volume of solution
No. of gram moles of H2S04
No of gram moles of H 2S04

100 g ; Density of solution =
3
1Mass
-02 gofcm"
solution _
(100 g)
Density
(l-02gcm"^>
98 0 cm3
(15-0g)
(98gmor1) =0-153 mol
(0-153 mol)
1-56 mol (dm3)"1 = 1-56 M
l 1000
Problems on Normality
Z:.
A solution has been prepared by dissolving 0-49 g of sulphuric acid in 100 ml
of the solution. Calculate normality of the solution.
Solutions
No of gram equivalents of HjSO*

Solution. Normality of solution (N) = ------------------ -.
. ...
J
Mass of H2S04 = 0-49 g ; Equivalent mass of H2S04 = Molar m =
Basicity
= 49 0 g equiv.-1
2
100
Volume of solution = 100 mL - "[QQQ" = 01 L

Mass of H2S04 / Eq. mass of H2S04
Normality of solution (N) - Volume of solution in litres
(Q-49g)/(49gequiv *)
(01 L)
1-
= 0-1 equiv. L-1
01 N
OEXAMPLE 3.15. Calculate the number of molecules of oxalic acid (H2C2O4.2H2O) in 100 mL of
2 N oxalic acid solution.
(Roorkee Entrance 1991)
SOLUTION. STEP I. Calculation of mass of oxalic acid
Mass of oxalic acid / Equivalent
Normality of solution
mass
Normality of solution Volume of solution in litres
1
= 0-2
N = mass
0-2 equiv.
Molar
2x 1 +L'2 x 12 + 4x 16 + 2x 18
Equivalent mass of acid = Basicity ~
2
= 63 g equiv.'
Volume of solution
126
100
100 mL = 1000
01 L
Mass of oxalic acid

(0'2 equiv. L-1) - (fi3 g equiv-^ (CM L)
Mass of oxalic acid = (0-2 equiv. L1) x (63 g equiv.'1) x (01 L)
= 1-26 g
STEP II. Calculation of no of molecules of oxalic acid.
Molar mass of oxalic acid = 126 g mol"1 Now, 126
g of oxalic acid has molecules = No = 6 022 X 1023
1-26 g of oxalic acid has molecules -
6-022 x 1023
(126 g)
X (1-26 g) = 6-022 x 1021
ÊXAMPLE 3.16. One litre of a solution of N/2 HCl was heated in beaker and it WAS observed that when
the volume of solution got reduced to 600 mL, 3-25 g of HCl was lost. Calculate the normality of the
resulting solution.
Mass of HCl / Equivalent mass
Solution. Normality of solut.on = Volume of solution in'Htres
Solutions
Mass of HC1
(36-5 gequiv"1") x (1 L)
Mass of HC1 = (0-5 equiv. L'1) x (36-5 g equiv-1) X (1 L) = 18-25g.
Mass of HC1 lost on heating = 3-25 g
Mass of HC1 left = 18 25 - 3-25 = 15 0 g
600
(0-5 equiv. L-1) -
Volume of resulting solution = 600 mL =
1000
= 0-6 L
Normality (N) = Mass of acid / Gram equiv. of acid

_ (15-0g) / (36-5 g equiv-1) (0 6
= 0-685 equiv. L-1 = 0-685 N
L)
O EXAMPLE .17. What is molality of 1 M solution of sodium nitrate if its density is 1-25 g cm~J ?
(Pb. Board 2003)
Solution. Volume of solution = 1000 cm3
Density of solution = 1 -25 g cm-3
Mass of 1000 cm3 of solution = (1000 cm3) x (1-25 g cm-3) = 1250 g
Mass of NaN03 (molar mass) present = 23 + 14 + 48 = 85 g
Mass of solvent (water) = (1250 - 85) = 1165 g = 1-165 kg.
,.
Mass of NaNCL / Molar mass
------Mass of solvent in kg-----=
(85g)/(85gmor')
--------------------------- =0 858 mo. kg-1
= 0-858 m.
1J Miscellaneous Problems on Concentration of Solutions
OEXAMPLE 3.18. Equal volumes of 30% by mass of H 2S04 (density 1-218 g ml'1) and 70% by
mass of H2S04 (density 1-610 g mL~') are mixed. If the density of the mixture is 1-425 g mL' 1,
calculate the molarity and molality of the solution.
(Ticklish Problem)
SOLUTION. STEP < Calculation of Molarity of solution.
Let V mL of each sample of H2SO4 be mixed
FOR 30% H2S04
Mass of H2S04 = 30 g ; Mass of solution = 100 g
Mass of solution _
(100 g) _
Volume of solution =
Density
100
1-218 mL of sample contains H2SO4 = 30 g
(1-218 g mL1)
100
1218
mL
3.15
Solutions
V mL of sample contains H2SO4
(30 g) x (V mL)
= (0-3654 V) g
(100/ 1-218 mL)
For 70% H2S04

Mass of H2S04 = 70 g ; Mass of solution = 100 g
100
1-610
Mass of solution
Density
(100 g)
(l-OlOgmL1)
100
1610 mL
mL of sample contains H2SO4 = 70 g

(70 g)(V mL)
V mL of sample contains H2SO4
= (1-127 V)g
(100 /1-610 mL)
On mixing the two samples of H2SO4
Total mass of H2SO4 = 0-3654 V 4- 1127 V = (1-4924 V) g Total
volume of solution = 2V mL = (0-002 V) L
Total mass of HZSQ4 / Molar mass
Molarity ot solution (M)
(1-4924 Vg)/(98 gmor1)
(0 002 V)L
= 7-614 mol L- = 7-614 M
STEP II. Calculation of Molality of solution.

Total mass of solution = D x volume = (1-425 g mL-1 x 2 V mL) = (2-85 V) g Total
mass of acid = 1-4924 V g
Mass of water (2-85 V - 1-4924 V) g = (1-3576 V) g = (1-3576 X 10"3 V) kg Mass
of H2S04 / Molar mass
Molality of solution (M) ~ Mass of solvent in kg
(1-4924 V)g/ (98 gmoP1)
= 11-217 mol kg*1 = 11-217 m

(1-3576 X10"JV) kg
OLXAMPLE 3.19. 4.Q g Qj NaOH are present in one decilitre of solution. Calculate
(i) Mole fraction of NaOH (ii) Molality of solution (Hi) Molarity cf solution.
(density of solution = 1-038 g/mL)
SOLUTION. STEP 1 Calculation of molarity of solution.
Mass of NaOH = 4 g ; Molar mass of NaOH = 40 g mol'1,
Volume of solution = 1 decilitre = 0-1 L
Molarity (M) =

(4 g)/(40 gmoF1)
(0-1 L)
= 1 mol L'1 = 1 M
3.16
Solutions
STEP II. Calculation of molality of solution

Volume of solution = 100 mL ; Density of solution = 1 038 g/mL
Mass of solution = V x D = (100 mL) x (1 038 g/mL) = 103-8 g
Mass of solvent = (103-8 - 4) = 99-8 g = 0-0998 kg
Molarity of solution (M) =
_ (4 g) / (40 g mol ) (0
= 1-002 mol/kg = 1-002 m
0998 kg)
STEP III. Calculation of mole fraction of NaOH
Mass of NaOH
No. of moles of NaOH ~
(4 g)
^TT = 0-1 mol
Molar mass (40 g mol 1)
XT F , F . MassofH20 (99-8g)
, ,.
No. of moles of water =-----------------i= 5.54 (18
moj g moF*")
Molar mass
n
(0-1 mol)
NaOH
Mole fraction of NaOH =
n
+n
NaOH H2o (0 1 mol) + (5 - 54 mol)
= 0-018
OKvample 3.20. The density of a 3M sodium thiosulphate solution (Na 2S203) is 1-25 g/mL. Calculate :
(i) The percentage by mass of sod. thiosulphate (ii) Mole fraction of sodium thiosulphate (iii)
Molalities ofNa+ and S20/~ ions.
SOLUTION. STEP I. Calculation of % mass of Na2S2Oi
Mass of Na2S203 in 1M solution = 2x 23 +2x 32 + 3x 16 = 158 g
Mass of Na2S203 in 3M solution = 3 x 158 = 474 g
Volume of solution = 1000 mL ; Density of solution = 1-25 g/mL
Mass of solution = (V x D) = (1000 mL) x (1-25 g/mL)
= 1250 g
mass
Mass of Na2S203
Na2S203 = M . JJJ * 100 - 77100 = 37Mass of solution '
(474 g) iriA
92
(1250 g)
STEP II. Calculation of mole fraction of sodium thiosulphate

MASS OF NA2S203 = 474 G
Mass of water = 1250 - 474 = 776 g
Mass
f 1 f XI C ^
f Na-^C^
(474 g)
No . of moles of Na2S203 =-------------------~ z - = -----------= 31
Molar mass
(158 g mol" )
No. of moles of H20 =
Mass of water _
(776 g) _ 43. j t
Molar mass (18 g mol-1)
mol
mol
3.17
Solutions Mole fraction of Na2S203 =
No of moles of Na2S2Q3
No of moles of Na2S203 + No of moles of water
(3 mol)
= 0-065
(3 mol +43-11 mol)
STEP 111. Calculation of molality ofNa+ ions and S2032~ ions.
Sodium thiosulphate ionises as :
Na2S203
2Na+ + S2032-
No. of moles of Na+ ions = 2 x 3 mol = 6 mol

No. of moles of S2032' ions = 1x3 mol = 3 mol
Molality of Na+ ions = No of mqlesof Na+ ions =
(6 mol) = 7.73 m
Mass of water inkg (0-776 kg)
......
No of moles of SiCK2- ions (3 mol) _ ,
(cn2..
Molality of S203 ions = ---------------------------1------------= 1---------- - - 3-86 m
Mass of water in kg (0 776 kg)
O EXAMPLE 3.21. Calculate the density ofH2S04 solution if its molality and molarity are 94-5 and
11-5 respectively.
(Pb. Board 1995 Supp.)
SOLUTION. STEP 1. Calculation of mass ofH2S04 in 115 M solution
Moles of HISQ4
Molarity =
(11-5 mol L-1) =

Moles of H2S04
OL)
Moles of H2S04 = (11-5 mol L'1) x (1 L) = 11*5 mol

Mass of H2S04 = (11-5 mol) x (98 g mol-1) = 1127 g
Step II. CALCULATION OF DENSITY OF SOLUTION.
Let the density of solution = D g mL-1
Mass of 1000 mL of solution = D X V =. (1000 mL) x (rfg mL"1) = (1000 D)g
Mass of solute (H2S04) = 1127 g
(1000 D - 1127)
Mass of solvent (water) =
kg
1000
Molality of solution (m) = 94-5 m = 9 4 - 5 mol/kg

Density can be calculated as follows :
_ Mass of H2SQ4 / gram molar mass
1
'
(1127 g) / (98 g molr *)
(l00O D - 1127)
5 mot Kg ) - rnwnjrnvr:
-------------kg
1000
3.18
or
Solutions
,0, ,
..
_
(11-5mol)
(94-5 mol kg ) - jjoOOd - 1127)
1000
kg
,, .
(1000 - 1127)
/n ,
or (94-5 mol kg'1) x -------------------- kg = (11-5 mol)
or
11-5 x 1000
(lOOOd- 1127) =------------ - = 121 *7
94-5
121-7 + 1127
d=
1248-7
1000 1000
= 1-2487
Density of solution = 1-2487 G ML"1

3 EXAMPLE 3.22. Express the concentration of 5 mass % solution of Na 2S203 in terms of (a) irity (b)
molality and (c) mole fraction of solution. The density of solution at 25C is 1 04 gm L' 1.
molarity
[Ticklish Problem]
Solution. Let the solution contain 5-0 g of Na2S203 and 95-0 g of water. The number of moles of the two
constituents are :
Mass of Na2S203
(5-0g)
_
,
No. of moles of Na2S203 =------------------------------n----------------rrr ~ 0-0316mol
LI J
Molarmass (158-0gmol )
Mass of water
No. of moles of water - w .------------------Molar mass
Mass
of solution
Density
{a) Calculation of molarity of solution.
(95-0g)
-rj = 5-278mol
(18-Og mol *)
= (j.QQ'Qs)
(1-04 g mL *)
.
,..
....
Moles of Na2S203
Molarity of solution (M) = ---------------------- -1 3-------Volume of solution in litres
(b) Calculation of molality of solution.

Molality of solution (M) = ^ês Na2S2Q3
Mass of water in kg
(0-0316 mol)
..
'
(0.095 kg) = O'333mol kg , 0-333 m.
(c) Calculation of mole fraction of solute.
Mole fraction of solute in solution may be calculated as :
Mole fraction of solute (xB) =
(0-0316 mol)
"B + A (0-0316 mol + 5-278 mol)
(0-0316 mol)
= 5-95 X 10-3.
(5-3096 mol)
B
= 9 6
1 5 m L
3.19
Solutions
3.3. TYPES OF SOLUTIONS
We have listed the different types of binary solutions in Table 3.1. Out of these, the solutions in which
liquid acts as the solvent or the liquid solutions are of greater utility. Such solutions may be :
Solid in liquid solutions
Liquid in liquid solutions
Gas in liquid solutions
The solutions in which water acts as the solvent are known as aqueous solutions while the solutions in
which solvent is not water are called non-aqueous solutions. For example, a solution of iodine in carbon
disulphide is a non-aqueous solution.
Let us briefly study the three types of solutions listed above.
Solid in Liquid Solutions
These solutions are the most common. As the name suggests, solid invariably acts as the solute (present
in small amount) while liquid plays the role of a solvent (present in excess). Water is the common solvent for
ionic and polar solids and organic liquids such as alcohol, ether and benzene can be used to dissolve the
organic substances in the solid form. In order to prepare such a solution, a certain amount of a particular
solvent is taken in a container say beaker and the solute is added in small instalments and each addition is
accompanied by vigorous stirring of the solution with a glass rod. Temperature is kept constant throughout. A
stage will be ultimately reached when no more of the solute dissolves in the given mass of the solvent and it
will start settling at the bottom of the container. The solution is known as saturated solution because it cannot
accept any more of the solute at a constant temperature. The amount of solute present in grams in 100 grams
of the solvent in a saturated solution represents the solubility of the solute.
Saturated Solution is a solution which has the maximum amount of the solute dissolved in it at a
particular temperature.
Solubility is given as the maximum amount of the solute in grams dissolved in 100 g of the solvent to
form a saturated solution at a given temperature.
A saturated solution represents a state of equilibrium between the solute present in the solution and
settled at the bottom of the container. If such a solution is heated, it becomes unsaturated in the sense that it
can dissolve more of the same solute. Similarly, if a saturated solution is cooled, the solubility of the solute
will decrease and it will start coming out of the solution and will appear on the surface. Such a solution is
known as super saturated solution.
Factors Influencing the Solubility of the Solute. The solubility of the solute in a liquid is guided by
nature of the solute and of the solvent and also the temperature employed.
1.Nature of the solute and solvent. The solubility, in general, is guided by the principle that LIKE DISSOLVE LIKE.
This means that a solute will dissolve in a particular solvent if both have the same nature. The ionic and
polar solutes generally dissolve in polar solvents while the non-polar solutes are soluble in non-polar
solvents. These are mostly organic in nature E.G. benzene, carbon tetrachloride, carbon disulphide etc.
However, there are many exceptions also. For example, non-polar solutes like sugar, glucose etc. dissolve
in water mainly because of hydrogen bonding. The polarities of the solvents are expressed in terms of
dielectric constant values.
For example, the value of dielectric constant for water is 80 while for methyl alcohol and benzene it is
33-5 and 2-3 respectively. Thus, ionic solutes readily dissolve in water while these are almost insoluble in
benzene,
It is a common experience that the ionic solids differ in their solubility in water. For example, MgS0 4 is highly
3.20
Solutions
soluble whereas BaS04 is almost insoluble. This is guided by two factors I.E. lattice energy and hydration energy.
Lattice energy is the energy required to separate the ions present in one mole of the solid whereas hydration energy is
the energy released because of hydration of one mole ions of the solid. Ionic solids (generally salts) with high lattice
energy are less soluble in water as compared to those with small lattice energy. Similarly, the solids with a greater
value of hydration energy are more soluble in water as compared to the solids with lesser hydration energy value.
The relative solubilities of the different salts in the same solvent such as water are compared in terms of their
SOLUBILITY PRODUCT CONSTANT VALUES* (KI/5). Thus, KSP value of MgS04 is more than that of BaS04.
1. TEMPERATURE. Temperature has a very important impact on the solubility. That is why solubility is always
expressed at specific temperature. It may be noted that if a substance dissolves in the solvent with the absorption of
heat, (process is endothermic), its solubility increases with the rise in temperature. If heat energy is released (process
is exothermic), the solubility will decrease with rise in temperature. The solubilities of the salts in water normally
increase with rise in temperature as the process is endothermic.
The solubility of GLAUBERS SALT (Na2SO4.10H2O) in water is quite interesting. It initially increases upto
32-3C and then starts decreasing Actually, upto the temperature which has been mentioned, the salt remains
hydrated and the process of dissolution is endothermic. Above this temperature, it changes to the anhydrous form
and the process is of exothermic nature. That is why, the solubility of salt initially increases and then decreases.
Liquid in Liquid Solutions
When the liquids are mixed, the molecules of one liquid move apart to accomodate those of the other and vice
versa. In some cases, the liquids are completely miscible E.G. benzene and carbon tetrachloride or alcohol and water.
However, miscibility is partial in case of ether and water or phenol and water. There are also many cases in which
they remain practically immiscible E.G. benzene and water or benzene and alcohol. We shall study in detail the
behaviour of these solutions under ideal and non-ideal solutions at a later stage in the present unit.
Gas in Liquid Solutions
Most of the gases are soluble in water as well in some other solvents such ethyl alcohol, benzene ETC. The
solubility of a gas in a solvent is expressed in terms of ABSORPTION COEFFICIENT (a) which was introduced for the
first time by BUNSEN. It may be defined as :
the volume of the gas reduced to N.T.P. which dissolves per unit volume of the solvent at the
experimental temperature and under a pressure of one atmosphere.
Gas
Water
Ethanol
Benzene
HYDROGEN
0017
0080
0-060
NITROGEN
OXYGEN
0015
0 028
0-130
0-130
0-104
0-165
CARBON DIOXIDE
0-88
3-00
The absorption co-efficients of a few gases at 293 K in three solvents listed above are given.
TABLE 3.2. Absorption coefficient (a) of some gases at 293 K and one atmosphere
pressure.
3.22
Solutions
Solutions
3.21
3.3. of
KHavalues
Factors InfluencingT
theTABLE
solubility
Gas of different gases in water
The solubility of a gas in a liquid depends upon a number of factors. These are briefly discussed.
1. The nature of the gas and the solvent (liquid). The solubility depends upon the nature of both the gas
and the solvent or the liquid. Generally, gases which can be easily liquefied are more soluble in water than
the gases which are liquefied with difficulty. For example, carbon dioxide is more soluble in water as
compared to hydrogen, nitrogen and oxygen. Similarly, polar gases like NH 3, HCl(g), SO2 are more soluble
in water than in ethanol (less polar than water) and benzene (which is non-polar).
GAS
TEMPERATURE (K)
KH(TORR)
2. Effect of temperature. In general, the solubility of a gas in a liquid decreases with the rise in
7
HE
10-9 X 10
temperature.
The process of293
dissolution is, exothermic
because the gas contracts in volume and energy is
7
H2 during contraction.293
5-2 X 10 principle, the increase in temperature favours the
released
According to Lechateliers
7
reverse
with
the
increase in temperature.
N2 process. Therefore, the
293 solubility decreases
5 75
X 10
N2
02
02
303
Gas + Liquid ^
293
303
6-68 X 107
^ Dissolved7gas ; AH = -ve
2-95 X 10
(solution)
3-52
X 107
3. Effect of Pressure. This

298 is a very important
1-24factor
X 106 because the solubility of any gas in a particular
CO2increases when it is compressed or the pressure is increased. This exercise actually brings the
liquid
H2S
298
4-12 X 105
molecules closer and they liquefy to be a part of the solution. The relation between pressure and solubility is
guided by Henrys Law. According to the Law,
the mass of a gas dissolved in a given volume of the liquid at a constant temperature depends
upon the pressure which is applied.
M cc P (at constant temperature)
The law was given by William Henry in 1802. At about the same time DALTON, a friend of Henry also
stated on the basis of the experimentation that the solubility of a gas present in a liquid is a function of the
partial pressure of the gas. In case the solubility of the gas be expressed in terms of its mole fraction, then
Partial pressure of the gas (P) Mole fraction of the gas in the solution
= KH x Mole fraction of the gas in the solution
or
______Partial pressure of the gas______

Mole fraction of the gas in the solution
Here KH is known as Henrys Law constant

To illustrate this, a graph has been plotted between the
values of the partial pressures of HC1 (G) dissolved in
cyclohexane and the corresponding mole fraction at 298 K.
The plot is shown in the Fig. 3.1. KH values of the number
of gases at specific temperatures have been determined in
the same way. These are given in table 3.3.
3w
i/i t
-U
.21
Mole fraction of HC1

in cyclohexane
A FIGURE 3.1. Mole fraction

* For the detailed study of the concept of solubility product please consult unit Equilibrium-II
Companion
of HCIfrom
in solution.
Chemistry for class XI.
3.24
Solutions
Solutions
3.23
3EXAMPLE 3.23. If N2 8as >s bubbled

how
many millilitres (at STP) of N 2 would
(0-80
atm)
*C2> through water
" at 20C,
dissolve in a litre of water ? Given that the partial
pressure
of
N
is
equal
to 742-5 torr and K H for nitrogen
2
"-H(N
)
2
(12-6 x 104atm)
= 5-75 x 107 torr.
_ P(.02
SOLUTION, s t o p I. Calculation of no. of moles
of >N_2.
(0-20 atm)
K
H(02)
l
(0 2 )
(7-01 x 104 atm)
According to Henrys Law.
Mole fraction of N2 (*N2 ) *(N2)
OCDCÔO
^02)
Partial pressure
of N2
(0-80 atm)
=
KH for N2 4
(12-6 x 10 atm)
(742-5 torr)
(7-01 x 104atm)
_
(5-75
107 torr)
(0-20x atm)
2'22
1 29 x 10"5
"N2
L.
*N2 =
n
+ ,l
n
H20two
H20solid components in a suitable
2
The solid solution, as the name suggests, is formed byNmixing
VAÂ manner.
yv
3
\
.A.
J
Such
solutions
are
of
two
types
:
above expression since the gas is very little soluble in water)
0CXA(rtN
O 2 has been neglected in theOO0OS0
1. Substitutional
solidit solutions.
In the that
solutions, some atoms, molecules, or ions belonging to one
From
the data collected,
is quite obvious
solid
substance
replace
similar
species
belonging
to theother
solid
its crystal
lattice
shown in of
the
5
(a) higher the value of KH for
in aingiven
solvent.
Thus,
*N,2a=gas,
1-29lesser
x 10"will
; "be
H2Oits= 2solubility
= 55-55
mol assolubilities
(
3.2(AN).2 The
common
of solid
solutions
arethe
theorder
alloys
E>
.
G-1.,
brass
is
an
alloy
of
copper
and
(18
gHmol
)
He,Fig.
H2 and
in water
at 293examples
K at the same
pressure
follow
N
>
He.
2
2
zinc. Similarly, coinage silver is an alloy of silver and copper.
(b) as the temperature increases the solubility
of
the
gas
tends
to
decrease.
Thus, nitrogen
is more
X
3
4
2 =
soluble in water at 293 K than atN
303
K.*N2 H2O = (I-29 x 10' x 55-55 mol) = 7-16 x 10" mol. Step II
CALCULATION OF VOLUME OFN2 AT S.T.P.
Remember
1 mole of N2 at S.T.P. occupy = 22400 mL
Helium is employed to dilute the oxygen used as breathing gas during deep- sea
4
diving
because
soluble
as=compared
to ^
all/7>1
the
This
7-16
x 10~
moleitofis Nthe
S.T.P,
occupy
(22400 mL)
g xgases.
io~4mol)
= gives
16-04 lesser
mL
2 atleast
bubbles in the blood during decompression
(1 mol)causing lesser discomfort to the divers.
3EXAMPLE 3.24.
Law constant
oxygen
dissolved
4 34 X 104with
atm increase
at 25 C.inIt
The
As Henry
the solubility
of both for
oxygen
and
nitrogenininwater
wateris decreases
partial pressure of oxygen
in air aquatic
is 0-2 species
atm. under
ordinary
atmospheric
conditions,
temperature,
live more
comfortably
in cold water
than in calculate the
concentration
(in moleswarm
/lit re)water
of dissolved
oxygensolubility
in waterof
inthese
equilibrium
with
air _____________________
at 25 C.
___________________
due to greater
gases in
water.
(C.B.S.E.
Sample Paper 2003)
Applications of Henry's Law
Now,
Solid Solutions
0( X X XX)
The law is useful in many ways both in industry and in explaining biological phenomena. For example,
Solution. According to Henrys Law,
(i) In order to increase the solubility of C02 gas in soft drinks and soda water, the bottles are
normally sealed under high
pressure.
x Partial
pressure of 07 -___________0 2 atm
= 4 - 6 x 1 0 -6
Mole fraction of
(4-34
x
10
atm)
(IT) As pointed above, oxygen______________________________
to be usedKby
JJ deep
for 02sea divers is generally diluted with helium inorder
to reduce or minimise the painful effects during decompression.
_ NQin
(HI) As the partial pressure of oxygen 02
in air is high,
2 lungs it combines with haemoglobin to form
V 2
+n
n
Now,
02 pressure
H20 Hof
20 oxygen is comparatively low, threfore
oxyhaemoglobin. In tissues, the partial
oxyhaemoglobin releases oxygen in order to carry out cellular activities. LIMITATIONS OF HENRY'S LAW
(o2 has been neglected in this expression since the gas is very little soluble in water)
Although Henerys Law has vital applications, but if does suffer from some limitations as well. These
are listed :
(lOOOg)
1
mo1
= 4-6only
x 10"*
i nHideal
) I55.E55
low pressure and high
2o (18gmol"
(i) The law is applicable *o
to 2gases
under
conditions
. under
temperature.
6
RTQshould
H2O
= (4-6 X or
10"associate
) X (55-55
mol) = 2-55
x ltHmol.
2 = X0L Xnot
(ii) The molecules of the gas
dissociate
in solution
I.E. the
gas has same
molecular
state
in
the
liquid
as
well
as
gaseous
phases.
OLxample 3.25. What is the ratio of the solubilities of N 2 and 02 in H20 at 373 K, given that K H (N 2 ) =
(iii) xThe
react
withAssume
the solvent
form
any compound.
For=example,
12-6
104gas
atmshould
and KHnot
(Of)
= 7chemically
01 X 10* atm.
that to
piNf
= 0-80
atm and p(Of
0-20 atm.
combines
with
water
to
form
NH
OHfa^
which
dissociates
as
follows
: mole fractions.
4
Solution.The ratio of the solubilities of the gases can be expressed in terms of their
NH
fol
+
H
0(/>
------>
NH
OHfa^
-------
NH,
F
(
AQ
)
+
OH
~(
AQ
)
3
2
4
According to Henrys Law,
Solutions
3.25
3.5. Calculate the molality of potassium carbonate solution formed by dissolving 2-5 g of it in one litre of
solution (density of solution = 0-85 g mL'1)
(Pb. Board 2000 Supp.) [Ans. 0'021 m]
3.6 100 mL of a solution containing 5g of NaOH is mixed with 200 mL of M/5 NaOH solution. Calculate the
molarity of the resulting solution.
[Ans. 0-55 M]
3,7. A sugar syrup of weight 183-42 g contains 3-42 g of sugar (C12H22O11). Calculate the mole fraction of
sugar.
(H.P. Board 2000) (Ans. 0 00099)
3.8 A commercially available sample of sulphuric acid is 1596 H 2S04 by mass (density = 1-10 g mL*1).
Calculate : (/) Molarity (ii) Normality (Hi) Molality of solution.
(A.I.S.B. 1999)
3.9. Concentrated HNO3 used in the laboratory is usually 69% by mass of HNO3. The density of HNOj
solution is 1-41 g cm*3. Find the molarity.
(Pb. Board 2000) |Ans. 15-44 M]
3,10. How much sodium chloride be dissolved to make 1 litre of 0-1 F solution ?
(Haryana Board 1997) [ANS. 5-85 G[
[Ans. (i) 1-68 M (ii) 3-36 N (Hi) 1-8 m]
3.11. How will you prepare 0-25 m CaCI2 solution ?
(H.P. Board 1999) [Ans. 27-75 g]
3.12. Calculate the molarity of pure water. Given that density of pure water is 1 g/mol.
[Ans. 55 55 M]
3.13. Calculate the mass percent of a solution obtained by mixing 100 g of 10% urea solution with 150 g of
15%
urea solution.
[Ans. 13 %)
3.14. Calculate the mole fraction of solute in 2-5 m aqueous solution.
(H.P. Board 2002) (Ans. 0-043]
3.15. Commercially available cone. HCI contains 38% HC1 by mass and has density of 1-19 g cm* 3. Calculate
the molarity of this solution.
(Pb. Board 2003) [Ans. 12-39 M)
3.1<' Calculate the mole fraction of ethyl alcohol and water in a solution in which 46g of ethyl alcohol and 180
g
Solvent (^) Solute
^ Solvent o Solute
of water are mixed together.
(Haryana Board 2003) [Ans. 0-09]
(A) Substitutional solid
(B) Interstitial
3.17. 6X10"3 g oxygen is dissolved

in per kg of sea water. Calculatesolid
the ppm
of oxygen in sea water.
solution
solution
FIGURE 3.2, Types of Solid(Pb.
solutions.
Board 2003 Supp. 2003) [ANS. 6 PPM)
Interstitial
3.18. 200-0solid
mL of
calcium Solid
chloride
solutioncan
contains
3-01
x 10 22when
Cl* ions.
molarity
the
solutions.
solutions
also be
formed
atomsCalculate
of smallthesize
occupyofthe
voids solution
or interstices that exist in the crystal lattices of certain metals. This leads to interstitial compounds.
Assume that
calcium (W)
chloride
ionised.
Board 2003(f.c.c).
Supp.) [Ans.
0- 125M]
For example,
tungsten
has isa completely
face-centred
cubic closed packed(Pb.
arrangement
In case
carbon
---------------------------------------------------------------------------------------------------------------
atoms occupy the vacant or interstitial sites, tungsten carbide (W c) results which is extremely hard and is
employed
3.4 VAPOUR
PRESSURE
OFand
PURE
LIQUID
for making
grinding
cutting
tools. The arrangement of components in such a solution has
Weshown
all know
that3.2(
the
been
in Fig.
B). molecules in a gas are constantly colliding with one another and during the
collisions the exchange of energy as kinetic energy is taking place. Thus, all the molecules of a gas donot
have the same kinetic energy at a given temperature but a certain fraction may have the same energy. That is
<
why we consider the average
kinetic energy of the gas molecules at a certain temperature. This is also true
for the liquids as well but the random motion of the molecules in a particular liquid is less as compared to
the gaseous state of the same liquid. When a liquid is taken in an open container at a certain temperature, the
A solution
naphthalene
in benzene
3% by or
mass
of naphthalene.
is the present
mass percent
molecules3.1.
present
on theofsurface
are being
pulled is
inwards
downwards
by the What
molecules
belowof
benzene
them. This inward pull or attraction prevents the surface molecules from escaping out the surface of the ?
liquid as vapours. However, some high energy molecules present
on the surface escape from it in[Ans.
order9796]
to
A solution contains 20 g sodium chloride in 95 cm 3 solution. The density of solution is 1-25 g cm -3.
increase their
free
movement
also
called
randomness.
In
doing
so,
they
take
up
certain
energy
from
the
rest
What is the mass percent of NaCl ?
[Ans.
16-84
of the molecules
resulting in their decreased average kinetic energy or fall in temperature. That is why
%)
cooling is observed in evaporation. Its magnitude is inversely proportional to the attractive forces which the
3.3. A solution has been prepared by dissolving 60 g of methyl alcohol in 120 g of water. What is the mole
moleculesfraction
in a liquid
experience.
of methyl
alcohol and water ?
(H.P. BOARD 1995) [Ans. (I) 0-220 (II) 0-780]
In an open container, the evaporation of the liquid continues because the decrease in average kinetic
3.4.
Calculate
the
molality
of
a
sulphuric
acid
solution
in
which
mole fraction
waterliquid
is 0-85.
energy or the loss of energy is compensated by the surroundings. Ultimately,
theofentire
evaporates
(A.I.S.B. 1999) [ARTS. 9 8]
jf^robleryiA 2ôr jf^ructice
Solutions
3.26
In case the liquid is taken in a close container or vessel, the picture is different. The evaporating
molecules cannot escape to the atmosphere. The molecules with higher kinetic energy leave the
surface of the liquid as vapours. As a result, the volume of the liquid initially decreases. These
vapours get collected in the space over the liquid surface.
They exert more collisions with the walls of the container
resulting in increased pressure on the surface of the
liquid. These molecules present in the vapour phase are
also colliding with the liquid surface. Those with lesser
kinetic energy condense at the surface of the liquid
because of the collisions that are taking place. Thus, the
condensation of molecules back to the liquid state is also
taking place. Inside in the vessel, the liquid changes to
vapours resulting in evaporation and the vapours are
changing back to the liquid state known as condensation.
At a particular temperature, the liquids and its vapours
are in state of DYNAMIC equilibrium also called phase
FIGURE 3.3. Representation
EQUILIBRIUM because this is present in the two phases of
of equilibrium
a certain substance say water.
H20 (L) -------H20 (G) or H2Ofg) ---------------> H20 (L)
The equilibrium has been depicted graphically in Fig. 3.3.
The pressure exerted by the vapours of the liquid at this stage is known as VAPOUR PRESSURE and
may be defined as :
the pressure exerted by the vapours of the liquid in equilibrium with liquid at a given
temperature.
It may be noted that the vapour pressure results simply because of a kinetic phenomenon and is
therefore, quite independent of the amount of the liquid. It depends mainly upon the temperature which must
be specified while expressing the vapour pressure of any liquid.
Factors Affecting Vapour Pressure.
The vapour pressure of a liquid depends mainly upon two factors. These are the nature of the liquid
and the temperature.
NATURE OF THE LIQUID. The vapour pressure of a liquid
is linked with its nature I.E., magnitude of the intermolecular
forces present in its molecules. When these forces are weak,
the molecules will readily change into vapours and the
equilibrium vapour pressure will be high. However, if these
forces are strong, then the molecules will not change into
vapours so readily and consequently the vapour pressure
will be comparatively low. From the curves listed in the
Fig. 3.4, it is quite clear that at a particular temperature,
the vapour pressure of diethyl ether is the maximum while
that of water is the minimum. Thus, the vapour pressure
predicts the magnitude of the intermolecular forces. Higher
the vapour pressure of a particular liquid, lesser will be the
magnitude of these forces.
Temperature
FIGURE 3.4. Vapour pressuretemperature curves for some liquids.
3.27
Solutions
Temperature of the Liquid. The vapour pressure of a liquid increases with the rise in temperature. When
the temperature is increased, the average kinetic energy of the molecules in the liquid also increases. This
will lead to a greater number of molecules in the vapour phase and consequently the vapour pressure of the
liquid will increase.
Remember
The vapour pressure is a measure of the escaping tendency of the molecules from the
liquid surface an d depends upon volatility of the liquid. It also depends upon the
temperature employed.
3.5 VAPOUR PRESSURE OF SOLUTION
We have studied that when a solute is added to a solvent and the two become miscible to give a
homogeneous mixture, a solution is formed. Now the solute may be non-volatile solid such as sugar, copper
sulphate, sodium chloride etc. while the solvent is a volatile liquid (E.G, water). A solution can also be formed
when both the solute and solvent are of volatile nature These are generally liquids E.G. alcohol and water or
benzene and toluene. Let us study the vapour pressure of both these solutions.
Binary solution containing a Non-volatile solute
Let us take pure water in a beaker and cover the same with a bell jar as shown in the Fig. 3.5(a). The
vapours of water above the liquid surface will exert certain pressure known as the vapour pressure. Now let
us add a small amount of a non-volatile solute such as sugar to the beaker so as to form the solution. Certain
particles of the solute will definitely occupy some surface area of the solvent as shown in the Fig. 3.5(b).
Since the solute is non-volatile, only the solvent or water moieeules will change to the vapours. But as
evaporation is a surface phenomenon, the molecules of the solvent will have less area available for
evaporation (surface is partially occupied by the panicles of the solute also). Th>s means that the rate of
evaporation will decrease. This will also adversely affect the rate of condensation of water vapours to form
liquid. Thus, both evaporation and condensation will decrease and consequently, the vapour pressure of the
sugar solution will be less than that of pure water. In otherwords, there will be a lowering in vapour pressure
of the solution as compared to the vapour pressure of pure solvent I.E. water.
FIGURE 3.5.(a) Vapour pressure of pure solvent (b) Vapour pressure of solution having a
non-volatile sotute.
3.28
Solutions
Binary solution containing volatile solvent and volatile solute
In case both the components present in the binary solution are volatile ( E.G. benzene and toluene or
alcohol and water) then vapours of both of them will be present in the empty space. In such a case, the
vapour pressure of the solution will be the sum of the partial vapour pressures of these volatile components
provided these are non-reacting in nature. This will be according to Daltons law of partial pressures.
3.6 RAOULT'S LAW AND VAPOUR PRESSURE OF SOLUTION
In 1886, a French chemist, FRANCOIS MARIE RAOULT, as a result of series of experiments gave relation
between the partial vapour pressure of a volatile component and its mole fraction in solution. This is known
as Raoults Law and may be stated as :
the partial vapour pressure of a volatile component present in a solution is directly
proportional to the mole fraction of that component at a given temperature.
For example, for a volatile component A present in a solution,
PA oc XA
or PA = K XK
[it - constant]
If JCA = 1 this means that the solution has only one component and the other is absent. Under the
condition,
PA = it x 1
Thus,
PA = P^xA
[PA = Vapour pressure of the component when present in pure form]
The RAOULTS LAW may also be stated as :
In a solution, the vapour pressure of a particular component at a given temperature is equal to
the mole fraction of that component in the solution multiplied by its vapour pressure when
present in pure form.
For a binary solution containing two volatile components,
PA = *A PA and PB = xBP^
The total vapour pressure P of the solution.
P = PA + PB = PA*A + PB*B
RaoulFs Law for solution containing non-volatile solute
In case the solute (component B) present in the solution is non-volatile, it will not have any partial
vapour pressure I.E. PB = zero
P = PA = PA*A
Thus, for a solution containing a non-volatile solute present in a volatile solvent, Raoults Law may be
stated as :
The vapour pressure of solution containing a non-volatile solute at a given temperature is
equal to the product of the mole fraction of the pure solvent and its mole fraction.
We can also account for the fact that there is a lowering in vapour pressure when a non-volatile solute is
added to the solvent to form the solution with the help of the above relationship. The maximum value of x A
for a volatile component in the solution will remain less than 1 simply because
X\ + xB = 1. Therefore, PA < P^
(VJCA < 1)
3.31
Solutions
3.29
Solutions
3.30
This means that the vapour pressure of liquid A is maximum when xA = 1 and is zero when *A = 0.
Thus
the
vapour
pressure
of that
the solution
containing
a non-volatile
solute
be
always
lessbewith
than
the
It2.
may
be noted
inalso
order
a solution
may
ideally,
solutewill
and
solvent
must
of same
Straight
linethat
(II)
indicated
by dotted
linebehave
represents
the the
variation
in
vapour
pressure
change
mole
fraction
for
nature.
if Aliquid
and BB.are
the two
components
of the
solution, there should not be any
vapour in
pressure
ofThus,
the pure
solvent
or there
willvolatile
be lowering
in vapour
pressure.
change
in the magnitude
of the forces
of then
interaction when
the Btwo
are mixed. This means that A...............B
When
xB =of1 the
(liquid
is pure),
PB = PgX
= Pg
Mole Fraction
in the
Vapour
Phase
interactions
must be the
sameComponents
as A................
A and
B...............
B interactions. When such solutions are
Thethere
moleshould
of be
theB
volatile
components
the
vapour
phase can
be obtained
helpThe
of
When
xfraction
(liquid
is absent)
then
PB = in
PgX
0 enthalpy
B = 0 not
B =
prepared,
any
change
in volume
and
the
change
must bewith
alsothe
zero.
Daltons
Law
partial
pressures.
the
mole
fraction
of the twowhen
volatile
A when
and B*in
This means
that
the vapour
pressure
ofas
the
liquid
B
xB components
- 1 and is zero
B =the
0
characteristics
of of
an
ideal
solution
are Let
listed
follows
: is maximum
vapour
phase
ofvapour
a solution
be Y
and
and
PAby
and
pressures.
3.It must
The
total
pressure
of
theYsolution
as and
indicated
thePnormal
linepartial
(III) isvapour
the linear
sum of
B respectively
B be their
(i)
obey
Raoults
Law
atPAall
concentrations
temperatures.
theLet
partial
pressures
B forces
presentofininteraction
the solution.
P(ii)
bevapour
the total
pressure
inthe
thr.
vapour
phase.
Thus,A andof
There
should
not of
be
anyvolatile
changecomponents
in the magnitude
when the components
are mixed.
pA P+ and
pB =Pp;*
A + PB*B
PpA == Y
(in vapour phase)
B = YBP
(iii)ItBoth
the components
theA solution
similar
structures
andinpolarity.
also indicates
that thepresent
vapourinpressure
of themust
idealhave
solution
at any
stage lies
between the vapour
(iv) Volume
change
PA =be
*Azero.
PA and PB = *BPB
(According to Raoults Law)
pressures
P^ and
Pg on mixing must
Non-Ideal Solutions AVmjXjng = zero or VSO|Vent +
* (ii) (iii) (iv)
(v) Solutions
Enthalpywhich
changefail
ontomixing
must
be zero,
I.E. AH
mixiideal
ng
fulfilVthe
an
solution are known as non-ideal solutions.
- x.Pl
r V
^4- is zero.
AP characteristics
A -of
For such solutions,
(i) Raoults Law is not obeyed I.E. PA * P^JC and PB * PgXB
Remember
Y.P = *Pi or Y . MS- =
A
It is very difficult
to have
anAideal
solution.
conditions mentioned above,
(if) A.......B interactions
are different
from
.............
A and BUnder
........Bthe
interactions.
Thus,
the
mole
of
each
volatile
component
of
binary
solution
is the the
ratioconcentration
of its partial of
the fraction
solutions
tend
to
become
ideal. Dilute
solutions
in which
(HI) There is a change in volume when the two components are mixed I.E. AV
mixing * zero.
the
solute
does
not
exceed
5
percent
are
generally
regarded
as
ideal
solutions.
vapour pressure and the total vapour pressure of the solution in the vapour phase.
(iv)
There isof
a change
enthalpy
when
the
two components
aresolutions
mixed I.Ebecome
. AHmixing
* zero.
Raoutt's
Law
as Solutions
a in
special
of
Henry's
Law
Examples
Ideal
: case
It has
been
pointed
out that the
ideal
in case
important
of to
theA
ideal
and
non-ideal
solutions
are are
compared
in the table (A)
3.2 in
soluteThe
andhave
solvent
arecharacteristics
of
similar
nature.
few examples
ideal
solutions
:
We
studied
that
according
Raoults
Law
theofvapour
pressure
of
volatile
component
a given(i)
solution is given as :
Benzene and toluene
PA = PAjrA
(According to Raoults Law)
(ii) n-Hexane and n-heptane
In the solution of a gas in a liquid, the gaseous component is normally so volatile that it exists as a gas
(iii) Ethyl bromide and ethyl iodide
and its solubility in the liquid is governed by Henrys Law according to which
(iv) Bromobenzene and iodobenzene
PAthe
of
KH
*Acharacteristics of ideal and non-ideal
(According
to Henrys Law)
Graphical
Representation
of
TABLK
3.2 Comparison
the
solutions
Behaviour
of Ideal Solution.
According we find that in both the cases, the partial vapour of the volatile
If we compare
the two expressions,
to
Raoults Law,
component
or gas is directly proportional to its mole fraction in the solution. However,
proportionality constants P^ and KH are different. Thus, Raoults Law may be regarded as a special
PA = Pi*A and PB = P^B
case of
Henrys
which
KH becomes
equal to P^.
This
meansLaw
thatin the
vapour
pressures
of
theIDEAL
components
present in SOLUTIONS
a solution
3.7
AND NON-IDEAL
are the linear functions of their mole
The binary solutions of the volatile liquids can be classified into two types. These are : Ideal solutions
fractions. Graphs showing the variation
and
Non-ideal
solutions
and are
discussedand
as follows :
between the partial
vapour
pressures
Ideal Solutions
the corresponding mole fractions for the
A solution is said to be ideal
components A and B for a binary solution
if itFig.
strickly
and temperatures.
are shown in the
3.6 obeys Raoults Law at all concentrations
FIGURE 3.6. Graphical representation of the
Thus,
are the the
two components
then of ideal solution consisting of
From if A
theand B
graph
following of the solution,
behaviour
components A and B.
generalisations can be made
1. Straight line (I) indicated by dotted line shows the variation in vapour pressure with the change
in mole fraction for liquid A.
When xA = 1 (liquid is pure) then PA = Pl*A = P^
jtA = 0 (liquid A is absent) then PA = Pl*A = 0
When
1. THE FORCES OF INTERACTION OF THE COMPONENTS IN THE
Non-ideal solution
FORCES OF INTERACTION OF THE COMPONENTS IN

THE THE
SOLUTION ARE THE SAME AS IN PURE COMPONENTS I.E. SOLUTION ARE DIFFERENT FROM THOSE PRESENT IN PURE
A...... B INTERACTIONS ARE THE SAME AS A... A AND
COMPONENTS I.E. A....B INTERACTIONS ARE DIFFERENT
FROM
B.....B INTERACTIONS.
A
......A AND B.... 1 INTERACTIONS.
THERE IS A CHANGE IN VOLUME ON MIXING THE

2. THERE IS NO CHANGE IN VOLUME ON MIXING THE COMPONENTS
COMPONENTS I.E. AVLNJXJNG = 0.
I.E. AVMJXJNG * 0
3. THERE IS NO CHANGE IN AH UPON MIXING THE THERE IS A CHANGE IN AH ON MIXING THE COMPONENTS
I,&, AHMIXING 0.
COMPONENTS I.E. AHMJXING = 0
4. COMPONENTS OBEY RAOUITS LAW AT ALL COMPONENTS DEVIATE FROM RAOULTS LAW I.E.
AND CONCENTRATIONS I.E.
PA = PA*A. PB = PB*B
TEMPERATURES
PA * PA** PFI * PB*8'
Normally, the solutions in which the components present are of different nature are non-ideal. Such
solutions are of two types :
Solutions showing positive deviations from Raoults Law.

Solutions showing negative deviations from Raoults Law.
3.33
Solutions
Solutions
3.32
E
XPLANATION
. Let us showing
analyse the
behaviour
of the solution
when ethyl
alcohol and cyclohexane are
Non-ideal
solutions
positive
deviations
from Raoulfs
Law
mixed.Non-ideal
In ethyl alcohol
molecules,
strongdeviations
intermolecular
hydrogenLaw
bonding
is on
present
because
of their polar
solutions
show positive
from Raoults
in case
mixing
the two
nature.
presenceofofthe
cyclohexane
naturally
reduce thedecrease
hydrogenI.Ebonding
and thus the
volatile The
components
solution, themolecules
magnitudewill
of forces
of interaction
. A.........................
B
escaping
of the
alcohol
willBincrease.
Same
willthe
happen
the molecules
interactiontendency
is less than
the A
..........Amolecules
and B...........
interactions.
Asthing
a result,
partialfor
vapour
pressure of
cyclohexane
because
thethepresence
of alcohol
in the
in-between
space will
attractive
of each component
and
total pressure
of themolecules
solution will
be greater
as compared
to reduce
an idealthe
solution.
forces which are mainly van der Waals forces. As a result, their tendency to escape in the space above the
liquid mixture will increase. This will lead to positive deviations because the vapour pressure of each
component and
also that of the solution
beB more than that of an ideal solution.
PA > Pas
A*aAwhole
and pBwill
>PV
I
I
C2H5
C2H5
6+ 6-
S+ 5'
S+ 6*
5+ 5
H-O-------H-0--------H-0............H-O-
FIGURE 3.7. Graphical representation of non-ideal solution having +ve deviation

from Raoults Law.
The behaviour of such a solution has been indicated by normal lines in the Fig. 3.7. The dotted lines
represent the behaviour of the two components present in the ideal solution and also that of the solution as a
whole. Apart from disobeying Raoults Law these solutions also suffer from the following limitations.
(i) AVmixlng is + ve. This is quite likely also because in the presence of weak forces of interaction the
volume of the solution is bound to increase.
(ii) AHraixinf. is +ve. Energy is needed to form the solution because the components of the solution have
to be brought closer to form the solution. Thus, the process of mixing is of endothermic nature. In case the
solute is a solid, its solubility in the solution is expected to increase with rise in temperature.
Examples of solutions : A few examples of such solutions which show positive deviations from Raoults
Law are :
(i)
(ii)
(iii)
(iv)
(v)
(vi)
Ethyl alcohol and cyclohexane

Acetone and carbon disulphide
Acetone and benzene
Carbon tetrachloride and chloroform
Ethyl alcohol and water
Acetone and ethyl alcohol
Solutions with -ve deviations
Solutions with + ve deviations
3.34
Solutions
A.... B INTERACTIONS ARE MORE THAN A A AND B....B
1. A...... B INTERACTIONS ARE LESS THAN A..... A AND
.
B.... B(IIINTERACTIONS
.
) AHmixing is negative.
Energy is expected toINTERACTIONS
be released because
of the increase in the forces
in nature or AH mixing is negative.

2- PAof>interaction.
PA*A ANDTherefore,
PB > P^B the process of mixing isPexothermic
A < P A*A AND PB < PBXB AVMIXING IS NEGATIVE AHMIXING
In case the solute is a solid, its solubility in the solution is expected to decrease with rise in
3- AV
MJXING IS POSITIVE
temperature.
IS NEGATIVE
SOLUBILITY
OF SOLUTE (IF
) WILL
DECREASEfrom
WITH
4. AHmijing
IS POSITIVE
Examples
of solutions. A few examples of the
solutions responsible
forSOLID
negative
deviations
RISE IN TEMPERATURE.
5. the
SOLUBILITY
OF
SOLUTE
(
IF
SOLID
)
WILL
INCREASE
Raoults Law are listed.
WITH RISE IN TEMPERATURE
(I) Chloroform and benzene

(II) Chloroform and diethyl ether
(HI) Acetone and chloroform
(IV) Water and hydrochloric acid
(V) Acetone and aniline
(VI) Water and nitric acid
Explanation. Let us study the nature of the deviations in a solution
containing chloroform and acetone. On mixing the two components,
weak hydrogen bonding will arise in the molecules of the two
components present in the solution. As a result, they will have lesser
tendency to escape out of the ^6^12
liquid mixture
when they were
C fcHj j than
C 6 H,2
present alone in their respective containers. This will, quite obviously,
Non-ideal
solutions
showing
negative
deviations
from Raoult's
Law.
decrease
the vapour
pressure
of each
component
in the solution
and
also that
of the solution
a whole.
Non-ideal
solutionsasshow
negative deviations from Raoults Law in case on mixing the volatile
The
important
characteristics
of the
non-ideal solutions
exhibit
positive and
negative
components of the solution, the forces
of interaction
increase which
I.E. A....
B interactions
become
moredeviations
from
Raoults
Law
are
compared
below
in
the
Table.
3.3
than A....... A and B.... B interactions. As a result, the partial vapour pressure of each component and
also that of the solution will be less as compared to an ideal solution.
PA < PÂ and PB < PgXB
Similarly,
TABLE 3.3
the acharacteristics
of non-ideal
solutionsinshowing
the Comparison
behaviour ofof
such
solution has also
been represented
the Fig.positive
3.8. As and
expected, it is
negative deviations from Raoults Law
opposite in comparison to the solution which shows positive deviation. These solutions also suffer from the
following limitations.
(Pure component A)
(Pure component B)
FIGURE 3.8. Graphical representation of non-ideal solution having -ve deviation

from Raoult's Law.
(I) AVmixing IS NEGATIVE. Because of the increased forces ot interaction, the molecules of the two
components will come closer and as a result, there is a decrease in the volume of the solution.
COMPONENTS
Solutions
A
Types of Azeotropic
Mixtures
ETHANOL, C H OH
WATER, H20
BOILING POINTS (K)
MASS % OF B
IN THE
AZEOTROPE
95-57
373
351-3
3.35
AZEOTROPE
351-1
Azeotropic liquid mixtures present in binary solutions are cf two types. These are known as minimum
Cboiling
HLOROFORM
,
E
THANOL
, C2H5OH
67 00
334
351-3
332-3
azeotropes
and
maximum
boiling azeotropes.
CHCI3
BENZENE
, CFIHE BOILING
ETHANOL
C2HJOH . These32-40
351-3
341-2
MINIMUM
A,ZEOTROPES
are formed in 353-2
case of binary
liquid mixtures
showing positive
deviations from Raoults Law. For examle, a liquid mixture having 95 57 mass percent of ethyl alcohol and 443 mass percent of water represents a constant boiling azeotrope. This will be boiling at 351 1 K temperature
which is less than the boiling point temperatures of both ethyl alcohol (351 -3 K) and of water (373 K). This
is known as MINIMUM BOILING AZEOTROPE because the partial vapour pressures of the two components in
the mixture are the maximum while their boiling points are the minimum. At this stage, both alcohol and
water will behave as if they were constituents of a pure liquid and will, thus, distil together if allowed to
distil.
Some examples of the minimum boiling azeotropes along with the related data are given in the Table 3.4
f
/CH3
ClCH
........Q=C
COMPONENTS T TABLF. 3.4. Minimum Boiling Azeotropes
BOILING POINTS
(K)
MASS % OF B
_______________I________________'CH3
Acetone
Cl B
A
B
A
AZEOTROPE
IN THE
WATER, M20
CHLOROFORM,
CHCI3
CHLOROFORM,
CHCI3
HYDROGEN CHLORIDE, HC1

ACETONE, (C^^CO
METHYL ACETATE,
CH3COOCH3
AZEOTROPE
20-20
20-00
23 00
373
Chloroform
334
334
188
383
329-25
330
347-7
347-8
MAXIMUM BOILING AZEOTROPES. Similarly, solutions showing negative deviations will also result in
constant boiling points at a certain specific mass percentages of their respective constituents. But in this case,
the vapour pressure will be lowered and consequently the boiling point will be raised. Such a liquid mixture
is known as MAXIMUM BOILING AZEOTROPE because the partial vapour pressures of the two constituents
present will be the minimum and boiling points the maximum. For example, a liquid mixture consisting of
20-2 mass percent of HC1 and 79-8 mass percent of water is a maximum boiling azeotrope. It boils at 383 K
and this temperature is more than the boiling point temperature of both HC1 (188 K ) and water (373 K).
Some examples of maximum boiling azeotropes along with the related data are given in the Table. 3.5.
TABLE 3.5. Maximum Boiling Azeotropes
3.8 CONSTANT BOILING LIQUID MIXTURES (AZEOTROPES)
We have studied that in solutions which show positive deviations from Raoults Law, the vapour
pressure of the components present in the liquid mixture and also that of the solution as a whole is more than
as compared to an ideal solution. This will adversely affect the boiling point of the solution which will
decrease. However, there will be a certain intermediate composition when the vapour pressure of the liquid
mixture or solution will be the maximum and consequently the boiling point will be minimum. At this point,
the composition of the constituents in the liquid and vapour phase will be the same. As a result, both the
components present in the liquid mixture will boil at the same temperature without undergoing any change
in composition. It is not possible to separate the components of liquid mixture by fractional distillation.
This type of liquid mixture which boils at the same temperature without undergoing any
change in composition is known as constant boiling mixture or azeotropic mixture or simply
azeotrope.
3 37
*Solutions
Solutions
Solutions
3.36
The liquids
vapour Xpressure
of mixing
ethanolform
and an
methanol
are 44-5The
mmvapour
and 88-7
mm ofofHg
EXAMPLE
3.28.the
Two
and
Y on
ideal solution.
pressure
the
mixture is
more than
boiling point
of any
of the two
components
in pure slate.
This has
been shown
respectively.
A
solution
is
prepared
by
mixing
60g
of
ethanol
and
40g
of
methanol.
Assuming
the
solution
to
solution
containing
3
mole
of
X
and
1
mole
of
Y
is
550
mm
Hg.
But
when
4
mole
of
X
and
1
mole
of
Y
are
in Fig. 3.10.
be
ideal,the
calculate
vapourofpressure
the formed
solution.is 560 mm Hg. What will be the vapour
(H.P. Board
2002)
mixed,
vapour the
pressure
solutionofthus
pressure
of the
pure XSolution
and pure: Y at this temperature ?
(A.l.S.B. 1996)
SOLUTION : Let the vapour pressures of pure liquids X and Y be p^ and PY respectively.
In first solution :
Mass of CHÔH
(40 g)
= 1 - 25
FIGURE 3.9. Boiling point diagram for

A FIGURE 3.10. Boiling point diagram for
mol
Gram molar mass (32gmol )
ethanol-water mixture leading to minimum
HCI-Water mixture leading to maximum
Vapour pressure
pure
mathanol
(PB) = 88 7 mm
Mass
of CjH.OH
(60g)
= 1-30
molazeotrope.
boilingofazeotrope
boiling
No. of moles of methanol (g) ~
=
1
Separation
ofpressure
the
from
a binary
Azeotropic
Mixture
No. of moles
of
ethanol
(nA)components
Gramethanol(P^)
molar
mass
)Partial vapour
Vapour
of pure
=(46g
44-5mol
mm
pressure of methanol
Wc have learnt that an azeotrope is a constant boiling mixture and it is not possible to separate the
Mole
fraction
methanol
(XB) =mm
B = 43-46
(1-25
mol)vapour
= 0-49
(Pg)of=from
Pg-^B
(88-7
0-49)
mm
Partial
pressure
of ethanol
(PA) = PisA*needed.
A
components
the~ mixture
byxfractional
distillation.
However
in some
cases,
the separation
For
example,
rectified
spirit
is
a
mixture
of
95-5%
alcohol
and
4-5%
water.
It
is
an
azeotropic
mixture.
nB + NA (1-25 mol + 1-30 mol)
=
(44-5pure
mmalcohol,
x 0-51) also
= 22-70
mmas
Since
the solution
in nature,
Completely
known
absolute
alcoholisisideal
needed
for certain experiments in the laboratory
=
Mole
fraction
of
ethanol
(x
)
=
A
(1-30
mol)
= 43-46)
0-51
A
pressure In
of order
solution
(P) = PAit,+rectified
PB (22-70
+
= a66-16
mm.amount of benzene
and also for Total
some vapour
other purposes.
to achieve
spirit
is
mixed
suitable
and isCTsubjected
to
fractional
distillation
known
as
azeotropic
distillation.
at 100C.
different
sample 3.27. j}xe vapour n
pressure
of anmol
aqueous
mm of fractions
mercury at
+ 1-30solution
mol) of glucose is 750Three
A + nB (1-25
temperatures
are
collected
Calculate the molality and mole fraction of solute.
(Haryana Board 2001f
(i) The fraction at 3318 K is a ternary azeotrope (constant boiling mixture), containing 7-4% water,
SOLUTION
:
Calculation
of
mole
fraction
of
solute
74-1% benzene and 18 5% alcohol.
(ii) The
second
fraction
obtained
azeotrope
in which benzene and alcohol are
Vapour
pressure
of pure
wateratat341-2
373KK(PisA)a=binary
760 mm
Hg Vapour
present in the ratio of 67-7% and 32-2% by mass respectively.
pressure
of aqueous
solution
373Kalcohol
(P) = 750
mm Hg
(iii) The last fraction
collected
at 351
K pureatethyl
or 100%
alcohol also called absolute
*
P
alcohol.
According to Raoults Law, P = p. JCA or XA = RPA
Tools for Numerical Problems
For binary solutions containing
volatile components
XA = (75 mm Hg) = 0-987 (760 mm
Hg) V.P. of component A
PA = PA*A '
= Partial
Mole fraction of solute (P
JCAb)==V.P.
1 - of
XA pure
= 1 - component
0-987 = 0-013.
A jrA =
STEP 1 Calculation of molalityMole
of solution.
fraction of component A
PAccording
PB = Partial V.P. of component B
B = PBxB r to available information,
Pg0-013
= V.P.mole
of pure
component
B xB and
= 0-987 mole of solvent (water)
1 mole of the solution contains
of solute
(glucose)
Mole
fraction
of
component
B
-1
Mass of 0-987 mole of water = 0-987 mol X (18 g mol ) = 17-766 g = 17-766 x 10"3 kg
P = PA + PB :No.
For of
ideal
solution.
moles
of glucose Molality of solution (M) ~
In the vapour phase :
From the above discussion, we can conclude that in case of minimum boiling azeotrope, the boiling
point of the azeotropic mixture of less than the boiling points of any of the two pure components. This has
3 V,ofP.ethanol
been illustrated in Fig. 3.9 by taking the
water.
How ever, in case of maximum
PA example
(Partial
of=A0-75
in and
vapour
phase)
:
MoleMole
fraction
of Xis =of
boiling azeotrope,
thefraction
trend
theAreverse.
Hence,
the
boiling
point
of
the
X + Y
3(0-013
+ 1 P(TotalV.P
4
)
mol)
0-73 mol kg'1
0-73m.
-3
ofkg)
B0-25
in vapour phase)
(17-766
10
YP. B (Partial
Mole fraction of Y =
1 V.x P.
J_=
P (Total V.P.)
Mole fraction of B :
X + Y
3+1
4
Solutions
According to Raoults Law,

Px x 0-75 + Py x 0-25 = 550 mm
IN SECOND SOLUTION :
Mole fraction of X =
NX
Mole fraction of Y =
+ nY
NY
NX +
4
4+1
nY
4+1
4 = 0-8
5
_ J_= 0-2
5
According to Raoults Law

Px x 0 8 + PY x 0 2 = 560 mm
Mole fraction of ethanol (xB) =
Mole fraction of methanol (xA) =
(lmol)
B
nA + nB (1 mol+ 2 mol)
(2 mol)
A
nA + B U mo1 + 2 mo1)
1
3
_2
3
Multiply equation (i) by 4 and equation (ii) by 5

3Px + p Y = 550 x 4 = 2200 mm 4Px + PY
= 560 x 5 = 2800 mm Subtract
- Px = (2200 - 2800) = - 600
mm
Px = 600 mm
...d)
...(H)
...(Hi)
...(iv)
Substitute the value of Px in equation (HI)

3 x (600 mm) + Py = 2200 mm or Py = 2200 1800 = 400 mm
,\ Vapour pressure of pure liquid X = 600 mm
Vapour pressure of pure liquid Y = 400 MM.
hxample 3.29. Methanol and ethanol form nearly an ideal solution. If the vapour pressure of pure
methanol and ethanol at 350 K are 81 X 104 and 4-5 X 104 Nnr2 respectively, calculate the volume
composition of the vapours over a mixture of 64 g of methanol and 46 g of ethanol at this temperature.
SOLUTION : Moles of ethanol (nB)
Moles of methanol (A)
________Mass of ethanol________
Molar mass of ethanol (C2HJOH)
________Mass of methanol________
Molar mass of methanol (CH3OH)
(46g)
= 1 mol
(46 g mol"1)
64 g
C32 g mol"1) = 2 mol
3.40
W1HWKWIKMI
Solutions
3.39
STEP II Calculation of mole fraction of benzene in the vapour phase.

Mole fraction of benzene in vapour phase = Partial vapour pressure ol benzene
Total vapour pressure
(22-5mm)
(37-9mm) = 0-59.
Vapour pressure of ethanol in mixture (PB) = PB x jrB (4-5 x 104 Nm 2) x
2
3 EXAMPLE 3.31. The vapour pressure of ethyl acetate
and
propionate
are 72-8 mm and 27-7 mm
= 1-5
X ethyl
104 Nm'
of Hg respectively. A solution is prepared by mixing 25g of ethyl acetate and 50g of ethyl
2 propionate.
2 (Pb. Board 2002)
X=
4
Assuming the solutionVapour
to be ideal,
calculate
its
vapour
pressure.
pressure of methanol IN mixture (PA) = PA (8'1 * 10 Nm' ) x
Solution :
2 COOC H
CH
2 3
5-4Mass
x 104 of
Nm'
.3
No. of moles of CH3COOC2H5 (nB) ~ (1-5 x 104 + 5 4 x 104) = 6-9 x 104 Nm'2
Molar mass
Total vapour pressure of mixture
4
(1-5 x 10 Nm2J_ x ]00 _ 21.74%
(25g)
(6-9 x 104 Nm-2) = 0-284 mol
Percentage of ethanol in mixture
(88gmol ')
(5-4 xMass
104 Nm
% (6 9 x 104
of C22H) 5xCOOC
H,
10Q = 7g.226
Percentage
of
methanol
in
mixture
-2
No. of moles of C2H3COOC2H5 (nA) -----Nm
---------) ^~SS
O EXAMPLE 3.30. The vapour pressures of benzene and toluene at 293 K are 75 mm and 22 mm Hg
(50g)
respectively. 23-4g of benzene and 64-4g of toluene are mixed. If the two form
an ideal
= 0-49
mol solution, calculate
(102gmor
) are in equilibrium with the
the mole fraction of benzene in the vapour phase assuming that the vapours
liquid mixture at this temperature.
(D.S.B. 1999)
________(0 284 mol)_______
fraction of
acetate
(xg)pressure
=
SOLUTION : STEP Mole
I. Calculation
of ethyl
the total
vapour
NA + NB (0-284 mol + 0-49 mol)
(23-4g)
_______Mass of benzene_______
0-3 mol
= 0-37 (C H )
Moles of benzene (nB)
Molar mass of benzene
6 6
(78g mol-1)
(0 49 mol)______
(92 g mol )
toluene=
Mole fraction of ethyl propionateMass
(JCa) of
= ^
Moles of toluene (A) = TT~,--------------------771 NA + NB (0-284 mol +0-49 mol)
-------------------------------------------------------------- 777TTT
=(0-3
0-63mol)
"B
= 0-3
Mole fraction of benzene (rB)
+ nB (0-3
+ 0-7
mol)
Vapour pressure of ethylnAacetate
(P^)mol
= 72-8
mm
of ethyl
(P^) =27-7 (0
mm
MoleVapour
fractionpressure
of toluene
(xA) =propionate
^ =--------------7 mol)--------= 0*7
nA + NB (0-3 mol + 0-7 mol)
Vapour pressure of ethyl acetate in solution (PB) = PB*B = (72-8 mm) x 0-37 = 26-94 mm
Vapour pressure of benzene in solution (PB) = PB x JCB = (75 mm) x 0-3 = 22-5 mm
Vapour pressure of ethyl propionate in solution (PA) = PA*A = (27-7 mm) x 0-63 = 17-45 mm
a
Vapour pressure
ofvapour
toluenepressure
in solution
(PA) = P=
mm) X 0-7 = 15*4 mm Total
A x
Total
of solution
PBXA+=P(22
A
= 26-94 mm + 17-45 mm = 44-39 mm.
vapour pressure of solution = PB + A = 22-5 + 15 4 = 379 mm.
P
3.41
Solutions
OKXAMPLR .1.32. The vapour pressure of water is 123 kPa at 300 K. Calculate the vapour pressure of
one tnolal solution containing a solute dissolved in it.
Solution : 1 molal solution implies one mole of the solute dissolved in lOOOg (1 kg) of solvent I.E.
water.
No. of moles of solute (nB) = 1 mo*
Mass of water _
(1000 g)
Molecular mass (18 g mol1) _ ^ 55 mol
No. of moles of water (n A)
(1 mol)
nB
Mole fraction of solute (JCb)
(1 mol + 55-55 mol)
B + *
1
56-55
= 0-0177
Vapour pressure solution (PA) = PA;cA = PA(1 - JCb)

= 12-3 kPa x (1 -0-0177)
= 12-3 ka x0-9823
= 12-08 kPa.
O KXAMPLE 3.33. An aqueous solution is made by dissolving 10 g of glucose (C 6Hn06) in 90g of
water at 300K. If the vapour pressure of pure water at 300K is 32-8 mm Hg. what would be the
vapour pressure of the solution ?
(D.S.B. 2000)
Solution :
Mass of glucose = lOg

Molar mass of glucose = 6 x 1 2 + 1 2 x 1 + 6 x 1 6 = 180g mol'1
Mass of glucose _
Moles of glucose (nB) Molar mass of glucose

Mass of water
Moles of water (nA) = Mole Molar mass of water
.
fraction of water (jtA) =
A "B
(10g)
(180g moF1)
= 0 056 mol
(90g)
= 5 mol
(18g mol ')
(5 mol)
(5 mol + 0-056 mol) 5-056
Vapour pressure of pure water (PA) = 32-8 mm

Vapour pressure of solution (PA) = PA x JCA
= (32-8 mm) x (0-9889) =
32-44 mm.
= 0-9889
3.42
Solutions
voblervid <L^'or f^ructice

Calculate the partial vapour pressure of C 2H4Br2 at 85C for an ideal solution with mole fraction of 0-25.
Vapour pressure of pure C2H4Br2 at 85C is 170 mm Hg.
[Ans. 42-5 mm Hg]
At 40C, the vapour pressure of water is 55-3 mm Hg. Calculate the vapour pressure at the same temperature
over 10% aqueous solution of urea [CCKNH^]. (D.S.B. 1995 Supp.) [Ans. 53-48 mm Hg]
Benzene and toluene form nearly ideal solution. At a certain temperature, the vapour pressure of pure benzene
is 150 mm Hg and of pure toluene is 50mm Hg. Calculate the vapour pressure of the solution containing
equal weights of benzene and toluene.
(A.I.S.B. 1993 Supp.) [Ans. 104-1 mm Hg]
* 3-22. Assuming that Raoults Law is followed, what would be the vapour pressure of a solution formed when 40g of
sugar (molecular mass 342) is dissolved in 360 mL of water at 25C ? At 25C, the vapour pressure of water
is 20 mm and the density is lg/mL.
[Ans. 19-884 mm]
At 25C, the vapour pressure of pure water is 23-76 mm of Hg and that of an aqueous dilute solution of urea
is 22-98 mm of Hg. What is the molality of the solution ?
(C.B.S.E, Sample Paper 1996)
[Ans. 1-896 m]
3.24. Calculate the vapour pressure of a 0-1 M urea solution at 298K. The vapour pressure of pure water at
298K is 20 mm Hg. Assume density of solution to be lg mL1.
[Ans. 199-6 mm Hgj
Two liquids A and B have vapour pressure of 500 mm Hg and 200 mm Hg respectively. Calculate the mole
fraction of A at which two liquids have equal partial pressures.
[Ans. 0-286]
At 20C, the vapour pressure of pure liquid A is 22 mm of Hg and that of pure liquid B is 75 mm of Hg. What
is the composition of these components that has the vapour pressure of 48-5 mm of Hg at this temperature ?
(Assuming ideal solution behaviour).
[Ans. Same no. of moles]
* 3.27.
A 95 mass percent solution of ethanol is further diluted with water. If the mole fraction of ethanol in
diluted solution is 0-25, what is the mole fraction of water in the diluted solution. Is it still an ideal solution ?
(A.I.S.B. 1996) [Ans. Solution is not ideal]
*
3 28. An aqueous solution contains 3g of urea dissolved in 50g of water. Calculate the vapour pressure of the
solution. The vapour pressure of water at the same temperature is 2267-7 Nm' 2. [Ans. 2227-6 Nm'2]
* 3.29.
The vapour pressure of pure liquid A and pure liquid B at 20"C are 22 and 75 mm of Hg respectively.
A
solution is prepared by mixing equal moles of A and B. Assuming the solution to be ideal, calculate the
vapour pressure of the solution.
(Pb. Board 2002) [Ans. 48-5 mm)
Vapour pressure of pure components A and B are 120 mm and 96 mm of Hg respectively. What will be total
pressure when the solution contains 1 mole of component A and 4 moles of component B if the solution is
ideal ?
(Pb. Board 2003 Supp.) [Ans. 100-8 mm]
--------------------------------- ---------------------- - -----------------------------------------------------

3.9. ÔLUGATIVE PROPERTIES
There are certain properties of the ideal or dilute solutions which depend upon the number of solute
particles (molecules or ions) in a definite amount of the solvent and are quite independent of all other
physical and chemical properties of the solute and solvent. There are in fact, four such properties which have
one common characteristic as listed above. In other words, these have been colligated ( COLLIGATE : to bring
together) with respect to the number of the particles of the solute or the molar concentration of the solute in
the solution but not on the chemical identity of the solute. Thus,
colligative properties of ideal or dilute solutions are properties which depend upon the
number of solute particles or upon the molar concentration of the solute in the solution.
3.43
Solutions
The main coliigative properties associated with ideal solutions are :

Relative Lowering in vapour pressure.
Elevation in boiling point temperature.
Depression in freezing point temperature.
Osmotic Pressure.
All these properties help in the experimental determination of the molar masses of the different
substances acting as solutes. These are known as OBSERVED MOLAR MASSES. A comparison of the same
with NORMAL MOLAR MASS or theoretical molar mass can help in predicting the behaviour of the solute in
a particular solvent. Let us discuss these coliigative properties one by one.
3.10. RELATIVE LOWERING IN VAPOUR PRESSURE
We have learnt that when a rton-volatile solute is added to a solvent, the vapour pressure of the
solution becomes less than that of the solvent. Actually, the particles of the solute occupy some surface of
the container from which the evaporation takes place. Therefore, lesser surface area is now available to the
particles of the solvent so that they may change to the vapours or evaporate. Thus, the vapour pressure of
the solution (Ps) which is actually the vapour pressure of the solvent over the
o
surface of the solution (PA) will become less than the vapour pressure of the pure solvent (PA).
According to Raoults Law, the vapour pressure of the solution (Ps or PA) is the product of the
o
vapour pressure of the pure solvent (PA) and its mole fraction (xA). Thus,
Ps = PA = PA*A
For a solution JCA +
= 1 or xA = 1 - xB
Ps = P;(1-*B) O R
Ps ,
!-*B
p^ - Ps = Lowering in vapour pressure of the solution

P A-
= Relative lowering in vapour pressure of the solution as compared

*A to vapour pressure of pure solvent.
Relative Lowering in Vapour Pressure or Coliigative Property.
The mathematical expression listed above shows that the relative lowering in vapour pressure of a
solution is equal to the mole fraction (x B) of the solute. In other words, it is proportional to the molar
concentration of the solution. Thus, it is a coliigative property.
Remember
Lowering in vapour pressure is not a coliigative property because it does not
depend upon the mole fraction of the solute. Only relative lowering in vapour
pressure is a coliigative property.__________________________________________
3.44
Solutions
Determination of the observed Molar Mass of the Solute.
The expression for the relative lowering in vapour pressure can help in determining the molar mass of
the solute also called its observed molar mass. We know that,
PA -
(Here JTB = Mole fraction of solute)
" *B
WB/MB
"B
B + A WB / MB + WA / MA
But
*B =
Here
WB = Mass of solute ;
MB = Molar mass of solute
WA = Mass of solvent ;
MA = Molar mass of solvent
Since an ideal solution is also dilute in nature, therefore, n B < < < nA and can be neglected.
Thus, the expression may be modified as :
p; - ps = WB/MB _ WBXMA
p; WA/MA " MBxWA
In case the solution is not dilute I.E. non-ideal, then nB cannot be neglected as compared to
The relation may be derived as follows :
P
or
*s _ T _ nB PA
A
NA.
B +
PA . a + A , . "A
------------------ 1 +
PA - PS B
= _EA______i = p;-(p;-ps) = _ps
or
"B p; - Ps
PA - PS = J}B_ =
Ps A MB x WA
p; - Ps PA - Ps
W
MA
If all other values are known, M B which is the molar mass of the solute can be calculated. The relative lowering in
vapour pressure can be determined with the help of Ostwald and Walker Method which has been discussed in the
Competition Kit. The molar mass, as pointed out earlier is the observed molar mass and it may not be always the same
as the normal molar mass as predicted from the molecular formula of the solute. This depends on whether the solute
remains as such or undergoes changes like association or dissociation in the solvent which may result in the change in the
number of particles of the solute.
^ Tools for Numerical Problems
For ideal or dilute solution :

PA ~ ps = "ft. = B *
MA
P A " A MB x
WA
W
Here
P
A
Solutions
3.45
WB = Mass of solute; WA = Mass of solvent MB = Molar mass

of solute; MA = Molar mass of solvent.
For non-ideal solution :
p;-ps =^= MA_
__________________________^________TLA MB WA_____________________________________
2 EXAMPLE 3.34. The vapour pressure of pure water at 20C is 17-5 mm of Hg. A solution of sucrose is
prepared by dissolving 68-4 g of sucrose in 1000 g of water. Calculate the vapour pressure of the solution.
(7>B. Board 2004)
SOLUTION. Solution is non-ideal as the concentration of solute is more than 5%. According to Raoults
Law,
p; - ps _ % _ wB MA
Ps A MB WA
p; = 17-5 mm, WB = 68-4 g; WA = 1000 g ; MB = 342 g mol'1; MA = 18 g mol'1

17-5mm - Ps _ (68- 4g) x (18g moP1)
(342g mol-1) x (lOOOg) 0 0036
Ps
17-5mm - 1 = 0 0036 or
or
Ps
(17-5mm)
1-0036
Ps
= 1 0036
17-44 mm.
Z> EXAMPLE 3.35. How much urea (mol mass = 60 g mol'1) must be dissolved in 50g of water so that
the vapour pressure at room temperature is reduced by 25% ? Also calculate the molality of the solution
obtained.
(Pb. Board 2001. A.I.S.B. 2001)
Solution :STCP I. Calculation of the amount of urea.
Solution has been assumed to be non-ideal. According to Raoults Law,
WB X MA
P^-Ps _ B
PS "A
MB WA
Let P^ = 1 atm, Ps = 0-75 atm and p^ - Ps = 1 - 0-75 = 0-25 atm

(0 25 atm) = WB
(0-75atm) (eOgmol-1) *
WB =
025
0-75
(iSgmor1)
(50g)
55-55 g
Solutions
3.46
STEP II, Calculation of the molality of solution.

(55-55 g)
(60 g moP^T
No. of moles of urea___

Mass of solvent (water) in Kg
55-55
1000
, . -i
= x mol kg = 18-52 molal.
O EXAMPLE 3.36 The vapour pressure of CS2 at 50C is 854 ton and A solution of 2 0 g sulphur in 100 g
of CS2 has a vapour pressure of 848-9 ton. Calculate the formula of sulphur molecule.
SOLUTION : STEP 1 Calculation of molar mass of sulphur.
The solution is ideal and according to Raoults law
p;-ps _ wB x MA ?; MB x
wA
PA = 854 torr, Ps = 848-9 torr, WB = 2-0 g, WA
= lOOg, MA(CS2) = 76g mol'1
(854 torr - 848-9torr) _ (2 0g)x (76-Ogmor1)
(854 torr)
"
Mx(100g)
(2-0 g) x (76-0 g mol"1) x (854 torr)
(5-1 torr) x (lOOg)
MB
254-52 g mol"1.
STEP II. Calculation of molecular formula of sulphur.

LET THE FORMULA OF SULPHUR = S
N X (32g mol"1) = 254-52gmor1.
H
(254 - 52 g mol"1)
-1
(32g mol )
Thus, the molecular formula of sulphur = Sg.

3 EXAMPLE 3.37. Find the molality of a solution containing a non-volatile sotute if its vapour pressure
is 2% below the vapour pressure of pure water.
(Ticklish Problem)
Solution. The solution has been assumed to be non-ideal and according to Raoults Law
p; - p.X "B
If is the number of moles of the solute present in 1000 g ol the solvent, then nB will represent molality
of the solution.
Solutions
3.47
Let = 1 atm ; Ps = 0 98 atm ; PA - Ps = 0 02 atm ; WA = 1000 g ; MA = 18 g mol'1

Pi - Ps % x MA
Ps
WA
(Ps - Ps)
B ' Ps
or
V
MA
(0-02 atm) .
(1000 g)
(0-98atm) X (lSgmor1) = l134rao1 = l-134m
Z IVAMPLE
The vapour pressure of a 5% aqueous solution of a non volatile organic
substance at 373 K is 745 mm. Calculate the molecular mass of the solute.
(P.S.B. 1999 S)
Solution : A 5% aqueous solution means 5g of solute in 100 g of solution.
Mass of solvent (water) = 100 - 5 = 95g Vapour pressure of solution at 373 K = 745
mm Vapour pressure of water ct 373 K = 760 mm
(at B.P. of water)
The solution is dilute (ideal) and according to Raoults Law,
p;-ps ..^^3 p; A MB WA
(760mm - 745mm)
(760 mm)
15
760
or
5 g x (18g mol ')

MB x (95g)
5g x (18g mol ')
MB x (95g)
(5 g) :< (18gmol~) x 760
(95g)x 15
Ms
48 g mol-1
IPLC At 298 K. 10 g of a non volatile solute is dissolved in 100 g of acetone (mol
mass = 58). The vapour pressure of the solution at this temperature is found to be 192-5 mm Hg.
Calculate the molar mass of the solute. The vapour pressure of pure acetone at 298 K was found to be
195 mm Hg.
R
Solution :
Mass of solute, WB = 10 g
Mass of solvent, WA (acetone) = 100 g
Molar mass of solvent MA (acetone) = 58 g mol"1
Vapour pressure of solution, Ps = 192-5 mm Hg
Vapour pressure of pure solvent (acetone), P^ = 195 mm Hg
*Solutions
3.50
Solutions
Solutions
3.49
a non-volatile
solute
is vapour
added
to
aColligative
volatile
solvent
(E.G. of
water),
Elevation
in boiling
pointProperty
Relative
lowering
of
pressure
= Mole
fraction
solutethe
(B)vapour pressure of the solution tormed
will From
decrease.
This
means
that
the
solution
will
have
to
be
heated
to a higher
temperature
in order that
its
the above relation, it is evident that elevation in boiling point
(AT*) is
directly proportional
to the
vapour
pressure
is
equal
to
the
atmospheric
pressure.
Thus,
the
boiling
point
temperature
molality (m) of the solution since K* is constant. Since AT* is related to molality or number of moles of the
(T*) ofper
thekgsolution
will be more
than that aofcolligative
the pure solvent
(Th) and there will be elevation or rise
solute
of the solvent,
it is therefore,
property.
in theMolal
boiling
point temperature.
Elevation
constant Mathematically,
or Ebullioscopic constant
As the solution is dilute, we can use the formula.
Elevation
in b.p. temperature
(AT*)=(T*
T*).
The elevation
or rise in boiling
point-temperature
is related to the molality of solution as :
- Ps
B _ wB with
;; MA
The variation of thePivapour
pressure
AT* =AK*m
Pi
MB WorA AT* = K* (if M = 1)
rise Molal
in temperature
can (AT*)
also may
be be
expressed
elevation constant
defined as-1:
graphically (195
by mm
plotting
between
- 192
5 curves
mm) _point
(l-Og)x
(58 gthe
molfor
) (195
Elevation
in boiling
temperature
one molal solution i.e. the solution in which one
temperature and mm)
the corresponding vapour
Bx(100g)
mole of the solute is dissolved inMone
kg of the solvent.
pressure of pure liquid (solvent) and also its
elevation
(K*)the
for pure
a particular
diluteMolal
solution.
Theconstant
curve for
solventsolvent has also been calculated from the thermodynamic
is indicated as AB while 00128
for the solution is
relationship.
=
represented as CD. The vapour pressure
curve
2
MB X (100 g)
MKT;
K
CD for solution lies
below the curve for the
B
pure solvent AB. This
is x quite
(1000
AHvap)expected also
(1-0
g) x (58
because the vapour pressure of
solution
is g mol )
M8 the
=of solvent
Here
M
=
Molar
mass
;
R
= Gas
less than that of the pure solvent. 1If P0128
represents
x (100
g) constant
the atmospheric pressure,
then
the
corresponding
T* = Boiling point ofsolvent;
45-31
g mol 1
temperatures T*AHand
T* are the boiling
point
vap = Molar enthalpy of vaporisation of the solvent.
1
temperatures
the: K/m
pure or
solvent
UNITS ofofK*
K kg and
mol'solution.
practice
ervt6that the value of K* depends
It may be noted
upon the nature of the solvent only and is quite
B.P.
(K)K*
independent
of therange
nature
of
the solute.
The
values
of some M
common
solvents
areINlisted.
OLAL
ELEVATION
CONSTANT
(K*) (K
ForThe
a small
of
concentration,
the
rise
4.
FIGURE
FOR
VARIATION
VAPOUR
vapour pressure of a solution containing 108-24 3.11.
g ofP
aLOT
non-volatile
solute
dissolved
inKG
lOOOg ot
in
3.31.
MOL"1OF
) BOILING POINT,
temperature
(AT*)
is
directly
proportional
to
PRESSURE
AND
ELEVATION
water at 293 K is 17-354 mm Hg. The vapour pressure of water at 293K is 17-54 mm Hg. Assuming the
the
decrease
in vapour
pressure
(AP).
Since
for of the solute.
WATER
373 mass
0-52 |Ans. 181-78 g mol 1
solution
to be ideal,
calculate
the molar
aETHYL
diluteALCOHOL
solution, the
decrease
in
vapour
pressure
is
proportional
to
the
molality
( M) of the solution,
1-20
351-5
1 \BI
3.6. of
Molal
elevation
constants
solvents
The vapour pressure
of I21%
an aqueous
solution
of Thus,
a of
nonsome
volatile
solute at 373 K is 755 mm Hg.
therefore,
in the same
way.
B3.32.
ENZENE AT* is also related to the molality
353
3
2-53
Calculate the molecular mass of the solute.
[Ans. 58-68 g moi-1]
AT* x M or AT* =334-4
K* M
CHLOROFORM
3-63
Here
3.33.
A solution
containing
g of benzoic
acid,503
C6HjCOOH
CARBON
TETRACHLORIDE
350
0
K* is a constant called
molal
elevation
constant or6molal
ebullioscopic
constant.in50g of diethyl
C2H50C307-8
2H5, has a vapour
2-02
ETHER ether,
Derivation
AT*
K* xCalculate
m
pressureofofthe
410relation
mm
Hg
at =
293K.
the molar
mass of the benzoic
CYCLOHEXANE
353-5
2-79 acid. Vapour pressure of
It has
beenether
pointed
that
theHg.
rise in boiling point temperature (AT*) is directly
diethyl
at 293out
K above
is 442
mm
[Ans, proportional
113-8 g mol ']
to decrease in vapour pressure (AP). But according to Raoults Law,
Decrease
3.34. in vapour pressure
The (AP)
vapour
of pure
x pressure
Mole fraction of solute
(xB) benzene at a certain temperature is 640 mm
Hg.
A
non
volatile
solute
AT* x XB or AT* = K XB
(Here K = constant of proportionality)
PM
weighing 2-175 g is added to 39-0 g of benzene. The vapour pressure of solution is 600 mm Hg. What is the
But3.35. The vapour pressure of pure

at a certain
is 200 mm Hg. At the same temperature
JCB benzene
= 2a-----/. AT*temperature
= K Os
the vapour pressure of a solution containing
solid in 78 g of benzene is
nA + nB 2g of a nonvolatile,nAnon
+ Nelectrolytic
B
Since195
ideal
mmsolution
Hg. What
is isalso
the dilute,
molecular
NB <
mass
< <ofNAthe
and
solid
can? be neglected.
(M.L.N.R. 1992) [Ans. 80 g mol ']
3.36. The vapour pressure of pure water at 30C is 31-80 mm of Hg. How many grams of urea (molecular
mass = 60) should be dissolved in lOOOg of water
knton lower the vapour pressure
K x MA by
x N0-25iimm of Hg ?
or AT* =
AT* =- KIrU i_
(Pb.
wl Board 2001) [ANS. 26-2 G]
WA / M.
"A
If nB moles of the solute are dissolved in lOOOg of solvent (WA = lOOOg or kg) then nB/WA
represents molality (M) of the solution.
3.11. ELEVATION IN BOILING
AT* = POINT
kMA x MTEMPERATURE
.
The
mass
of solvent
(MAis) is
Therefore,
K xitMboils
(K*) where
K*surface
is molalof the
A = constant
Themolar
boiling
point
of a liquid
theconstant.
temperature
at which
or the pressure
on the
elevation
constant.equal to the external pressure. If the external pressure is one atmosphere, the boiling point
liquid becomes
Thus,
AT*normal
= K* X
M
temperature
of the liquid is called
boiling
point temperature. If a small amount of
Solutions
3.51
All other values being known the observed molecular mass of the solute can be calculated. It can
match the normal molecular mass provided
(i) the solute is non-volatile
(ii) the solution is dilute
(iii) the solute behaves normally in solution I.E., it does not undergo any association or dissociation
leading to the change in number of particles.
^ Tools for Numerical Problems________

AT/, = K, X m
ATh
Kfc *
MB X WA
MRT;2
1000 X AH. ,
_____________ ___________ . ... _____________________________________
Z\ RUMPLE 3,41 A solution containing 12-5g of non-electrolyte substance in 175g of water gave boiling
point elevation of 0-70K. Calculate the molar mass of the substance. Molal elevation constant (K b) for water
is 0-52 K kg mob1.
(A.I.S.B. 1997)
Solution :
MB
K, x WB
AT, x WA
According to available data.

Mass of solute (WB) = 12 5 g
Mass of water (WA) = 175g = 0-175 kg.
Molal elevation constant (K,) = 0-52 K kg mol"1
Elevation in boiling point temperature (AT,) 0-70K
MB = (Q'52 K kg mol-1) x (12 5g) =
(0 70K)x (0-175kg)
W EXAMPLE 3.41. The boiling point of a solution containing 50 gm of a non-volatile solute in 1 kg

of solvent is 0 5 higher than that of the pure solvent. Determine the molecular mass of the solute
(Given Molecular mass of solvent = 78 g moT1 and Kbfor solvent = 2 53 km'1)
(Haiyana Board 2003)
Determination of Observed Molar_Mass

K, xWofB Solute
We know
Solution
: that,
AT* =MBK*
AT,x XMWA
WB = 50 gW
;W
=B1_kg
= 0-5
W;R AT,
x 1000
MK ;
B /AM
(Molality)
- 2-53 km'1, or
~ MBKx kg
WAmol'1
K, =
10002-53
M = <2 53Kkgmorl)xK(50
g)
h x WB x 1000
B
AT* = Kt>(0-5
* m K)
= x (1 kg) X
MB WA
= 253 g mol"1.
Kfc x WB x 1000
AT* x WA '
Solutions
3.52
OEXAMPLE 3.42 On dissolving 3-24g of sulphur in 40g of benzene, boiling point of the solution was
higher than that of benzene by 0-81K. The molal elevation constant (K b) for benzene is 2-53 K kg moT1.
What is the molecular formula of sulphur (Atomic mass of S = 32 g moT1) ?
(D.S.B. 2000)
SOLUTION : STEP l.Calculation of molecular mass of sulphur (SJ
WB
AT, x WA
MB
Mass of sulphur (WB) = 3-24 g Mass of

benzene (WA) = 40 g = 0 04 kg Molal elevation
constant (K*,) = 2-53 K kg mol'1 Elevation in boiling
point (ATfc) = 0-81 K
MB (2 53 K kg mol~| )_xJ3; 24_g). = 2 mol-l (0-81 K)
x (0 04 kg)
STEP U. Calculation of molecular formula of sulphur.
Gram atomic mass of sulphur = 32g mol"1 In S, N x (32 g mol"1)= 253 g mol"1
N=
<253 g mol ') = 7.9 = 8 (32g

mol"1)
Molecular formula of sulphur is Sg.

O EXAMPLE 3.43. Calculate the boiling point of a solution containing 0-456 g of camphor (molar
mass = 152 g mol~') dissolved in 31-4g of acetone (b.p. = 329-45 K). Given that the molecular elevation
constant per lOOg of solvent is 17-2 K.
SOLUTION : STEP I. Calculation of elevation in boiling point (Tb).
AT _
x WB B MB x
WA
Mass of camphor (WB) = 0 456 g Mass of

acetone (WA) = 31-4 g = 0 0314 kg
Mola
elevation constant (Kfc) = 17'2K per l00 = 1-72 K kg mol"1

1000
Molar mass of camphor (MB) = 152 g mol"1

AT _ (1-72 K kg mol ) x (Q 456g) _ Q.^K B (152 g
mol"1) x (0-0314kg)
3.53
Solutions
STEP II. Calculation of boiling point of solution.

Boiling point of acetone = 329 45 K
Elevation in b.p. temperature = 0-16 K
Boiling point of solution = 329-45K + 016K = 329-61 K.
Z>EXAMPLE 3.44. lOg of a non-volatile solute when dissolved in
boiling point by 1 C. What is the molecular mass of the solute ?
(Kb for benzene = 2-53 K kg mol'1)
Solution :
_ KtxW
MB
100 g of benzene raises its

(Pb. Board 2000)
Mass of solute (WB) = 10 g Mass of

benzene (WA) = 100 g = 01 kg Elevation in b.p.
(ATfc) = 1DC = IK Molal elevation constant (KB) =
2-53 K kg mol'1
(2-53 K kg mol )x (10 g)
(1 K) x (0-1 kg)
MB
253 g mol'1
W EXAMPLE 3.45 . 0-90 g of a non-electrolyte was dissolved in 87-9g of benzene. This raised the
boiling point of benzene by 0-25C. If the molecular mass of the non-electrolyte is 103 0 g mot 1, calculate
the molal elevation constant for benzene.
(D.S.B. 2003)
Solution:
_ AT,, x MB x WA
w
Kfr
*B
WB = 0-90 g ; WA = 87-9 g = 0 0879 kg ; MB = 103-0 g mol'1 ; ATfc = 0-25

K
KB
_ (0-25 K) x (103-0 g mol'1) x (0 0879 kg)

~
(0-90 g)
= 2-52 K kg mol'1.
O EXAMPLE 3.46. Calculate the molal elevation constant for water given that 0-2 molal solution of nonvolatile and non-electrolyte solute increases the boiling point of water by 0104 K.
(H.P. Board 2003)
Solution :
ATfr
AT =Kj Km or Kj, =
= 0-2 m ; ATj, = 0-104 K
(0-104 K)
0-52 Km'1 or 0-52 K kg mol'1
KB
(0-2 m)
M
3.54
Solutions
- I \ANI| U * A solution containing 0 5126 g of naphthalene (molar mass = 128g mol~ l) in 50 0 g of

carbon tetrachloride gave a boiling point elevation of 0-402K while a solution of 0-6216 g unknown solute
in the same mass of carbon tetrachloride gave a boiling point of elevation of 0-647K. Find the molar mass
of the unknown solute.
Solution : In case of naphthalene
Mass of naphthalene (WB) = 0-5126 g Mass of
carbon tetrachloride (WA) = 50-0 g = 0 050 kg Molar mass
of naphthalene (MB)= 128 g mol'1 Elevation in boiling
point (AT,) = 0-402 K
= MB x AT, x WA
wB
_ (128 g mol'1) x (0-402 K) x (0-050g)
(0-5126g)
502K k8 010,1
In case of unknown solute

Mass of solute (WB) = 0-62I6g Mass of
solvent (WA) = 50-0g = 0 05 kg Elevation in b.p.
(AT,) = 0-647K Molal elevation constant (K,) = 5
02 K kg mol'1
- x WB MB AT, x WA
(5-02 K kg mol )x (0-6216 g)

(0-647K)x (0 05 kg) = 96-46G MOL' .
C EXAMPLE 3.48. Calculate the molal elevation constant of water if molar enthalpy of vaporisation of
water at 373K is 40-585 kJ mol'1.
Solution :
KB
AH
..
MR(T;)2
1000 x (AHvap)
(VAP) =
40-585 kJ mol'1 = 40585 J MOL'1
R = 8-314 JK'1 MOL'1, = 373K

M = 18g MOL'1
=
(18 g mol'1) x (8-314 JK-1 mol'1) x (373K) B

1000 x (40585 J mol'1)
= 0-5l3 Kkg mol'1 = 0-513 K/m.
3.55
Solutions
3.56
Solutions
The curves showing the variation in the

vapour pressure and the temperature for the
solid and liquid states of a pure liquid and its
. dilute solution
A solution
of 7g of abynon-volatile
in 250g of water boils at 100-26C. Find the molecular mass of
obtained
adding a solute
non-volatile
soluteinK
forFig.
water
is 0-52 K kg mol'1.
lAns- 56S m01 1
solute arethe
shown
the
3.12.
.
A temperatures
solution containing
0-45 g of urea
The
corresponding
to in
the22-50g
pointsof water gave a boiling point elevation of 017 K.
Calculate
the
molal
boiling
point
elevation
constant for water. Molar mass of urea is 60g mol'
where these states meet represent the freezing
[Ans. 0-51 K kg mol"1]
points of pure solvent (Ty) and that of the
solution The
Cl/).boiling
Sincepoint
T/isoflower
ethanolthan
is 78'C
T andthere
its molal boiling point elevation constant per lOOOg is 115 K. A
solution
of 1'12 g of camphor
in 32g of ethanol
is lowering
or depressionin
the freezing
point has a boiling point of 78-28C. Calculate the molecular mass
(A.LS.B. 1996) [Ans. 143-75 g mol"1]
(AT/). of camphor.
A solution containing 0*90g of a non-volatile solute in 100 mL of benzene has density 0-88 g mL at 298 K,
Just and
as itinboils
caseat of
elevation 0-25
in boiling
a temperature
higherpoint
than benzene. Calculate the molecular mass of solute. Molal boiling
temperature,
the
depression
is
freezing
point
point elevation constant for benzene is 2-52
K kg mol
[Ans. 103' 1 g mol ]
temperature
is alsoof proportional
to the solute
molality
A solution
12-5g of an unknown
in 170g water gave a boiling point elevation of 0-63K. Calculate
(M) of thethe
solution.
Thus,
molar mass
of the solute. (K^ = 0-53 K kg mol'1).
1
Board
1991,
AT/QC M(Pb.
or AT/
= K/
X MD.S.B. 1997, A.l.S.B. 1997, H.S.B. 1997 S) [ANS. 61 -85G MOL' ]
Here K/ is the molal depression constant
1
Calculate
of aF.P.
solution
containing l-8Molal
g of a non-volatile
dissolved
in kg
90gmol'
of benzene.
and is also
knowntheasboiling
molalpoint
cryoscopic
constant.
(K)
depression solute
constant
(K/) (K
)
The boiling point of pure benzene is 353-23 K, Kj, = 2-53 K kg mol 1. [Molecular mass of solute = 58g
If
M = 1 molal, AT/ = K/.
mol'*]
(A.l.S.B. 1994) [Ans. 354-1 K]
molalpoint
depression
may
be defined
as : if 3g of a non-volatile solute is dissolved in 20 mL
. s 4Thus,
The boiling
of water constant
is 100C and
it becomes
100-52C
Water
273'0
1 86
of it. Calculate the molecular weight of the solute. (K6 for water is 0-52 K kg mol 1 density of water = 1 g
Depression or lowering 155-7
in freezing point temperature for 1 molal
solution i.e. the solution in
Ethyl alcohol
1 -99
mol'1).
which one mole of the solute
(D.S.B.
1992 Supp.) [Ans. 150 g mol'1]
Benzene
278-6is dissolved in kg of the solvent.
5-12
The molal depression constant (K/)
can also be calculated from the thermodynamic
relationship.
Chloroform
209-6
4-70
2
Calculate the molecular
mass
of
a
substance,
1-0
gram
of
which
when
dissolved
in
100
gram
of solvent gave an
Carbon tetrachloride
250-5
31-8
MR(T})
elevation of 0-307K in the boiling
point. (Molar elevation constant = 1 -84 K
kg
mol ).
Ether
156-9
1
79
KF
[Ans. 59-93 g mol'1]
~ 1000 x AH~
Cyclohexane
279-5
20-2
Here
= Molar
= constantsolute is dissolved in 100 mL of it.
. t.4M
? The
boilingmass
pointof
of solvent,
water becomes 100-52C if 1 -5g of a R
non-volatile
Calculate
the
molecular
weight
of
the
solute.
(K*
for
water enthalpy
= 0-6 K kgofmol
'). (density
water =
T} = Freezing point of solvent,
AH^,, = Molar
fusion
of theof
solvent
1 g mL'1)
(H P- Board 1994) [Arts. 17-31 g mol'1]
1
Units of K/: KJM or K kg mol' .
The boiling point of 5% solution (W/W) of non-volatile solute in water is 100-45C. The boiling point of pure
Just like
elevation
constant,
themass
value
of solute
K/ also
upon the nature 1of the solvent and is
watermolal
is 100C.
Calculate
the molar
of the
(Kdepends
t for water = 0-52 K kg mol' )
quite independent for the nature of the solute. The K/ values of some solvents are listed.
[Ans. 60-8 g mol'1]
y,
_____________________________________________
3.12. DEPRESSION
IN FREEZING
POINT
TEMPERATURE
TABLE
3.7. Molal
depression
constants of some solvents.
The freezing point of a liquid is the temperature at which the liquid begins to freeze or solidify. It is
also the same temperature at which the solid begins to melt. Thus, at this temperature, both the solid and
liquid states of a substance co-exist, are in a state of equilibrium and have also the same vapour pressure.
When a non-volatile solid is added to the liquid to form the solution, the vapour pressure of the solution
decreases. Since freezing point is the temperature at which the vapour pressure of the liquid and solid
phases of a substance are equal, with the decrease in vapour pressure of the solution freezing will occur at a
lower temperature or there is a depression in the freezing point temperature of the pure solvent. The
freezing point temperature (TY) of the solution will be less than that of pure solvent (TY).
Depression in f.p. temperature (ATY) = (TY - TY).
Solutions
Depression in Freezing Point - a Colligative Property.

From the above relation, it is evident that the depression in freezing point (AT,-) is directly
proportional to the molality of the solution I.E., moles of the solute dissolved per kg of the solvent. It is
therefore, a colligative property.
Antifreeze Solutions
In severe cold, the temperature usually falls below 0C. As a result, water used in the
radiators of cars and other automobiles is expected to freeze. This will cause expansion leading to
the bursting of the radiator. In order to avoid this, antifreeze solutions are used. The most
important solution is a mixture of water and ethylene glycol (HOCH 2CH2OH). It is popularly
known as coolant. A mixture of ethylene glycol and water in equal proportion by volume freezes at
-36C. This can be safely added in car radiators even under sub-zero weather conditions. The
basis for the lowering in the freezing point is that the presence of impurities lowers the freezing
point of a liquid.
Determination of Observed Molar Mass of Solute
We know that,
AT^ = Ky x M
w B / M B w B xiooo A FIGURE 3.12. Plot for variation in vapour
pressure and freezing point.
MBX WA
"(Molal,l),> "
K7 X WB X 1000
AT>-
MB x WA
KF x WB x 1000
or
ATF x WA
Thus, if all other values are known, the observed molar mass of the solute can be calculated. It can match
the normal molar mass provided
(i) the solute is non-volatile
(ii) the solution is dilute
(HI) the solute does not undergo any change in number of particles because of dissociation or
association.
[71 Tools for Numerical Problems

ATf = Kf x M
_ K f x WB
AT, MB x WA
MRT,
K/ =
1000 x AHfus
O l - A a m p h 3 Art aqueous solution of an organic compound containing 0-6g of it dissolved in 21-7g of

water, freezes at 272 187 K. If the value ofK f i s 1-86K kg mol'1 for water which freezes at 273 K, calculate
the molecular mass of the organic compound.
(Haryana Board 20011
K J x W,
Solution :
AT7 x W
3.58
Solutions
Mass of compound (WB) = 0-6 g

Mass of water (WA) = 21 -7g = 0 0217 kg
Depression in freezing point (ATy) = (273 - 272-187) = 0-813K
Molal depression constant (KY) = l-86Kkgmol'!
(1-86 K kg moP1) x (0-6g)
MB = (0-813 K) x (0-0217kg)
= 63-26 g mol'1.
OPXAMPH 3 :
The freezing point of pure nitrobenzene is 278-8K. When 2-5g of an unknown
substance is dissolved in lOOg of nitrobenzene, the freezing point of the solution is found to be 276 8K. If the
freezing point depression of nitrobenzene is 8-0 K kg mot 1, what is the molar mass of the unknown substance ?
(A.I.S.B. 1997)
Solution :
MB =
x Wn
AT) x WA
Mass of solute (WB) = 2 5g Mass of

nitrobenzene (WA) = 100g = 0-1 kg Depression in
freezing point (AT-) = 278 8 - 276-8 = Molal depression 2K
constant (Ky) = 8 0 K kg mol'*
_ (8 OK kg mol'1) x (2-5 g)
-------------(TicTMO-lkg)---------- = 100g mo1
WL \ AM PI I
]n coitf ciiMATE. water freezes causing damage to the car radiator. Ethylene
glycol is used as an antifreeze agent. Calculate the amount of ethylene glycol to be added to 4 kg of water to
prevent it from freezing at -6C (K f f or water = 1-85 K kg mot').
(Roorkee 1992)
MB
MB x AT- x WA
WB ~----------7}-----------K
f
Molar mass of ethylene glycol (OHCH2CH2OH), MB = 62 g mol'1
Solution :
Depression in freezing point (ATY) = 06 - (-6C) = 6C = 6K Molar

depression constant (KJ) = T85 K kg mol'1 Mass of water (WA) = 4 kg
f62g mol 1) x (6K) x (4 kg)
*='
~ (T-85 K kg mol'1)
8OF SAMPLE 3 Calculate the amount of ice which will separate on cooling a solution containing 50g of
ethylene glycol in 200g of water to - 9-3C. (K f f or water = 1-86 K kg mol'1) (Roorkee 1995)
SOLUTION : STT P I Calculation of the amount of water present in the antifreeze solution.
W
Mass of ethylene glycol (WB) = 50g Molar mass of ethylene glycol

(MB) = 62g mol"1 Depression in freezing point (ATY) = 0 - (- 9-3C) = 93C = 9-3K
3.59
Solutions
Molar depression constair K,) = 1-86 K kg mol'1

WB x K,
Mass of water (WA) MB x AT, "
_ (5Qg) x (1-86K kg mol'1)

(62g mol'1) x (9 3K)
= 016129 kg = 161*29 g
ST. | 11 calculation of the amount of ice separating on cooling.
The water which is not a part of antifreeze solution will separate as ice on cooling. It may be
calculated as 200g - 161 -29g = 38-71g.
SL X.IMPK 3.53. The molal freezing point depression constant for benzene (Cfld is 4-90 K kg mol' 1.
Selenium exists as a polymer of the type Se x. When 3-26g of selenium is dissolved in 226 g of benzene, the
observed freezing point is 0-112C lower than that of pure benzene. Deduce the molecular formula of
selenium (Atomic mass of Se = 78-8g mol'1).
(Delhi Board 2002)
SOLUTION : U P (. Calculation of molar mass of selenium (SeJ
K F x WB MB AT, x WA
Mass of selenium (WB) = 3-26 g Mass of
benzene (WA) = 226 g = 0-226 kg
Depression in freezing point (AT,) = 0-112C = 0-112K
Molar depression constant (K,) = 4-9 K kg mol"1
(4-9 K kg mol *)x (3-26 g)

(0-112 K) x (0-226 kg)
631-08 g moT1
Su, Gram atomic mass of selenium = 78-8 g mol 1 In Se*,

X
(78-8 g mol'1) = 631-08 g mol"1

X
= (631-08g mol *) _ g
(78 8g mol-1)
Molecular formula of selenium = Seg.

; I X,IMPI,. T.?4. Molal enthalpy of fusion of water at 273K is 6 0246 kJ mol'1. Calculate molal depression
constant for water.
Solution :
K = MR< V
(AHmsioo)
AH(fusion, = 6-0246 kJ mol'1 = 6024-6 J mol'1

M = 18g mol'1 = 0-018 kg mol"1
R = 8-314 JK'1 mol"1, T = 273 K
_ (0-018 kg mol"1) x (8-314 JK mol'^x (273K)2 K/~
mol"1)
= 1-85K kg mol"1 = 1-85 K m"1
(6024-6J
3.60
3.62
Solutions
Solutions
3.61
Solutions
Osmosis and Diffusion
Apparently both osmosis and diffusion are similar as they involve the movement of the particles but
actually they represent different phenomena. Diffusion is the free intermixing of the particles (molecules or
The freezing
point of aand
solution
containing 18g ofmembrane
a non-volatile
solute dissolved
200gOsmosis
of water is
decreases
ions) of different
substances
no semipermeable
is needed
for the in
same.
rather
1
by
0-93.
Find
the
molecular
mass
of
solute,
for
water
is
1-86
K/m.
[Ans.
180
g
mol'
]
selective in the sense that only the particles of the solvent can diffuse and that too through a semipermeable
membrane.
osmosis
be reversed
or even
stopped
by applying
the solution
3.48Moreover,
A solution of
l-25g ofcan
a certain
non-electrolyte
in 20
0 g of water
freezes atpressure
271-94 K.onCalculate
the but
this is not possiblemolecular
in diffusion.
distinction
between
osmosis
diffusion
are listed
in1]
mass The
of themajor
solute.points
Kf for of
water
is 1-86 K/m.
(Haryana
Boardand
1996)
[Ans. 109-67
g mol'
the Table A3.8.
solution containing 62-5g of non-volatile solute per lOOOg of water has a freezing point 1 06C less than
1
*
PURE _
WATER
that of water. Calculate the molecular mass of the solute. (K^ = 1 -86 K kg mol'1).
TABLE
3.S. Difference between osmosis and diffusion
[Ans. 109-67 g mol'1]

.^ (molar
mass
_ _'= 342g/mol) is prepared by dissolving 68-4g in lOOOg of water. What
-S-M. A solution of sucrose
is
the (i) freezing point and (ii) boiling point of the solution ? K/for water is 1 -86 K/m and K* = 0-52 K/m.
lAns. t.p. = 272-63K. b.p. = 373-1K]
3.SI. On dissolving 0-25g of a non-volatile substance in 30 mL of benzene (density 0-8g mL' 1), its freezing
"
point decreases by 0-40C. Calculate the molecular mass of the non-volatile substance. Ky-for benzene is
5-12 KmA
'1.FIGURE 3.13. Process of osmosis through
(Himachal
Board 2000
S) (Ans. 133-33 g mol'1]
semipermeable
membrane
The spontaneous
movement
of the
solventinmolecules
from pure
solvent
into
the issolution
A solution
containing 25-6g
of sulphur
dissolved
lOOOg ofeither
naphthalene
whose
melting
point
80-lC,
dilute
solution
intooftheO^C.
concentrated
through
a semipermeable
membrane.
gave or
a from
freezing
point
lowering
Calculate solution
the formula
of sulphur.
Kf for naphthalene
is 6-8
K/m
__________________
[Ans. Sg]
3.
Semipermeable
Membranes
A solution containing
18g of a non-volatile solute in 200g of water freezes at 272-07 K. Calculate the
1
These
are the
membranes
which allow
molecules
through
them.
molecular
mass
of the solute.(Given
K/ =only
1-86 the
K/m)movement of the solvent
(D.S.B.
1993) [Ans.
180 g mol"
]
These Normal
may be freezing
either naturally
as A
parchment,
bladder
goatsolvent
or pigcauses
and a
point of aoccurring
solvent issuch
150C.
0-5 molal cellophone,
solution of urea
in theofthis
52 other
some
cell
membranes.
these
are not
perfect
for measurements
in the laboratory.
freezing
point
depression ofHowever,
two degrees.
Calculate
the molal
depression
constant.
Semipermeable membranes have also been prepared chemically. For example, when aqueous solutions 1
(Haryana
Board 1998)
[ANS. 4 of
K M' ]
of potassium ferrocyanide and copper sulphate are mixed in a porous pot,
the gelatinous
precipitate
3.55.
The
freezing
point
of
cyclohexane
is
279-65K.
A
solution
of
14-75g
of
a
solute
in
500g
of
cyclohexane
has
a
copper ferrocyanide fills in the pores of the porous pot and acts as semipermeable membrane.
freezing point of 277-33 K. Calculate the molar mass of the solute. (Given Kf = 20-2 K kg mol-1).
2CUS04 + K4[Fe(CN)6]--------* Cu2lFe(CN)6] + 2K2S04
1
(Haryana Board 1996) [Ans. 256-85 g mol' ]
In addition
this, ga ofvariety
of polymer
such as
polymer lowers
cellulose
acetate point
are from
also
Addition to
of 0-643
a compound
to 50mLmembranes
of benzene (density
0-879g/mL)
the freezing
of the compound.
available.5-51C to 5-03C. If Ky = 5-12 km"1, calculate the molecular mass______________________________
1
(Haryana
[ANS
. 156G themMOL' ]
In order to demonstrate the osmosis, remove outer shells of two eggs
of theBoard
same2001)
size by
placing
in dilute hydrochloric acid for sometime. Put one of these in water while the other in brine (NaCl) solution.
The '-------------------------------------egg placed in water will swell in size
after certain time interval while the other kept in brine solution
-------------------------------------------------------------
shrink
in size. In
theOSMOTIC
first case, water
enters the egg which contains a concentrated fluid through the egg
will
3.13.
OSMOSIS
AND
PRESSURE
walls acting as semipermeable membrane. In the second case, water present in the fluid comes out of it as a
Osmosis
result of osmosis and passes into sodium chloride solution which is more concentrated. Thus, swelling takes
to understand
phenomenon
letcase.
us take an inverted thistle funnel with mouth tied
placeIninorder
the first
case while the
shrinkage
occursof
in osmosis,
the second
by a semi permeable membrane such as parchment membrane as shown in the Fig. 3.13. It is such that only
the molecules or particles of solvent and not of solute can pass through it. Fill the funnel with sugar solution
and lower the same in a beaker containing water. It is observed that the level of the solution inside the stem
of the thistle funnelOSMOSIS
starts rising. It is quite obviously due to the flowDof
solvent (water) into the solution
IFFUSION
through the semipermeable membrane. This is known as osmosis (In Greek, OSMOS = to push). This was
first time
by APLACE
BBE NOLLET
IN 1748.
1. THE observed
PROCESS for
OF the
OSMOSIS
TAKES
THROUGH
A IN DIFFUSION, NO SEMIPERMEABLE MEMBRANE IS
REQUIRED.
SEMIPERMEABLE
.
Brine (NaCl)
OsmosisMEMBRANE
can also take
place when the two solutions with different concentration
of the same solute are
solution
placed
in
contact
and
are
separated
by
a
semipermeable
membrane.
It
will
occur
from
the
solution into
2. THE PROCESS OF OSMOSIS INVOLVES THE MOVEMENT OF IN DIFFUSION BOTH THE SOLUTE AND dilute
THE SOLVENT
concentrated
solution
orDIRECTION
from the solution
withMOLECULES
lesser solute
into the DIRECTION
solution with
higher
THEthe
SOLVENT
MOLECULES
IN ONE
ONLY.
CANconcentration
MOVE BUT IN OPPOSITE
.
concentration
FIGURE
of
the
3.14.
solute.
Demonstration
Osmosis
may
of
be
the
defined
phenomenon
as
:
of
osmosis
(Normal
lines
represent
size
3. IN OSMOSIS, MOLECULES OF SOLVENT MOVE FROM A REGION IN DIFFUSION, THE MOLECULES (SOLUTE AND SOLVENT)
before osmosis and dotted lines represent size after osmosis).
OF LOWER CONCENTRATION OF SOLUTE INTO A REGION OF MOVE FROM A REGION OF HIGHER CONCENTRATION INTO
HIGHER CONCENTRATION.
A REGION OF LOWER CONCENTRATION.
4. OSMOSIS CAN BE STOPPED OR REVERSED BY APPLYING IT CANNOT BE PREVENTED OR STOPPED.

ADDITIONAL PRESSURE
CONCENTRATION.
ON
THE
SIDE
OF
HIGHER
5. THE PROCESS OF OSMOSIS IS COMMON IN LIQUIDS ONLY.
THE PROCESS OF DIFFUSION IS COMMON IN LIQUIDS AS

WELL
AS IN GASES.
3.63
Solutions
One of these is fitted with a narrow glass tube

External
through which solvent can be filled. The other
compartment is fitted with a wider tube having a
water tight and frictionless piston. Solution is taken
in this compartment. The molecules of the solvent
(generally water) will try to pass into the solution
through the semipermeable membrane and the piston
will tend to move upwards and the level of solvent
in the narrow tube will obviously fall. However, if
some external pressure (generally in the form of
weight) is applied on the solution, the entry of the
solvent into the solution can be prevented or even
stopped. This can be confirmed by the level of the
solvent in the narrow tube which will remain constant
under the conditions. The pressure which is applied
FIGURE 3.16. Representation of
on the surface of the solution is also osmotic pressure
osmotic pressure.
and may be defined as :
the external pressure that has to be applied on the solution to prevent the osmosis of the
solvent into it through a semipermeable membrane.
Osmotic pressure is normally indicated as
is represented as P.
in order to distinguish it from atmospheric pressure which
Remember
A solution of its own has only vapour pressure. It will develop osmotic pressure only
Osmotic Pressure
when osmosis takes place by placing it in contact with a solvent or less concentrated
solution through
a semipermeable
membrane.
In order to understand
osmotic
pressure, deposit
the _________________________________
Reverse
Osmosis and
its Application
artificial
semipermeable
membrane
of copper ferrocyanide
It is interesting
notea that
external
in a porous
pot fittedtowith
longifglass
tube pressure
with the higher
help ofthan the osmotic pressure is applied on the
solution,
solventFill
willthe
startporous
flowingpot
fromwith
the solution
the pure solvent and the level of solvent in the
rubber the
stopper.
aqueousinto
sugar
smaller
tube
will
start
rising.
This
process
is
known
as
reverse
solution and place them in water taken in a beaker as osmosis and is useful in a number of ways.
The
desalination
of sea water is also based on reverse osmosis which helps in converting sea water containing
shown
in Fig. 3.15.
dissolved salts into pure water. Sea water is taken in a tank provided with a rigid semipermeable membrane
Osmosis
will The
occur
and the in
level
solutionto will
of cellulose
acetate.
membrane,
fact,ofis the
permeable
water but impermeable to the impurities as well
rise inin the
glass Pressure
tube. After
a than
few osmotic
days, the
level is applied on it. Reverse osmosis occurs and
asslowly
ions present
sea water.
more
pressure
will water
become
stationary
and
further osmosismembrane
will occur.
pure
forces
it way out
of no
the semipermeable
because of reverse osmosis. This is quite good
Actually
hydrostatic
called osmotic
pressuredesalination
develops plants to meet the requirement of drinking
for
drinking
purposes. pressure
Many countries
have employed
water.
on the surface of solution which stops osmosis. The osmotic
pressure
may be defined
as :
Experimental
Determination
of Osmotic Pressure
excess hydrostatic
that the
develops
A numberthe
of methods
are availablepressure
to determine
osmotic pressure of a solution. These are :
duemethod
to osmosis at a particular temperature.
Pfeffers
definitionmethod
of osmotic pressure. Osmotic
Alternate
Berkley-Hartleys
pressure
can
also
be
defined
in an alternate manner. To
de Vries plasmolytic method
understand it, consider a glass vessel divided into two
Morse-Frazer method
compartments with the help of a semipermeable membrane
FIGURE 3.15. Representation of
as shown in Fig. 3.16.
osmotic pressure.
Townsends reverse osmosis method.
The commonly used method is by Berkley and Hartleys. The principle underlying this method is the
alternate definition of osmotic pressure according to which
it is the external pressure which is applied on the surface of the solution just sufficient to
prevent the entry of the solvent into it.
3.64
Solutions
The apparatus consists of a porous pot

containing the semipermeable membrane of
copper ferrocyanide. The porous pot is filled
with water and is surrounded by a vessel
containing the solution whose osmotic pressure
is to be determined. The porous pot is Fitted
with a capillary on one side and a water reservoir
on the other side (as shown in Fig. 3.17). Water
from the porous pot will try to pass into the
solution through the semipermeable membrane
as a result of osmosis. It is indicated by the fall
in level of water in the capillary tube. A pressure
is applied on the solution in order to maintain
the water level in the capillary tube at the same
level. This excess pressure measured by the
FIGURE 3.17. Berkley and Hartleys Method
for osmotic pressure.
pressure gauge gives the osmotic pressure.
Advantage : This method is better than the other methods in a number of ways :
(i) It is quick and the results are accurate.
(ii) The concentration of the solution does not change because solvent is not allowed to enter
the solution.
(HI) Since the external pressure balances the osmotic pressure, there is no strain as such on the
semipermeable membrane and the danger of its bursting because of fast osmosis is ruled
out.
Van't Hoff Theory of Dilute Solutions
Vant Hoff on the basis of the experimentation stated that there exists an analogy between gases
and dilute solutions in the sense that the gas laws which are applicable to gases can also be applied to
dilute solutions. Thus, the following laws hold good for the dilute solutions of non-electrolytes.
1. Boyle-Vant Hoff Law. According to the law, the osmotic pressure (rr or P) of a dilute
solution is directly proportional to its concentration provided temperature is constant. Thus,
7i ac C (At constant temperature)
Here C = n/V where n is the number of moles of the solute dissolved in *V volume of the
solution. It may be noted that the osmotic pressure of a solution in which one mole of the solute is
dissolved per litre of the solution at 0C (273K) is 224 atm.
2, Gay Lussac Vant Hoff Law. The law states that concentration remaining the same, the
osmotic pressure of a dilute solution is directly proportional to the kelvin temperature (T).
Thus, 7t oc T or 7t/T = constant
Combining the two laws, we get :
it QC CT or it = RCT
where R is a constant known as solution constant and its value is the same as that of the gas
constant (R) I.E., 0 0821 litre-atm K~ mol'1.
Since C is equal to n/V, therefore the relation can be put as :
nRT
it =
or 7tV = nRT
(IT) The solution is dilute I.E., the concentration of the solution is not more than 5%.
3.65
Solutions
As osmotic pressure is also denoted by the sign P, therefore,

PV = nRT
This equation is known as Vant Hoff Equation for dilute solutions.
Osmotic oressure-a colligativc property. It has been stated that the osmotic pressure depends upon the
molar concentration (C) of the solution, I.E. upon the number of moles of the solute ( N) dissolved in a given
volume (V) of the solution. It is, therefore, a colligative property.
Determination of the observed Molecular Mass of the Solute.
According to Vant Hoff equation : trV = nRT But

n = WB/MB
_ WB
V = Mr RT
Here WB = Mass of the solute, Ma = Molar mass of the solute. All other values being known, the
observed molar mass of the solute can be calculated as :
WpxRxT
n x V
Thus, observed molar mass of the solute can be calculated. It can match the normal molar mass
provided.
(I) Solute is non-volatile.
(HI) The solution does not undergo association or dissociation in the solution.
Note. We have studied that all the four colligative properties are helpful in determining the molar mass of
the solute. Out of these osmotic pressure is the best although it is sometimes inconvenient to prepare different
semipermeable membranes. In fact, osmotic pressure can be determined at room temperature whereas other
colligative properties such as elevation in boiling point and depression in freezing point can not be evaluated at
room temperature. It is particularly useful for biomoiecules and polymers with high molecular masses such as
proteins because in their dilute solutions both elevation in boiling point (AT*) and depression in freezing point
(AT/) are too small to be measured accurately. Moreover, the polymers and biomolecules are generally not
stable at higher temperature._________________________________________________________
Isotonic and Isomotic Solutions
According to Vant Hoff equation of dilute solution; n = CRT. This means that
two dilute solutions with same molar concentration at given temperature have also the same osmotic
pressure. Such solutions are known as ISOTONIC OR ISOMOTIC solutions.
In case such solutions are placed in containers that are separated by a semipermeable membrane, no osmosis
will occur. However, if two solutions have different molar concentrations of the solute, they will also have
different osmotic pressures. The solution having a higher solute concentration is called hypertonic solution while
the one with lesser concentration of the solute is known as hypotonic solution. In case, such solutions are
separated by a semipermeable membrane, osmosis will occur from hypotonic solution into the hypertonic solution
till the two acquire the same solute concentration or become isotonic.
3.66
Solutions
Biological significance of Osmosis
Phenomenon of osmosis is of immense significance both in human beings as well as in plants.

1. In human beings. The blood plasma or RBC have a number of species present . The concentration of
these species is equivalent to 0-9% aqueous solution of NaCl also called saline water. This means that blood
plasma and saline water are isotonic with respect to each other. In case blood cells come in contact with
pure water, the latter will be hypotonic in nature. As a result, molecules of water will rapidly move into the
cells which will swell and ultimately burst. This is called hemolysis. Similarly, in case the blood plasma
comes in contact with a solution with concentration more than 0-9%, then the plasma will be hypotonic and
the fluid inside will come out resulting in the shrinkage of the cells. This is known as plasmolysis. Keeping
this in veiw, the injectable medicines are generally dissolved in saline water (0-9% solution of NaCl) before
being injected. This prevents the cell walls from either undergoing shrinkage or bursting. Osmosis also
plays a vital role in the functioning of kidneys.
2. In plants. Osmosis also plays a significant in the absorption of water by the plant roots from the soil
and its movement to different parts of the plant body. Actually, a plant body is made up of a large number of
cells which contain fluid known as cell sap. The walls of the plant cells are made up living cytoplasmic
membranes which behave as semi-permeable membranes. These cell saps have generally higher osmotic
pressure and they take up water from the soil since soil water has less osmotic pressure (hypotonic in
nature). The water then travels to other parts of the plant body such as branches, leaves and flowers etc. The
problem arises when the plants grow in marshy land or marshy soil. The cell saps develop high osmotic
pressure of the order of twenty five atmospheres due to high concentration of the particles. These saps may
therefore, absorb excess of water from the soil which may lead to bursting of root hair and ultimately to the
decay of the plants. In such cases, use of fertilizers is recommended. They are likely to raise the osmotic
pressure of the soil water. As a result, the cell saps are not now in a position to absorb excess water and the
decay of the root or of the plant as a whole is checked or prevented.
^ Tools for Numerical Problems

Vant Hoff Equation :
KV
= nRT
= RT = CRT V
For Isotonic Solutions :
WB x R x T
or MB =
MB x V
WB X R X T
nxV
JI
Osmotic pressure in atmospheres Volume of
solution in litres Solution constant (0-0821 L
atm K"1 mol1)
N2
or Vi v2
r^RT n2RT
3 67
Solutions
jmtteeeHtiwaws
#*
OEXAMPLE 3.55. Calculate the osmotic pressure of 5% solution of canesugar (sucrose) at 15C.
WXRxT
Solution : Osmotic pressure (n)= -------------- ; Mass of sucrose (WB) = 5 g
Mo x V
Molar mass of sucrose (C12H22OH) MB = 342 g mol*1
100
Volume of solution in litres (V) - lOOmL-
1000
= 0-1L
Solution constant (R) = 0 0821 L-atm K 1 mol 1

Temperature (T) = 15C = 15 + 273
288K
N = (5g)x (0-0821 L atm K"1 mor*)x (288K) = 3.457 atm
" 71
(342 g mol*1) x (0-1L)
3 EXAMPLE 3.56. One litre of aqueous solution of sucrose (molar mass = 342g mol'1) weighing
1015g is found to record an osmotic pressure of 4-82 atm at 293K. What is the molality of the
solution ?
(D.S.B. 1997)
SOLUTION : STEP I. Calculation of number of moles of solute.
_
nRT __
JtV
jr -------- AX N -----------V
RT
1
rt = 4-82 atm, V = 1L, R = 0 0821 L atm K'1 mol*
=
0-2
mol.
n=
(0 0821 Latm K'1 mol-1) x (293K)
T = 293K
Step II, CALCULATION OF THE MOLALITY OF SOLUTION.
Mass of solute (sucrose) = (0-2 mol) X (342g mol-1) = 68-4g
Mass of solution = 1015g
Mass of solvent (water) = 1015 - 68-4 = 946-6g = 0 9466 kg
.. ,
, , Mass of glucose / Gram molar mass
Molality of solution (M) =--------------s--------------------------------Mass of solvent in kg
(68-4g)
= 0-2113 moles/kg = 0-2113 m
(342gmol )x (0-9466kg)
3H\AMPK 3.57 Calculate the osmotic pressure of a solution obtained by mixing 100 mL of 4-5%
solution of urea (mol mass = 60) and 100 mL of 3-42% solution of cane sugar (mol mass = 342) at
300K. (Given R = 0 0821 L atm K'1 mol'1)
SOLUTION : Step I. Calculation of the osmotic pressure of solution containing urea.
WjxRxT
' ~ MB x V
3.68
Solutions
Solutions
1
WB = 4-5g,
B = 60g mol- , T = 300K
ÊXAMPLE 3.59. At what concentration
of M
solute
'P' the solution will be isotonic with a 5 percent
solution of urea ? (Molar mass of P = 342 g mol~*)
(Pb. Board 2003)
R = 0 0821
L atm
K"1 mol'1. V = (100 + 100) = -2L- = 0-2L
Solution : Since solutions are isotonic,
rc(Solute
) = 7t(rea)
1UUU
WB X R x T
-1
-1
"(urea) ~ M(4-5g)
B x V x (0 0821 Latm K mol ) x (300K) _
TCt
" - -
1);V=-01L
,---------------- mil)
WB = 5g ; MB = (60
g mol'
(60 g mol *) x (0-2L)
(5g)x
R x T containing sucrose.
Step II. Calculation of the osmotic_pressure
of solution
"(urea) ( w i . m n r h x m , m
w
WB = 3-42g, MB = 342 g mol-', T = 300K
R = 0-0821 L atm K'1 mol-1, V = (100 + 100) =

(3-42g) X (0-0821 LatmK-1 mol-1) X (300K)
(342 g mol-1) x (0-2L)
712
lUOU
= 0-2L
= 1>23 atm
S t e p I I I . Calculation of the total osmotic pressure of solution.

^(solute)
Total
Equating
(i) osmotic
and (ii) pressure (JI) = Jtj + 7*2 = (9 236 + 1-23) = 10-47 atm.
O Example 3.58. A solution containing 10-2g of glycerine per litre is found to be isotonic with 2%
(5g)x R x T
solution of glucose (molar mass = 180 g mol"1). Calculate the molar mass of glycerine.
(Pb. Board 2001)
Solution : Since solutions are isotonic; tt(g|ycerine) = Jt(g|UCOse)
WB =
or
1
(60 g mol" ) x (0-1L)
= WB X R X T
^{glycerine)
MB x V
WB x R x T
10-2g, V = 1L
W
B
MB x V
(342 g mol-1); V = 0-1 1
= (10'2g) x R x T 71
W j x Rx T
(342 g mol-*)x (0-1 L)
W x Rx T
(342 g mol-1)x (O IL)
(glycerine)
17
MB x (1L)
WB X R X T
MN x V
(glucose)
WB = 2g, MB = (180 g mol'1), V = 100 mL = O IL
(5g)x (342 g mol-1)
(2g)x R x T
(180g mol-1) x (0 1L)
%'ucose)
(60 g mol - ) "
Equating (i) and (ii) :
(10-2 g) x R x T =
(2g) x R x T
(Mb) x (1L)
(180 g mol-1) x (0-1 L)
1
...(it)
(10-2g) x (180g mol-1) x (0-1L) (lL)(2g)

= 91-8 g mol-1 Molar mass of glycerine =
91-8 g mol-1.
w
...(H)
Concentration of solute = 28-5 g /100 mL or 28-5%

OEXAMPLE 3.60. What is the molar concentration of solute particles in human blood if the
osmotic pressure is 7-2 atm at normal body temperature of 37C ?
(A.I.S.B. 1999 Supp.)
Solution :
ft = CRT
or
RT
7i = 7-2 atm,
R = 0-0821 L atm K"1 mol"1,
T = 37C = 37 + 273 = 310K
______________(7-2atm)_____________
Molar concentration (C) (o.0821L atm K-1 mol-1) x (310K)
= 0-283 mol L- = 0-283 M.
3 EXAMPLE 3.61 .A beaker containing 0010 mol of C}2 H22 OilIN 1000 g of water and a beaker
containing 0 020 mol of C12H220ll in 100-0 g of water are placed in a chamber and allowed to equilibrate.
What is the concentration of C I 2H220I I in the resulting solution ? (Ticklish Problem)
Solution : Since the two solutions have initially different concentrations, water vapours will be
transferred from dilute solution to the concentrated solution till the two solutions acquire same mole
fraction of sucrose and are in a state of equilibrium.
Let the no. of moles of H2O transferred = N mol.
Solutions
3.70
3.71
Solutions
3.14. ABNORMAL MOLECULAR MASSES
At the equilibrium, the mole fractions of sucrose in the two solutions are the same and are represented
as : We have studied in detail all the four colligative properties associated with ideal and dilute solutions
and have obtained an expression in each case for the molecular mass of the solute. We have also seen that
mol) proportional to the molecular mass
(0-of020mol)
the colligative property (0-010
is inversely
the solute. Accurate values of
(0 010 mol
+ lOOg
moF1) - n(H
(0-020
+ lOOg / 18g and
mol'1donot
) + nHundergo
the molecular
masses
can/ 18g
be obtained
provided
the solutes
aremol
non-electrolytes
either
20)
20
dissociation or association in solution. But in many cases, the solutes are electrolytes I.E., acids, bases
(0-010 mol)
(0- 020 they
mol) are likely to undergo either dissociation or
and salts. When these are dissolved in solvents
(5-56mol)
- n(H2in
0) the number
(5-57mol)
+ nHparticles.
association leading
to change
of the
Since the colligative properties are
20
dependent
uponmol
the+number
of the
solute
particles,
these
are
also
likely
be affected.
Molecular masses
or 0-0557
(0-010 mol)
N (H
O)
=
0-1112
mol
(0
020
mol)
nH20to0-030
N
z
of the solutes which are inversely proportional to the colligative properties must have different values
(H20) =these
(0-1112
0-0557) mol
0-0555and
mol.are also called observed
from their normal values. In other words,
are- abnormal
in =nature
molecular masses. Let us briefly study some examples of association and dissociation.
Association of Solute Particles
_ (0-0555 mol)
1-85 mol
In certain solvents (generally non-polar)
the particles of the solute undergo association I.E., two
(0-030)
or more molecules of a solute combine to form a bigger molecule. As a result, the total number of
Concentration of sucrose in resulting solution.
NA
(A)
(O-OlOmol)
0-010
(Single molecules)
(Associated molecule)
= 0 00269
solute molecules in the solution will decrease.
The
colligative
properties
(5-56mol) - (l-85mol)
3-71 are expected to decrease
while the molecular masses of the solutes involved are expected to increase. It is quite expected also
< stated above, varies inversely as the colligative property.
since the molecular mass, as
2~ôr jf^ractice
For example, in benzene solvent, both acetic acid and benzoic acid exist as dimers because of the
presence of intermolecular hydrogen bonding
3.5 Osmotic pressure of blood is 8-21 atm at 37C. How much glucose should be used per litre for an
2CH3COOH
-----that
- -^ is(CH
2C6H?5COOH -------------- -(Pb.
-^ (C
3COOH)
6H5COOH)
2
intravenous
injection
isotonic
with2 ;blood
Board
1999) [Ans.
58-068g]
ProLL
How much glucose, QHÔg must be dissolved per litre of the solution that yields osmotic pressure of
C6H5
2- 72 atmospheres at 298 K ? R = 0-0821 L atm K" 1 mol"1.
[Ans. 20-0116 g]
,0 = C-(X
. 3-0g of non-volatile solute when dissolved in 1 litre water, shows as osmotic pressure of 2 atmosphere at
CH3
H litre atm K" 1 mol"
,H 1). (H.P. Board 1996)
300 K. Calculate the molecular
mass of the solute. (R = 0-082
I
y
\o-c=o
[Ans. 36-9 g mol"1]
.o=c-o\
I
3.60. The osmotic pressure
containing 1 -0g protein in 200 mL of aqueous solution at 27C has been
H of a solution ,H
C6H5
1
found to be 2-0 \x 10"
atm. Calculate the molecular mass of protein.
(R = 0-082 L atm mol" 1 K"1).
0-C=0'
Benzoic acid
(A.I.S.B.
1990) [Ans. 615-7 g mol"1]
I of acetic acid is 60 amu. and its observed molecular
The normal molecular mass
mass is expected
CH
Osmotic
a solution
containingundergo
2g dissolved
protein per
cm 3 of solution
is 20
of Hg
to be 120
amu pressure
in caseofall
the3 molecules
association
in 300
benzene.
Similarly,
themmnormal
Acetic
molecularat mass of benzoic
acidacid
is 122 amu. and its observed molecular
mass
must
be
244
amu.
in
27C. Calculate the molecular mass of protein. (R = 0 0821 L atm K" 1 mol"1).
case of complete association. However, in most of the cases the association is not hundred percent or1
6238-6 g mol" ]
complete which means that all the molecules of both the solutes mentioned(D.S.B.
above 1992)
donot[Ans.
get associated.
3.62. Osmotic pressure of a solution containing 7g of a protein per 100 mL of solution is 25 mm Hg at 310 K.
Dissociation of Solute Particles
Calculate the molecular mass of the protein. (R = 0-0821 L atm K" 1 mol"1),
Solute particles in case of electrolytes are expected to undergo dissociation
in1993)
polar[Ans.
solvents
like
(A.I.S.B.
54159-3]
water as follows
3.63
10g of an: organic compound is dissolved per litre of the solution and gave an osmotic pressure of 1*18
atmosphere at 273 K. Calculate
mass of the compound.
AB - -- -the
-A+molecular
+ B'
(Pb. Board 1994 Supp.) [Ans. 189-94 g mol"1]
As a result, the number of the ions (or particles) formed will increase. The colligative properties
3.64
A 5%
of sucrose
(Ci2Hand
isotonic with
0-877%masses
solution
urea.
Calculate
the molecular
220n)
in turn,
are solution
also likely
to increase
theisobserved
molecular
ofofthe
solute
must decrease
mass of urea (Atomic mass C = 12, H = 1 , 0 = 16).
(Pb. Board 1996 Supp.) [Ans. 59-99]
3.65. What is the volume of a solution containing lg mole of sugar that will give rise to osmotic pressure of
1 atmosphere at 0C ?
(A.I.S.B. 1998 Supp.) [Ans. 22-4L]
3.66. Find the osmotic pressure of M/20 solution of urea at 27C (R = 0-0821 L atm K" 1 mol"1).
[Ans. 1-2315 atm]
* 3.72
Solutions
The value of t predicts the nature of the solute in solution.

accordingly. For example, sodium chloride (NaCl) undergoes dissociation in aqueous solution to form Na +
and Cl" ions.
NaCl 7=^ Na+ + C1
Thus, we conclude that abnormal values of the molecular masses are expected if the solutes undergo
change in number of the particles in solvent either because of association or dissociation.
Van't Hoff Factor (i)
Vant Hoff has introduced a factor known as Vant Hoff Factor, denoted as I to predict the nature of a
particular solute in the solution. It is in fact, the ratio of the experimentally determined value of colligative
property (observed colligative property) and the normal value as predicted when the solute behaves ideally
in the solution without undergoing any dissociation or association. Thus,
. _ Observed colligative property
Normal colligative property
Vant Hoff factor can also be expressed in terms of molecular masses as follows :
. Normal molecular mass
f =---------------------------------Observed molecular mass
Colligative property is always inversely proportional to molecular mass.
If i => 1, solute behaves normally in solution.

If i > 1, solute undergoes dissociation in solution.
If i < 1, solute undergoes association in solution.
The mathematical expressions for the colligative properties are also modified in case association
or dissociation is to be considered.
Elevation in boiling point (ATt) = i Kbm
Depression in freezing point (ATy) = iKfn
Osmotic pressure (tt) = /CRT
Relation between
Electrolytes in solutions.
Van't
Hoff
Factor
and
Extent
of
Association
or
Dissociation
of
the
We have discussed that some electrolytes undergo association or dissociation in solutions. However,
it is not complete in most of the cases. This depends upon the nature of the electrolyte and also some
other factors governing its dissolution. The extent is also represented as degree and is denoted as a.
It may be defined as :
the fraction of the electrolyte undergoing association or dissociation in solution.
No. of moles of the electrolyte associated
Total no. of moles of the electrolyte
No. of moles of the electrolyte dissociated
Total no . of moles of the electrolyte
Vant Hoff factor (i) both in association and dissociation.
Degree of association
Degree of dissociation Let us
try to co-relate a and
3.73
Solutions
Relation between a and i in Association
Let us suppose that n molecules of the electrolyte A get associated to form bigger molecule (A)
nA v. s (A)
I.E.
Let A be the degree of association of the electrolyte.

If we start with 1 mole of the electrolyte A, then
No. of associated moles = a IN
No. of unassociated moles = (1 - a)
Total no. of moles after association = (1 - a + a IN)
(I.E. observed no. of moles)
No. of moles of electrolyte after association_________
I
No. of moles of electrolyte without considering any association

(1 - a + a IN)
1
or i -l = a (1/n - 1)
I-1
1 / N- 1
(For association)
Relation between a and i in Dissociation
Let us suppose one molecule of the electrolyte dissociates to give N ions in solution. If we start
with one mole of the electrolyte and a is the degree of dissociation of the electrolyte, then
No. of moles of the ions formed = na
No. of moles of the electrolyte undissociated = 1- a
Total no. of moles after dissociation = 1 - a + na
(I.E. observed no. of moles)
I
No. of moles of the electrolyte after dissociation_______
No. of moles of electrolyte without considering any dissociation

I
1 - a + na
=
1
or i - 1 = a (n - 1)
- 1 n
-1
I
(For dissociation)
Note. The value of Vant Hoff factor (/) is the ratio of the normal molecular mass and observed
molecular mass and can be easily calculated. By knowing the value of n in association or dissociation a can
be calculated.
ools for Numerical Problems

Van't Hoff factor (0 =
Observed colligative property _ Normal molar mass

Normal colligative property Observed molar mass
Solutions
3.74
Solutions
3.75
SEXAMPLE 3.64. Solution A contains 6g of urea in 100 inL of it at 27C while solution B has 6g of acetic
In associatioh/riissociation :
acid in 100 mL of the solution at the same temperature. Are the two solutions equimolar as well as isotonic ?
ATft = /K^m; ATy = /Kym; N = /CRT.
(Ticklish Problem)
Solution. Comparing the molarities iof- the
two
solutions.
I
(For association) :
a ,=XMX Mass of urea / Molar mass of urea
X. ,
1
I
N-1
Molarity (M) =---------------------------------------------For solution A
(For dissociation) :
a= /-1
n-1
(egmeogmor1)
- ----------oTE----------= 1 mol L 1 = 1 M
I SAMPLE 3 62. Assuming complete dissociation, calculate the expected freezing point of a
Mass of acetic
Molar
of 0-1
acetickgacid
solution prepared by dissolving 6 0g of Glauber's
salt.acid
Na 2/S0
of water. (Given
4,10Hmass
2O in
Molarity
(M)
=
For
solution
B
1
value of Kf 186 K kg mol' ).
(D.S.B. 1998)
Solution : Na2S04 .IOH2O dissociates in aqueous solution1 as :
_ (6g) / (60 g moF )
= 1 mol L -i _ 1 M
Na2S04 .IOKJO------- 2Na+ + S0420-1
' + (10H
L 2O)
2 +1
. ..and
.... B
- are EQUIMOLAR
... No. of
Solution A
. particles after dissociation
Van t Hoff factor (1) =--------------------------------------------1
Comparing the osmotic pressures ofNo.
the of
twoparticles
solutions.
originally present
(IOH
O molecules
are not consideredN as
these are the
part
of the solvent)
FOR JSOLUTION
A *.
= i'CRT=lx(l
mol
L~')x(0-0821
L atm K"1 mol_1)x300 K
ATy = i x K y x m = r xwKn y x
= 24*63 atm.
FOR SOLUTION B : Acetic acid ionises in aqueous solution as :MB x WA

+
CH3COOH +
H20 W
----=-----(AQK
) +=H1*86
30 (AQ)
I = 3,
6 0 ^g,CH3COOW = 0-1 kg,
K kg mol"1
B
In this case,
Hoff
factor
> 1X 23) + 32 + (4 x 16) + (10 x 18) = 322 g mol'1
MVant
(Na S0
.10H
O) (=I) (2
B
n = /CRT > 24-63 atm.

3 x (1 86K kg mol"1) x (6g) = 1-04K 1
Since the two solutions have different osmotic pressures, these are NOT ISOTONIC.
(322gmol
)x(O-lkg)
SEXAMPLE 3.65 The freezing point of
a solution
containing 0 3g of acetic acid in 30g of benzene is lowered
Freezing point ofbysolution
(TY) = TYVan't
- ATy
273K -(Kffor
104K benzene
= 271-96K.
0 45. Calculate
Hoff= factor.
= 512 K kg mol'1) (A.I.S.B. 2001)
Solution : STEP 1. Calculation
of observed
molar
masschloride
of aceticwhich
acid (CH
Calculate the
amount of
sodium
must3COOH).
be added to one kilogram of
water so that the freezing point of the solution
is
depressed
by
3K.
(Given
value
of Kf = 1-86K kg mol'1).
K F x WB
(A.I.S.B. 1997)
Solution : Sodium chlorideM (NaCl) dissociates as :
B AJ
fXW
NaCl
----->ANa+ + Cl'
WB = 0-3g, WA = 30-0g, = 0-03 kg AT/ = 0 45 = 0-45K K/ = 5=
Vant Hoff:
l
12K
kgmol
factor (/)
- N
of particles
after dissociation _ 1 + 1 _ J
No. of particles originally present

(5-12K kgmor1) x (0-3g)
= 113-8 g mol1
MB = ATy x MB x WA
(0-45K) x (0-03 kg)
WR =
x K,
Step II. CALCULATION OF VAN'T HOFF FACTOR Normal molar mass of CH3COOH
i = 2, WA
=12 + 3x1 + 12 + 2 x 1 6 + 1
= 12= +13 +kg,

12ATy
+ 32 +=13K,
= 60Ky
g mol-1
1
= 1-86 K kg mol'
MB
-1
-1
Normal
molar
,,
_ (3K)
x (58-5g
molmass
) x _(1(60-0
kg) g mol ) _
WB
-1
-1
~
2 x (113-8
(1-86Kg kg
mol
) =
mol
)
Observed
47-2molar
g.
Solutions
DFXAMPLE 3.66. A solution contains 0-8960g of K2S04 in 500 mL. Its osmotic pressure is found to be 069 atm at 27C. Calculate the value of Van't Hoff factor,
(A.I.S.B. 2001)
SOLUTION : STEP I. Calculation of observed molar mass of K2S04
WB x R x T
Mr nxV
WB = 0-8960g, V =
500
1000 = 0-5L, T = 27C = 300K

1
R = 0 0821 L atm K* mol*1, N = 0-69 atm.

(0-8960g)x (0 0821 LatmK~1mol~1) x (300K)
(0-69atm) x (0-5L)
STEP II. Calculation of Van't Hoff factor
Normal molar mass of K2S04 = 2x 39 + 32 + 4 x 1 6
= 7 8 + 3 2 + 6 4 & 1 7 4 g m o l *1
=
MB
Vant Hoff factor O') =
Normal molar mass _

Observed molar mass
(174 g mol )
(63-97 g mol-1)
= 2>
=63-97g mol*1
72.
3 EXAMPLE 3.67. An aqueous solution containing 1-248 g of barium chloride (molar mass =
208-34 g mol~') in 100 g of water boils at 100-0832C. Calculate degree of dissociation of barium
chloride (Kbfor water - 0-52 K kg mol~1).
(A.I.S.B. 2003)
SOLUTION : STEP I. Calculation of observed molar mass of barium chloride.
MB =
or
_ K, x WB
AT, x WA
WB = 1 -248g ; WA = 100 g = 0-1 kg ; AT* = 0-0832C

0 0832 K ; K, = 0 52 K kg mol*1
MB
- (0 - 52 K kg mol"1) x (1 248 g)
(0 0832 K) x (01 kg) -788mo1'
STEP II. Calculation of Vant Hoff factor

Normal molar mass (208-34 g mol-1)
j = ---------------------------- = ----------s--------L = 2 - 6 7
Observed molar mass (78 0 g mol-1)
Step III. CALCULATION OF DEGREE OF DISSOCIATION Barium chloride in solution dissociates are :
(aq) S
BaCl2 ^---------Ba2+ (AQ) + 2C\~(AQ)
Value of N = 3, I = 2-67
Degree of dissociation (a) - ^
(i-'l)
(2-67-1)
1-67
^
^--------- = 0-825
Degree of dissociation of barium chloride is 0-835 or its percentage dissociation = 0-835 x 100
= 83-5%
Solutions
= 104 g
OEXAMPLE 3.68. Calculate the boiling point of one molar aqueous solution (density
mL'1) of potassium chloride (K f , 0-52 K kg mol'~I).
(A.I.S. B. 1995)
SOLUTION : STEP I. Calculation of molality of the solution.
1 molar solution means that 1 gram mole of KC1 is dissolved in one litre of solution.
Mass of 1L of solution = V x D - (1000 mL) x (104 g mL"1) = 1040g
Mass of KC1 (one mole) = 39 + 35-5 = 74-5g
Mass of solvent (water) = 1040 - 74-5 = 965-5g = 0-9655 kg
No. of moles of solute
Molality of solution (m) =
(lmoi) 1- 0357 mol kg 1 = 1-0357 m.
(0-9655 kg)
Step II. CALCULATION OF ELEVATION IN BOILING POINT (ATB) KC1 dissociates in aqueous solution as :
(aq)
KC1 (s) -----> K+ (AQ) + Cl' (AQ)

No. of particles after dissociation 2 Van t Hoff tactor (/) No.of
particles originally present i
Kfe = 0-52 K kg mol"1, M = 1 -0357 mol kg"1, I = 2 AT6 = f x Kft x M = (2) x
(0-52 K kg mol"1) x (1 0357 mol kg'1) = 1-078 K.
ST< Calculation of boiling point of solution.

Boiling point of solution (T*,) = TB + ATfc = 373K + 1 078K = 374-078K.
OK\AMPLE 3.69. 17-4% K2SO J solution at 27C is isotonic with 4% NaOH solution at the same temperature.
If NaOH is 100% ionised, what is the degree of ionisation of K2S04 in aqueous solution ?
(Ticklish Problem)
SOLUTION : STEP I. Calculation of molar concentration of both the solution.
...
. F KIrm
Mass of NaOH / Molar mass
Molar concentration of NaOH solution = -------------------------------------
_ (4g) / (40g mol'1)
(0-1 L)
= 1-0 mol L'1 = 10 M
Mass of K2S04 / Moiar mass Molar concentration of K2S04 solution - Vo!
ume of solution in litres
(17-4g)/(174gmor1)
(0-1 L)
= 1-0 mol L'1 = 1*0 M
3.78
Solutions
Calculation of Van 7 Hoff factor (i) for K2S04.

Since the two solutions are isotonic, they have same osmotic pressure.
For NaOH : a = 1, N 7 I - 1 / - 1
.'. a =-------------- or 1 = 7 or I = 2 ; C = 1M
n- 1
2-1
=
JlNaOH iCRT = 2 X (1M) X R X T
For K2SO4 : C = 1 M ; / = ? (to be calculated)
n
K2S04 (CRT = j'(l) x R x T
As the two solutions are isotonic,
TTNAOH
= 71
K2SO4 OR
2xRxT = ixRxT
OR T
=2
STEP III. Calculation of degree of ionisation of K2SO4.

For K2S04 ; a = -^7 =
= | = 0-5
1 3-1
2
,\ The degree of ionisation of K2S04 = 0-5 or its percentage ionisation = 0-5 x 100 = 50%.
EXAMPLE 3.70. 2-0 g of benzoic acid dissolved in 25 0 g of benzene shows a depression in freezing
point equal to 1-62 K. Molal depression of constant (Kf for benzene is 4-9 K kg mol' 1. What is the
percentage association of the acid ?
(Roorkee 1990)
SOLUTION :
Calculation of observed molar mass of benzoic acid
N
K/ x WB
= WA x ATF
WB = 2-0g, WA = 0-025 kg, KF = 4-9 K kg mol-', AT/ = 1 62 K
MB
= (4-9Kkgmor1) x ( 2 0 g )
B
(0-025 kg)x (1-62K)
=
g
Calculation of Van 7 Hoff factor (I)

Normal molar mass of C6H5COOH = 6 x 1 2 + 5 x 1 + 1 2 + 2 x 1 6 + 1
= 72 + 5 + 12 + 32 + 1 = 122g mol"1
Normal molar mass
(122 e mol"1)
_______
Vant Hoff factor (1) - 7-----------7:---;---------- =
-------T- = 0 -504
w
Observed molar mass
(242 g mol )
STEP I! Calculation of percentage association of acid (a)
Benzoic acid associates in benzene as :
2C6H5COOH (C6HSCOOH)2
Value of 71 = 2
1 - 1 = 0-504 - 1 _ (-0-496)
1/n - 1
1 / 2 - 1 ~ (-0-50)
.-. Percentage association of acid = 0-992 x 100 = 99-2%.
=
0-992
* 3.79
Solutions
CPXAMPLE 3.71. Three particles of a solute A, associate in benzene to form species (A) J. Calculate the
freezing point of 0-25 rnolal solution. The degree of association of solute 'A' is found to be 0-80. The freezing
point of benzene is 55 C and its cryoscopic constant is 512 K m~*.
SOLUTION :
Calculation of Van't Hofffactor (i)
Since three particles of solute A associate to form (A)3
Value of N = 3, a = 0 8
i-1
_ I- 1
~l/-l or 08
(1/3-1)
Calculation of depression in freezing point (AT})
a
ATy = i
I
or 1
0-467
x Kj-xm
= 0-467, KF = 5-12 km'1, M = 0-25 rnolal ATY = (0-467) x
(5-12 km'1) x (0-25m) = 0-6K = 0:6C -'Hi) 5 CALCULATION OF FREEZING POINT OF SOLUTION
Freezing point of solution (TY) = TY - ATY = 5-5C - 0-6C = 4*9C.
Jftrob &FVI5 fôr jf^ractice
Decinormal solution of NaCI developed an osmotic pressure of 4-6 atmospheres at 300K. Calculate the degree
of dissociation.
(Pb. Board 1994) [Ans. 87 %]
3. How many grams of KCI should be added to 1 -0 kg of water to lower its freezing point to - 8C.
-1
(Ky for water = 1-86 K kg mol )
(A.l.S.B. 1996 Supp.) [Ans. 162-2g]
3.60 The freezing point of a solution containing 0-2g of acetic acid in 20-0g of benzene is lowered by 0-45C.
Calculate the degree of association of acetic acid in benzene. (Ky for benzene = 5-12 K kg mol* 1).
(Roorkee 1994) [ANS. 94-6%)
* 3 70. A solution containing 3- lg of BaCl 2 in 250g of water boils at lOO-OSS'C. Calculate the ratio of the Vant Hoff
factor and molality of BaClj in this solution. (K ft for water = 0-52 K nr*. Molar mass of BaCl 2 = 208-3g
mol'1).
(A.l.S.B. 2001) [Ans. 45:1] _
3.7 . A solution containing 7-45g of KCI per litre of solution has an osmotic pressure of 4-68 atm at 300K.
Calculate the degree of dissociation of KCI in solution.
(D.S.B. 2000 Supp.) [Ans. 90%]
Calculate the osmotic pressure of potassium ferrocyanide solution whose 01M aqueous solution dissociates
at 45% at 298K.
(Pb. Board 1999) [Ans. 6-85 atm]
Osmotic pressure of a 0-0103 molar solution of an electrolyte was found to be 0-70 atm at 27C. Calculate
Vant Hoff factor.
(A.l.S.B. 2003) [Ans. 3]
The freezing point depression of 0 1 m NaCI solution is 0-372 C. What conclusion would you draw about the
state of its formula ? (Ky for water = 1-86 K kg mol"1).
(A.l.S.B. 2003)
[Ans. a = 1, % dissociation = 100]
The freezing point depression of 0-1 rnolal solution of benzoic acid in benzene is 0-256 K. For benzene
Ky is 5-12 K kg mol'1. Calculate the value of Vant Hoff factor for benzoic acid in benzene. What conclusion
can you draw about the molecular state of benzoic acid in benzene ? (C.B.S.E. Foreign 2003)
[Ans. Benzoic acid is a dimer in benzene]
3.81
Solutions
3.80
Solutions
PROBLEM 3 2 g of urea when dissolved in 200 g of certain solvent decreases the freezing
point by 0*2C. 3*2 g of an unknown substance when dissolved in 160 g of same solvent depresses the
freezing point by 0*36C. Calculate the molar mass of unknown substance.
Problems with Solutions
K , x WB
Solution.
PROBLEM 1
MB
AT, x WA
At 40C, the average osmotic pressure of blood is 8-8 atm. Find the
of K, will of
remain
the sameconstituents
as the solventinis the
the same.
total Value
concentration
the various
blood. Assuming that the concentration is the
1
sameFor
as the
find
the freezing
solution.
water = 1 86, K Kg mol'1)
Ureamolality,
: MB = 60
g mol"
; WB = 2point
g : WofA =the
200
g = 0 2 (Kyfor
kg
SOLUTION. Step I. Calculation of
concentration
of K
the solution
AT,
= 0-2C = 0-2
ACCORDING TO VANT HOFF EQUATION.
K, x (2g)
)
(60 g mol"1) x (0
=(0-2K)
CRT or
C 2kg)
=
WB = 3-2 g; WA = 160RT
g = 0-16 kg
For Unknown Substance
it = 8-8 atm, T = 40C = 40+ 273 = 313 K,
AT, = 0-36C = 0-36 K 1
R = 0 0821 litre-atm K' mol"1.
K,
x (3- 2g)
(8-8atm)
(H)
Ma =
C = (0-36K) x (0-16kg)
1
(0.0821 L - atm K^moP ) x (313 K)
Divide eqn. (II) by eqn, (I)
= 0-34 mol L' (M)
K, x (3*2g)
. (0-2K) x (0-2 kg) _ j n
M
F
Step II. Calculation of freezing
point of the solution
(0-36K)
x
(0-16kg)
*
K,x
(2
g)
-1
mol )
DEPRESSION IN FREEZING(60g
POINT OF SOLUTION (ATy) =
MB - 111 x (60 mol'1) = 66*67 g mol'
Ky
Xm
PROBLEM 4. Ethylene glycol is used as 1antifreeze. What relative proportions of ethylene
M =0-34 mol kg' (same as molarity as given)
glycol and water (by weight) should be mixed to form
an antifreeze solution that will not start
1
KY =
1 -86 (K,for
K kg mol'
freezing until the temperature reaches
- 37C
water = 1*86 kg mol"1) ?
1
1
ATtheory
Y = (1-86 K kg mol' ) x (0 34 mol kg' ) = 0-63 K = 0-63C
Solution. According to vant Hoff
of dilute solution
Freezing point of solution = 0 - (0-63C) = - 0-63C
PROBI
When 18 g of a solute having empirical
AT, formula CH20 is dissolved in 300 g
of water, the solution freezes at -AT,
0-93C.
What
is
the
molecular formula of the solute ? (K<- for
= iK, M or m
iK f
water = 1-86 K kg mol-1)
SOLUTION Step l.Calculation of molar mass of the solute.
Since ethylene glycol (HOCH2CH2OH) is a covalent compound, the value of vant Hoff
factor I' - 1.
_ *V
AT, = 0 - (- 37C) = 37C = 37MKB =; K,
= 1*86 K kg mol'1
ATy X WA
37 K
WB * 18 g ; WA = 300 g M= =0-3 kg ; ATy =-^y0 =-20mol
(- 0-93C)
=
kg'*
1 x 1-86K kg mol
0-93C = 0-93 K.
This value of M shows that 20 moles
ethylene
KY =of1-86
K kg glycol
mol'1 are dissolved per 1000 g (kg) of water.
1
(1-86K
kg
mol
*) x (18g)
Molar mass of HOH2CCH2OH
= = 62 g mol'
= 120g mol
(0-93K)
x
1(0*3 kg)
Mass of 20 moles of HO-CH2-CH2-OH * (62 g mol" ) x (20 mol) = 1240 g.
Step
Calculation
of the molecular
formulaglycol
of the and
solute.
TheII.relative
proportions
in which ethylene
water must be mixed
1
Empirical formula mass of solute (CH20)

= 12 +: 1000
2x 1 += 16
= 30
g
= 1240
1*24
: 1*00.
Molecular mass of solute 120 g mol'1 = 120 g
n~
Molecular mass of solute _ (120 g) _ Empirical

formula mass of solute (30 g)
Molecular formula of solute = 4 (CH20) = C4H804
3.82
Solutions
How many mL of 0-05 M KMnOj solution is required to oxidise 2-0 g of FeS04 in

the presence of dilute sulphuric acid.
~'>luti Step I. CALCULATION OF THE AMOUNT OF KMN04 REQUIRED The
redox reaction involved is as follows :
10FeSO4 + 2KMn04 + 8H2S04 ----------> K2S04 + 2MnS04 + 5Fe2(S04)3 + 8H20
lOx 152 g 2xl58g
10 x 152g of FeS04 react with KMn04 = 2 x 158g
1
0 g of FeS04 will react with KMn04 = ^ x 8) x (2-0 g) = 0-416 g

(10 x 152 g)
STEP II. Calculation of the volume of the KMn04 solution.
Molarity (M) of the solution is given as :
Molarity (M) =
(0-05 mol L'1) =

Mass of KMn04
Molar mass of KMn04
Volume of solution
(0-416 g)
(158 g moL1)
Volume of solution
0-416g
(158 g mol1) x (0-05 mol L)
= 0-527 L = 52-7 mL
PROltt
Calculate the vapour pressure of a 0-1 M urea solution at 298 K. The
vapour pressure of pure water at 298 K is 20 mm of Hg.
Solutioi 0-1 M urea solution contains 0-1 mole of the urea in 1000 mL of solution.
Mass of 1000 mL urea solution = V x D
= (1000 mL) x (lg mL1) = 1000 g
Mass of 0-1 mole of urea = (01 mol) x (60 g mol-1) = 6g
Mass of water = 1000 g - 6g = 994 g
(994 g)
Moles of water (nA) ~ (18gmo|-i) = 55-22 mol
(55-22 mol)
Mole fraction of water (,A) - (55.22mol + O.lmol) = 0 998
Vapour pressure of solution (P) = PAxA = (200 mm) x (0-998) = 199-6 mm Hg.
PROBLEM 7. The density of 2-0 M acetic acid solution is 1-02 g/mL. Calculate the molality of the
solution.
Solution.
Volume of solution = 1000 mL
3.83
Solutions
Density of solution = 1-02 g/mL

Mass of solution = Volume x Density = (1000 mL x 102 g/mL) = 1020 g Mass of
acetic acid = 2 x 60 = 120 g.
Mass of solvent (water) = (1020 g - 120 g) = 900 g
(Massofaceticacid/Molarmass)
120x 1000
(120g)/(60gmol )
(900/1000 kg)
(mol kg'1) = 2-22 mol kg'* = 2-22 m
60 x 900
PROBLEM 8. 0-5 g of a sample of an oxalate was dissolved in water and the solution was made
uptolOO mL. On titration, 10 mL of this solution required 15 mL of acidified N/20 KMn0 solution.
Calculate the percentage of the oxalate ions in the sample.
Solution. Step 1. Calculation of amount of oxalate ions in the sample.
Volume of KMn04 solution (V|) = 15 0 mL
Normality of KMn04 solution (N]) = N/20
Volume of oxalate solution (V2) = 10 0 mL
The normality (N2) of oxalate solution can be calculated with the help of normality equation :
NtV, * N2V2
4
(KMn04) (Oxalate)
x (15 0 mL) = N2 x (10 0 mL)

(15 mL)
20 x (10 mL) 40
Strength of oxalate ions per litre of the solution
= Normality X Equivalent mass of oxalate ions
N, =
Eq. mass of C204 - 88

2
3
88
X
~ 40 2 =
3-3 g/L
Amount of oxalate ions per 100 mL of the solution =
33
x 100 = 0-33 g
luUu
STEP II. CALCULATION OF THE PERCENTAGE OF OXALATE IONS IN THE SAMPLE

Amount of the sample = 0-5 g
Amount of the oxalate ions = 0-33 g
Amount of oxalate ions
Percentage of the oxalate ions =
Amount of sample
0-33
x 100 = 66%
0-50
x 100
3.84
Solutions
ADDITIONAL ûiy,ER'cA^
PROEMS (OR PRACTICE
1 A bottle of commerical sulphuric acid (density = 1-787 g mL'1) is labelled as 86 per cent by mass.
(i) What is the molarity of the acid ?
(ii) What volume of the acid has 1o be used make 1 litre of 0-2 M H2S04 ?
2.
[Ans. (i) 15-7 M (ii) 12-7 mL]

How will you prepare 1 0 kg of an aqueous solution of acetone (CH3COCH3) in water in which mole
fraction of acetone is 0 19 ?
[Ans. Mass of acetone = 431 g ; Mass of water = 569 g]
3.
One litre of an aqueous solution contains 15g of the solute of molar mass 150 g mol-1. If the density
of solution is 1 -OOSg/mL, calculate the mole fraction of the solute.
[Ans. 0-00181]
4.
100 cm3 of an aqueous solution of BaCI2.2H20 is found to contain 6-022 x 1022 Cl'1 ions. Calculate
the molarity of the solution.
[Ans. 0-5 M]
5.
What volume of 95% sulphuric acid (density = 1 -85 g mL -1) and what mass of water must be taken to
prepare 100 mL of 15% solution of sulphuric acid (density = 1 -1 g mL'1) ? [Ans. 9 37 mL ; 92-67 g]
6.
A non-volatile hydrocarbon has 5-6% hydrogen. When 3g of the hydrocarbon is dissolved in 100 g of
benzene, the relative lowering in vapour pressure is 1-306 x 10'2. Determine the molecular formula of the
non-volatile hydrocarbon (Molecular mass of benzene is 78 a.m.u.)
[Ans. C,4H10]
7.
The vapour pressure of pure water at 25C is 23-62 mm. What will be the vapour pressure of a
solution of 1 -5 g of urea in 50 g of water ?
[Ans. 23-41 mm]
8.
Two liquids A and B are miscible over the whole range of composition and may be treated as ideal. At
350 K, the vapour pressure of pure liquid A is 24 0 kPa and that of pure liquid B is 12-0 kPa. A mixture of
60% of A and 40% of B is distilled at this temperature. What is the pressure in a close container from
which air is excluded ? A small amount of distillate is collected and redistilled at the same temperature.
What is the composition of the second distillate ? [Ans. 19-2 kPa ; 85-7% of A]
9.
The vapour pressure of a solution of 5g of acetic acid in 100 g of water at 25C was 23-40 torr and of
the same mass of acetic acid in 100 g of benzene was 70 torr. Assuming acetic acid to be non volatile,
find out its physical state in the two solutions. Give PH2O = 23-756 and PC6H6 = 72-5 torr at 25C.
[Ans. Monomer in water and Dimer in benzene]

10. How much ethyl alcohol must be added to 1 -0 litre of water so that the solution may freeze at - 10C.
(K,for water = 1-86 K kg mol-1, density of water = 1 g mL-1).
[Ans. 247-3
g]
11. The normal boiling point of water is 100C at 760 mm pressure and the heat of vaporisation is 40-7 kJ
mol'1. Find out the vapour pressure of water at 85C.
[Ans. 438-52 mm]
12. The elevation in boiling point of a solution of non-electrolyte in CCI 4 is 0-60. What is the depression in
freezing point for the same solution ? Kf(CC!4) = 30 K kg mol'1 ; K^CCU) = 5-02 K kg mol'1.
[Ans. 3-59 K]
13. A solution is prepared by dissolving 26-3 g of CdS04 in 1000g of water. The depression in freezing
point of the solution was found to be 0-284 K. Calculate Vant Hoff factor. The cryoscopic constant for
water is 1-86 K kg mol'1.(Given molar mass of CdS04 = 208 4g mol'1).
[Ans, 1-21]
Solutions
3.85
Solutions
5
A solution of glucose in water is labelled as 10 percent W/W. What would be molality
and mole fraction of each component in the solution ? If the density of the solution is
1 gets associated in water to form double molecules. 0-6677 g of phenol dissolved in 35-5
14 Phenol
5OH)
1*2(Cg6H
mL'
, then what should be the molarity of the solution ?
g of water depresses the freezing point of water by 0-215. (K,for water = 1-86 K kg'1 mol-1). Calculate
Ans.
Step I. Calculation of molality of solution.
(i) Observed molar mass of phenol
Mass of glucose in solution = 10 g
(ii) Degree of association of phenol.
[Ans. 162-47 g mol-1 ; 0-842]
solution
= 100
15. The osmotic pressureMass
of aofurea
solution
is g500 mm of Hg at 10C. The solution is diluted and its
of to
water
in solution
(100 that
- 10)the
= 90
g = 0 pressure
09 kg of the solution is reduced to 105temeprature isMass
raised
25C.
It is now =found
osmotic
3 mm.
Determine
extent(C
of6H
dilution
[Ans. 5 times]
Molar
mass ofthe
glucose
6 the
x 12solution.
+ 12 x 1 + 6 x 16 = 180 g mol'1
1206) =of
Molality of solution (M) = Mass of giucose ' MOJA-LSS of glucose

Text Book
Questions
with Answers
10g/(180gmol
*)
= 0-617 mol/kg = 0-617 m.

(0 09 kg)
Define the term solution. What kinds of solutions are possible ? Write briefly about each
Step II. Calculation of mole fraction of each component in solution.
type of solution with an example.
text-part.
>
NOconsult
. OF MOLES
OF GLUCOSE =
Ans. For answer,
Mass2.
of glucose
<18
g)
=
0-055
mol
Suppose a solid solution is formed between two substances, one whose particles are very large and the
Molar mass
(180 gparticles
mol
other whose
are very
small.=What type of solid solution is this likely to be ?
No. *)
of moles
of water
MassAns.
of glucose
The solution (90
likely
g) to be
= formed
50 mol is interstitial solution. For further details, consult text-part. 3.
-1
Define
Molar
mass the following
(18 gMole
molterms
) : of glucose =
fraction
(
I
)
Mole
fraction
(
II
) Molality fill) Molarity (IV) Mass percentage.
n
(0-055
mol)
cH12oFor
answer, consult
text-part.
6
Moleacid
fraction
of
=
n Concentrated nitric
Ans.
used
in water
the laboratory
work is 68% nitric acid by mass in 4. aqueous
"C6H,2O6 + H20
(0-055 mol) + (5-0
mol)
solution. What should be the molarity of such a sample of acid if the density of the solution is 1*504 g
1 - 0-01 = 0-99
mL"1 ?
OLUTION.
Mass of HN03 in solution = 68 g ^ns100 g
Molar mass of HNO3 = 63 g mol-1
1-2 g m L'1
Mass of solution = 100 g Density
Mass of solution
000 g)
ml
of
solution
= 1-504 g mL-1
-1
Density
(1 - 2 g mL ) O J J J 111 Li
St'X.'l'l
Mass of solution
Volume of solution - Density 0f solution
qoog)
(1-504 g mL-1)
= 66 -5 mL = 0 0665 L
Mass of HN03 / Molar mass of HNQ3

Volume of solution in Litres
(68g/63gmol )
(0-0665 L)
= 16-23 mol L-1 = 16-23 M.
3.87
Solutions
**#H666beK; S x-x-
Mass of Na2C03
(JC g)
Moles of Na2C03 = -----------1-----1 =
Molar mass (106 g mol )
106
Moles of NaHCC>3
Mass of NaHCO 3 .
Molar mass
(1 ~X)G
(84 g moP1)
= ~R^7 mol
1 - x 84
11101
According to available data :

Moles of Na2C03 = Moles of NaHCC>3
(T56 ") * (-1
-X
84 mol
106
84* = 106 - 106* or * = -y^- = 0-557g
or
Mass of Na2C03 in the mixture = 0-557 g

Mass of NaHC03 in the mixture = (1 - 0-557) = 0-443 g Step
II. CALCULATION OF TOTAL MASS OF HCL REQUIRED.
Na2C03(j) + 2HCl(a<7)------- 2NaCl(a?) + H20(/) + C02(g)
I06g
73g
NaHC03(s) + HCl(a^) --------> NaCl(a?) + H2O(0 + C02(g)

84g
0-01
36-5g
Now, 106g of Na2C03 require HCl = 73 g
(73g)x (0-557g) A
0-557g of Na2C03 require HCl =---------- (1Q6gj------------ = 0-384g
Similarly, 84g of NaHCQ3 require HCl = 36-5g

(36-5g) x (0-443g)
.
0-443g of NaHC03 require HCl =---------------- (g4g)------- = 0 - 192g
= 0 08333 L.
Total mass of HCl required
= (0-384
+ 0-192)
= 0-576g
Step
Mass
of glucose
/ Molar
mass of
glucose
Molarity of solution (M) =
III. CALCULATION OF VOLUME OF HCL REQUIRED.
6.
(10 g)/
Mass of HCl required = 0-576
g (180 g mol)
(0-08333 L) = 0-67 mol L'1 = 0-67 M
Molarity of HCl solution = 0-1 M
How many mL of a 0-1 M HC1 are required to react completely with lg mixture of Na CC>3
and NaHC0 containing equimolar amounts
of of
two
? / Molar mass of HCl
Mass
HCl
Molarity
of
solution
(M)
Step I. Calculation of mass of constituents in the Volume
mixture. of solution (V)
2
Mass of the mixture = 1-0 g Let (0-576

the mass
Na2C0
3 = jr g
g) of
/ (36-5
g/mol)
01 mol L"1 V
MassofNaHC03 = (1 jc)g
0-576 x 1000
= 01578 L
36-5 x 0-1
= 157-8 mL.
Solutions
**7- Calculate the percentage composition in terms of mass of a solution obtained by mixing 300 g of
a 25% and 400 g of a 40% solution by mass.
Ans.
Mass of one component (A) in solution

Mass of other component (B) in solution
(300 g)x 25
= 75g
100
(400g)x 40
= 160g
100
Mass of A
Mass per cent of component (A)
x 100
Mass of solution
(75g)
(235g)
x 100 = 32%
Mass of B
Mass of solution
Mass per cent of component (B) -
(160 g)
(235g)
100
X 100 - 68%
**x An antifreeze solution is prepared from 222-6 g of ethylene glycol CjHÔH^ and
200 g of water. Calculate the molality of the solution. If the density of the solution is
1- 072 g mL'1, then what shall be the molarity of the solution ?
Step I. Calculation of molality of the solution.
Mass of ethylene glycol = 222-6 g
Molar mass of ethylene glycol = 2 x 1 2 + 6 x 1 + 2 x 1 6 = 6 2 g mol-1
Mass of water = 2 0 0 g = 0 - 2 kg
Mass of ethylene glycol / Molar mass
Molality of solution (M) =
_ (222-6 g) / (62 g mol-1) 0-2
17-95 mol kg ,-t
kg
= 17-95 m.
STEP II. Calculation of the molarity of the solution.
Total mass of solution = Mass of solute + Mass of solvent
= 222-6 + 200 = 422-6 g
Density of solution = 1 072 gmL~1
Mass of solution
Density of solution
= 0-3942 L.
(422-6 g)
(1-072 grnL*1)
= 394-2 mL
3.89
Solutions
Mass of ethylene glycol / Molar mass

(222-6 g) / (62 g mol-1)

(0-3942 L)
9.
Ans.
9-10 mol Ll= 9*10 M.
A sample of drinking water was found to be severely contaminated with chloroform (CHCI 3)
supposed to be carcinogen. The level of contamination was 15 ppm (by mass).
(i)Express this in percent by mass.
(u)Determine the molality of chloroform in water sample.
(i) Percentage (%) by mass of CHCI3
= MASS f CHCl3 X 100 = (1-5 -^-e-- X 100 = 15 X 10~4 Mass of
solution
(10 g)
(ii) Molality of solution.
Mass of solute = 15 g Mass of solution = 106 g
Mass of water = (106 - 15) 106g.
Mass of CHCI3
15 g
m
Molality of solution (m) = --------Molar mass-----_ 019.._5 lL
Mass of water in kg (106/1000 kg)
= 1-25 x 10-4 mo! kg'1 = 1*25 x 10"* m What role
does the molecular interaction play in solution of alcohol in water ?
In case of alcohol as well as water the molecules are interlinked by intermolecular hydrogen
bonding. However, the hydrogen bonding is also present in the molecules of alcohol and water in
10. the solution but it is comparatively less than both alcohol and water. As a result, the magnitude of
Ans. attractive forces tends to decrease and the solution shows positive deviation from Raoults Law.
This will lead to increase in vapour pressure of the solution and also decrease in its boiling point.
Why do gases nearly always tend to be less soluble in liquids as the temperature is raised ?
The dissolution of a gas in a liquid is exothermic in nature because the gas contracts in volume.
Gas + Liquid ^ s Dissolved gas ; AH = - ve
Any increase in temperature will favour the reverse process since it is of endothermic nature.
11. Therefore, the solubility of the gas in solution decreases with the rise in temperature.
State Henrys law and mention some of its important applications.
For answer, consult text part.
The partial pressure of ethane over a saturated solution containing 6-56 x 10" g of ethane is 1
bar. If the solution contains 5*0 x 10' g of ethane, what shall be the partial pressure of the
gas ?
According to Henrys law,
12. The mass of the gas (M) dissolved in solution Partial pressure (/?) (At constant temperature)
2
Ans.
13.
Ans.
Solutions
(6'56 x 10 2 g) oc 1 bar
(5-0 x 10~2 g) <x P
=
or
( 5 - O x 10 g ) ^ ba _ 0.762 bar
(6-56 x 10~2g)
14.
What is meant by positive and negative deviations from Raoults law and how is the sign of AH S0|
related to positive and negative deviations from Raoults law ?
Ans. For answer, refer to text part.
15. An aqueous solution of 2 percent non-volatile solute exerts a pressure of 1-004 bar at the boiling
point of the solvent. What is the molecular mass of the solute ?
Ans. Solution is an ideal solution. According to Raoults Law
PA ~ Ps = xB = nB _
B
Pi
("A + B) "A MB *
_ W B x MA
W
PA (for water) 1-013 bar ; Ps = 1 -004 bar ; WB = 2g ; WB = 100 - 2 - 98 g ;

MA = 18g mol'1.
(1 013 - 1-004) bar = ( 2 g ) x (18 g mol'1)
1-013 bar
MBx(98g)
. . _ (2 g) x (lSgmor1) x (1-013 bar)
MB
(0-009 bar) x (98 g)
16.
A ns.
- 41-35 g mol
Heptane and octane form ideal solution. At 373 K, the vapour pressure of the two liquid components
are 105-2 k Pa and 46-8 k Pa respectively. What will be the vapour pressure in bar of a mixture of
25-0 g of heptane and 35-09 of octane ?
No. of moles of heptane (nB)

No. of moles of octane (nA)
Mole traction of heptane (jcB)
Mole fraction of octane (JCa)
Mass of heptane (C7H16) _

Gram molar mass
(25 g)
y 0-25 mol
(100 g mol )
Mass of octane (C8H18)

(35 g)
Gram molar mass (114 g mol-1)
= 0-307 mol
nB _ __________(0-25 mol)
= 0-449
(0-25 mol + 0-307 mol)
B + A
______(0-307 mol)
% + nA (0 25 mol + 0-307 mol)
- 0-551
Vapour pressure of pure heptane (P^) = 105-2 kPa Vapour pressure of pure octane (P^)
=46-8 kPa Partial vapour pressure of heptane (PB) = PB*B = (105-2 kPa x 0-449) = 47-23
kPa
Partial vapour pressure of octane (PA) = PA*A = (46-8 kPa x 0-551) = 25-79 kPa. Total
vapour pressure of solution (P) = PA + PB = (47-23 + 25-79) = 73-02 kPa.
3.91
Solutions
3.92
WMM5KSWKB5WIK4 jJl
Solutions
wsa
17.
The vapour pressure of water is 12-3 k Pa at 300 K. Calculate the vapour pressure of
1 molal solution in it.
(5 mol)
Mole fraction of water (JCa) =
+ LOOOG <1 KG) OF SOLVENT I.E.
Ans. 1 molal solution implies one mole
of
the
solute
dissolved
^5
mol
+ mol j (5 in
n
A+%
water.
Vapour
pressure
of solution
No.
of moles
of solute
(B) 1(PmAl) = 2-8 kPa
or
5Mto+Raoults
30~ TF Law
* T P74
According
A = PAJCA
Mass of water
(lOOOg) = 55 55 mol
No.
of
moles
of
water
(n
1-159 (5M + 30)= 6M + 30 A)
Molar mass
(18 g mol-1)
(2-8 kPa) = Pi
5-795 M + 34-77= 6M + 30
nB ____________(1 mol)______
0-205 M=of4-77
or M
Mole
solute
(xB=) fifj + nA (1 mol + 55-55 mol)
In the second
casefraction
:
Molar mass of solute 23-27 g mol-1 30
,
No. of moles of solute (ha) _Jmol
____
M
0-0177
56-55
Mass
of
water
(108 g) ,
,
No. of moles of water (nA)
~
- | o mol
Molecular
mass
(18
g
mol
)
Vapour pressure solution (PA) = PAxA = PA(1 - xB) = 12-3 kPa x (1 - 0-0177)
or
or
FU
or
...fti
= 12-3 ka xO-9823
12-08 KPA.
(6 =mol)
Mole
fraction
of
water
(
JC
)
=
a
18. Calculate the mass of a non-volatile solute (molecular6mass
mol +40)
which
moi . should be dissolved in 114
A + B
M
g of octane to reduce its pressure to 80%.
Ans. The solution is assumed to be non-ideal. According to Raoults Law,
Vapour pressure of solution (PA) = 2-9 kPa
Ft)
P
M
According to Raoults
A
A - PLaw,
S = PA = pA_,*_Wg_
x A_
Ps nA MB WA
(2 9 kPa) = PA
Let PA = 1 atm, Ps = 0-8 atm ; PA - Ps = 0-2 atm ; MB = 40 g mol'1; WA = 114 g ;
MA (CgHlg) = 114 g mol'1.

Dividing eqn. (I) by eqn. (II)
FIJ
...(H)
xs(6M
) MB +x 30)
WA PS
(2-8 kPa) (P; 5- P
6
x
(5M
+
30)
B
(2-9W
kPa)
MA
28 6 16-8
6M + 30 (0-2 atm) (40g mol ) x (114g) (0-8
atm)
(114gmor)
19.
Ans.
A solution containing 30 g of a non-volatile solute exactly in 90 g of water has a vapour

pressure of 2-8 k Pa at 298 K. Further 18g of water is then added to the solution and the new
vapour pressure becomes 2-9 k Pa at 298 K. Calculate
(i) Molecular mass of the solute.
(ii) Vapour pressure of water at 298 K.
Solution. Step I. Calculation of molecular mass of solute.
In the first case :
mol
Mass of solute
(30 g)
M
No. of moles of solute (nB) - TT^ i T ~ /u ,-u
Molecular mass (Mg mol )
5 mol
Mass of solute _
(90 g)
-1
No. of moles ot water (nA) Molecular mass (18 g mol )
Solutions
or
(2-8 kPa) = PA
f5+-*U
- P Â
- p 5
5+ 1 29 A 6-29
l 23-27 )
= (2-8 kPa^) x 6- 29 = 3.52 kPa
or
20. A 5% solution (by mass) of cane sugar in water has freezing point of 271 K. Calculate the freezing
point of a 5% glucose in water if the freezing point of pure water is 273-15 K.
K, x WB
AT
/ MB x WA
Ans.
WB = 5g ; WA = 100 - 5 = 95 g = 0 095 kg ;
MB = 342 g mol'1
ATr = 273-15 - 271 = 2-15 K
K/ x (5g)_________
For cane sugar solution :
2-15K
For glucose solution :
...Q)
(342gmorr)x (0-095 kg)
WB = 5 g ; W = 100 - 5 = 95 g ; = 0-095 kg
MB = 180 g mol-1
K/ x (5g)
=
AT _
/ (180 g mol'1 )x (0 095 kg)
Divide eqn. (II) by eqn. (I)
...(H)
( K / ) x (5g)
AT/
(2 15 K) (180 g mol'1 )x (0-095 kg^
(342 g mol ])x (0-095 kg)

(K/)x(5g)
(342gmoF1)
,,
AT, ~ nen ---------Frrx215K = 4-85 K
!
(180 g mol )
Freezing point temperature of glucose solution = (273-15 - 4-085) K = 269-07 K.
21 Two elements A and B form compounds having molecular formulae AB 2 and AB4. When
dissolved in 20 g of benzene, 1 g of AB2 lowers the freezing point by 2-3 K whereas 1 g of
AB4 lowers it by 1*3 K. Molal depression constant for benzene is 5-1 K kg mol"1.
(A.l.S.B. 2004)
Calculate atomic mass of A and B.
Ans.
K / x WB
4-77
B AT/ x WA
0-205 = 23-27
STEP I. Calculation of the molecular masses of the two compounds.
For the compound AB2 :
Step II. Calculation ofvapur
water
WBpressure
= 1 g ; Wof
A = 20 g = 0 02 kg ; AT/ = 2-3 K ; K/ = 5According to Raoult's Law, 1 K kg mol'1
K kg mol"1) x ( l g ) = j 10.87 g mol-t (2-3 K)x (0M _ (5-1
p
A = P>A or <2'S kPa) = PA
02 kg)
5+B
M
* 3.94
Solutions
For the compound AB4 ;

WB - 1 g ; WA = 20 g = 0-02 kg ; AT, = 1-3 K ;
= 5 -1 K kg mol'1.
(5-1 K kg mol'1) x ( l g )
<1-3 K) x (0-02 kg)
MR =
= 196-15 g mol-1.
STEP II. Calculation of the atomic masses elements of A and B.
Let the atomic mass of element A = A
Let the atomic mass of element B = B
Molecular mass of AB2 = A + 2B
Molecular mass of AB4 = A + 4B
According to available information
A + 2B
= 110-87
A + 4B = 196-15
Subtract eqn. (I) from (IIJ

2B = (196-15 - 110-87) = 85-28 or B - 85-28/2 = 42-64
Substituting the value of B in eqn. (I)
A + 2(42-64) = X10-87 or A = 110-87 - 85-28 = 25-59
Thus, Atomic mass of element A = 25-59
Atomic mass of element B = 42*64
...a)
: (i i )
At 300 K, 36 g glucose present per litre in its solution has osmotic pressure of 4-98 bar
If the osmotic pressure of the solution is 1*52 bar, at the same temperature, what would
22,
be its concentration ?
CRT
V
Ans.
n=
1st case
N=
4-98 bar ; C _
W,'B _
(36 g)
MB (180 g mol ')
T = 300 K ; V = 1 L
( 0 - 2 mol) x R x (300 K)
(4 -98 bar) =
(1 L)
Ilnd case :
-0-2 mol
...(i)
n = 1*52 bar ; T = 300 K, V = 1 L
= C x R x (300 K)
( 1 5 2 bar) =
1L
Divide eqn. (II) by eqn. (I)
(1-52 bar)
(4-98 bar)
0 2 mol
C=
(1-52 bar)
(4 98 bar) X (0-2mol) = 0-061 mol
= 0-061 mol L'1 - 0-061 M.
...(H )
3.95
Solutions
0% Concept Based Questions

Which solution has higher concentration; 1 molar or 1 molal having the same solute ?
(Pb. Board 2004)
The relative concentrations of the solutions will depend upon the density of the solvent.
(a)
IF the density of solvent is lg/mL. In aqueous solution, the density of water is normally
Ans
.
taken as one. This means that lm solution has 1 mole of the solute dissolved in 1000 g or
1000 mL of the solvent. At the same time, 1M solution contains 1 mole of the solute in
1000 mL solution which is the volume of both the solute and the solvent present in the
solution. This clearly shows that the solvent present in 1M solution is less as compared to
1 m solution. THEREFORE, 1M SOLUTION IS MORE CONCENTRATED THAN 1 M SOLUTION.
(b) If the density of the solvent is less than lg/mL. This means that the volume of solvent
(mass/density) will be more as compared to its mass. Thus, 1 M solution will be less
concentrated than lm solution.
(c) If the density of the solvent is more than lg/mL. This means that the volume of solvent
will be less than its mass. Under the circumstances, 1 M solution will be more concentrated
than 1 m solution.
W'hy is molality of a solution preferred for expressing concentration than molarity ?
In molality, the mass of the solvent is considered while in expressing molarity, volume of
solution is taken into account. Since mass does not change with temperature while volume
Ans. changes, molality does not change with temperature but molarity changes. Hence, molality is
better for expressing the concentration of solution than molarity.
Will elevation in boiling point temperature be same for (MM NaCl and 0-1M sucrose
solution ?
No, it will not be the same because colligative property does not depend upon molar concentration
alone but also upon the number of particles (ions) in solution. Sodium chloride (NaCl) is an
ionic solid and will form more number of particles (ions) in solution than sucrose (Ci2H220 n)
Ans.
which is a molecular solid. Thus, the elevation in boiling point for 0-1M NaCl solution will be
more.
What is the expected deviation from ideal solution behaviour when acetone and chloroform
are mixed to form a solution ?
The molecules of acetone and chloroform will get linked by
intermolecular hydrogen bonding. This means that the volume of
the solution will be less than for ideal solution. Therefore, AVtmix)
Ans.
will be negative and solution will show negative deviation as CH3.
.-Cl
^C=0......HCCf
compared to ideal solution.
3 HC1. If one is kept in
Outer hard shell of two eggs are removed by placing them in dilute
pure water and the other in sodium chloride (NaCl) solution, what will you notice ?
(Pb. Board 1998)
3.96
Solutions
Ans. The egg placed in water will swell in size because water (hypotonic in nature) will enter the
semipermeabie membrane of the egg due to osmosis. However, in the second case, fluid from the
egg (hypotonic) will come out and will pass into sodium chloride solution which is at a higher
osmotic pressure (hypertonic). Therefore, the egg placed in sodium chloride solution or saline water
will shrink in size.
When 50 mL of ethanol and 50 mL of water are mixed, predict whether the volume of the
solution is equal to, greater than or less than 100 mL.
(West Bengal J.E.E. 2002)
Ans. In both ethanol and water, the molecules are hydrogen bonded. When these are mixed to form the
solution, the molecules of one liquid will tend to break the hydrogen bonds in the molecules of the
other liquid and vice versa. The attractive forces in the molecules will decrease and this will lead to
increase in volume (AVmixing is + ve). Therefore, the volume of the solution will be more than 100
mL.
Relative lowering in vapour pressure is a colligative property. Explain.
Ans. Relative lowering in vapour pressure (p^ - Ps)/p^ is equal to mole fraction (j:B) of the solute.
In other words, it depends upon the number of moles of solute (n B) in a given solution. It is
therefore, a colligative property.
Are equimolar solutions of urea and sodium chloride iso-osmotic ? Justify your answer.
ANS. No, these are not. The osmotic pressure of sodium chloride (NaCl) solution will be higher than that of
urea solution because being an electrolyte, it will furnish more number of ions in solution than urea
which is a molecular solid.
When fruits and vegetables which have been dried are placed in water, they swell slowly in
size and regain their original form. Assign reason. What is the effect of temperature on this
process ?
Ans. The cell walls of the fruits and vegetables act as semipermeabie membranes. In the dry state, the
concentration of the fluid inside cell saps decreases. When these are placed in water, the molecules
of the latter will enter the cell walls because of osmosis. Slowly and slowly, they will get fully
hydrated again and thus, will regain their original form and shape. The process of osmosis will be
accelerated with the increase in temperature because osmotic pressure increases with rise in
temperature (N = CRT).
Osmotic pressure is generally preferred for the determining the molecular masses of proteins.
Explain.
(A.I.S.B. 1994)
ANS. Other methods of determining the molar masses such as elevation in boiling point and depression in
freezing point are not useful because the change in temperature (AT) is very small. Moreover, at
elevated temperature, the proteins are likely to decompose as these are unstable at high temperature.
The osmotic pressure is the most suitable for determining the molar mass of proteins and other
polymers.
When a pressure higher than the osmotic pressure is applied on the surface of the solution
separated from a solvent by semipermeabie membrane, what will happen ?
Ans. Reverse osmosis will take place I.E. the molecules of the solvent present in the solution will come out
of the solution through semipermeabie membrane. Therefore, the level of the solution in the
container will fall.
DEFINE A SOLUTION.
6
3.97
.
Solutions
GIVE AN EXAMPLE OF A SOLUTION IN WHICH SOLUTE 7.
2. IS A SOLID WHILE SOLVENT IS A LIQUID.
Plants grown in marshy lands generally decay after sometime. Assign reason.
3. DOES THE SOLUTION OF OIL AND WATER REPRESENT A 8
Ans. Plants that are grown in marshy lands have developed
high osmotic pressure because of the presence
.
TRUE SOLUTION ?
of
extra
salt
particles
in
the
cell
saps.
Therefore,
they
may absorb excess of water from the soil
DEFINE SOLUBILITY. HOW IS IT EXPRESSED ?
4.
which will lead to the bursting of root hair. The plants will therefore, slowly decay.
5. THE SOLUBILITY OF NACL IN WATER INCREASES WITH 9.
Calcium chloride
used OF
to clear
snow
RISE
IN TEMPERATURE
WHILE isTHAT
CUSO
4 in cold countries. Explain.
DECREASES
. calcium chloride is added to snow which is ice, the freezing point of water gets lowered because
ANS. When
1.
impurities lower the freezing point of a substance. This means that ice will start melting at the
prevailing temperature. This operation helps in clearing snow in cold countries.
Out of 1M H2S04 and IN H2S04 which is more concentrated and why ?

Ans. 1M H2SO4 solution is more concentrated than IN acid solution. Actually 1M solution ot acid is
prepared by dissolving 98g of the acid (1 gram mole) per litre of the solution while IN solution of
acid is prepared by dissolving 49 g of the acid (1 gram equivalent) in the same volume of the
solution. Since 1M solution has a greater amount of solute dissolved in it, this solution is more
concentrated that IN solution of the acid.
4% NaOH solution (weight/volume) and 6% urea solution (weight/volume) are equimolar
but not isotonic. Explain.
Ans. Both the solutions have the same molarity or molar concentration (1M) but do not have the same
osmotic pressures. Actually NaOH dissociates into ions in aqueous solution whereas urea
(NH2CONH2) remains as molecular solid. Thus, the osmotic pressure of NaOH solution is more
than that of urea solution. Therefore, the two solutions are not isotonic in nature.
What is the difference between molal elevation constant and molecular elevation constant ?
(Uttaranchal Intermediate 2003)
Ans. Molal elevation constant is the elevation in boiling point produced when 1 mole of the solute is
dissolved in 1000 g of the solvent. On the other hand, molecular elevation constant is the elevation
in boiling point when one mole of the solute is dissolved in 100 g of the solvent. Mathematically,
Molecular elevation constant (K) = 10 x Molal elevation constant (10 K/,)
Assignment
TYPES OF SOLUTIONS AND SOLUBILITY
1. MOLES/KG.
3.96
2. IT CHANGES.
4. MOLALITY IS BETTER.
10. Carbon tetrachloride and water are immiscible
10 VOLUME IS NOT INVOLVED IN CASE OF MOLALITY
ethyl alcohol and water are miscible in all
. MOLE whereas
AND FOR
FRACTION
BUT
IS
proportions.
Explain,
EXPRESSING
CONSIDERED
MOLARITY
AND
11. Give the
of a solution which has liquid as
. example
11 NORMALITY
1M theHsolute
2SO
4and solid
IS as the
MORE
solvent.
. CONCENTRATED.
Hints and Answers
Solutions
4.
5.
6.
7.
8.
2. Solution of soluble salts in water.
Units of solubility = g/IOOg of the solvent.

Solubility increases with rise in pressure
according to Henrys law.
It becomes unsaturated.
Ethyl alcohol and water are both polar while
CC14 is non-polar.
Hydrated salts.
3. No. it is not a true solution.
CONCENTRATION OF SOLUTIONS
1.
2.
3.
4.
Define molality. What are its units ?

(H.P. Board 1994)
What is the effect of temperature on molarity of a
solution ?
What is molality of a solution ? How does it differ
from molarity ?
(D.S.B. 1994, Haryana Board 98 Supp.)
Out of molality and molarity which is better for
expressing the concentration of a solution ?
5.
Explain the terms mass fraction and mole fraction.
6.
Define molarity and mole fraction.
(A. I. SB. 1994)
7.
8.
9. Define (i) normality (ii) molarity (iii) mole fraction.

(D.S.B. 1994; A.l.S.B. 1993)
10. Molality and mole fraction of the solutions are not
affected by change in temperature while molarity
and normality change. Explain.
11. Out of 1M H2SO4 and IN H2SO4 which is more
concentrated and why ? (Pb. Board 2003 Supp.)
12. Why does molality (m) remain unchanged with
temperature but molarity (M) changes ?
(Pb. Board 2003)
13. Why is 1 M solution more concentrated than 1m
SOLUTION ?
(Pb. Board 2004)
Hints and Answers

Define normality of a solution.
Define the terms molarity and molality of a solution.
How does the rise in temperature change molarity
and molality values of the solutions. (D.S.B. 2001)
How does pressure influence the solubility of a gas in

a liquid ? State the law which governs it.
The solubility of C02 in water increases with increase
in pressure but decreases with the increase in
temperature ? Explain.
What is a saturated solution ? What happens if the
temperature of the saturated solution is increased ?
Why are ionic solids soluble in water but insoluble in
polar solvents ?
Why ?
>
3.99
Solutions
proportions Co-relate the above behaviour with

9. Mention the characteristics of ideal solution. What
molecular structure of these compounds.
causes deviation of non-ideal solutions from Raoults
(A.I.S.B. 2003)
LaW 7
(Pb. Board 1999)
18. What are non-ideal solutions ? Explain as to why
10. Discuss the behaviour of the non-ideal solutions
non-ideal solutions deviate from Raoult's Law.
showing positive and negative deviation from
Raoults Law.
(D.S.B. 2003)
11. Carbon tetrachloride and water are immiscible while 19. State and derive Raoults Law for a solution
containing
ethyl alcohol and water are miscible in all
proportions. Co-relate the above behaviour with
(a) Volatile solutes (b) Non-volatile solutes.
structural nature of the molecules of these
(H P. Board 2003)
compounds.
(D.S.B. 2001)
20. Why is vapour pressure of solvent lowered on adding
non-volatile solute to it ? (Pb. Board 2004)
12. Give the main points of distinction between non ideal
solutions showing positive and negative deviations
21. Mixing of acetone and chloroform occurs with
from Raoults Law.
reduction in volume and is endothermic process.
13. Draw a suitable labelled diagram to express the
What change will occur in vapour pressure ? Explain
relationship for ideal solutions of components A and
your answer.
(Pb. Board 2004)
B between vapour pressures and mole fractions of
22.
State
Raoults
Law
for
solution
containing
components at constant temperature ?
volatile
(D.S.B. 2002)
liquid maxture.
(C.B.S.E. Foreign 2004)
14. What are ideal solutions ? Explain non-ideal
23.
Ethanol
and
water
form
a
solution
showing positive
solutions showing negative deviation from Raoults
deviation from Raoults Law. Explain.
Law with diagram.
15. Explain the relation between mole fraction and
(H.P. Board 2004)
Raoults Law for solutions having volatile solutes
lints and Answers
with the help of diagram. (Haryana Board 2002) 6. Maximum boiling : 20-2% HC1 and 79-8% water
16. What is Raoults Law ? Why does a solution of
by mass
ethanol and cyclohexane show positive deviations21. Vapour pressure of the solution will decrease.
from ideal behaviour ? (Pb. Board 2003 Supp,)
17. Carbon tetrachloride and water are immiscible
whereas ethanol and water are miscible in all
COLLIGATIVE PROPERTIES OF SOLUTIONS

1.
2.
3.
4.
7.
How will you show that depression in freezing point

temperature is a colligative property ?
(Pb. Board 2001)

8. Illustrate elevation in boiling point with the help
of vapour
pressure temperature curve of a solution.
RAOULTS LAW (IDEAL AND NON-IDEAL
SOLUTIONS)
3. How can Raoult's Law be used to calculate the
Show that elevation in boiling point is a colligative
molecular mass of a dissolved substance ?
property.
(A.I.S.B.
2000, Pb.
Board 2001)
Define the vapour pressure of a liquid. What are the
5. Distinguish
between ideal
and non-ideal
solutions.
factors which influence the vapour(Haryana
pressure Board
of the2002)
(Haryana
1999,
2001)
9. Explain why freezing
point ofBoard
solution
is lowered
7 will you show that relative lowering in vapour 6. Certain solutions show positive deviations from
4.liquid
How
when
a non-volatile
presentdeviations.
in it.
Raoults
Law
while somesolute
show is
negative
Explain
why the
pressure
of ?a solvent gets
pressure
is a vapour
colligative
property
(A.I.S.B. 2001)
What
does
it
signify
?
lowered when a non-volatile solute is added
it. 2001)
(Pb.toBoard
7. Explain
an graphically
azeotrope. Give
each of of a
10. Show
how one
the example
vapour pressure
(D.S.B. 1993, H P. Board 1995)
solvent
and solution
changeboiling
with temperature.
maximum
boiling
and minimum
azeotrope. Show
State
Raoults
Law.
Derive
its
expression
for
a
5. Define boiling point of a liquid. Why does the boiling
on this graph the boiling points
the solvent
(H.P.of
Board
2000) and
solution containing non-volatile solute in a volatile
point of a liquid rise when (Pb.
a non-volatile
solute is8. Rectified
solution.
higher andmixture.
why ? How will
spiritWhich
is an is
azeotropic
solvent.
Board 1996)
to itideal
?
you prepare absolute alcohol from rectified (A.I.S.B.
spirit ? 2001)
What added
is an
solution ? What are the
characteristics
for
ideal solution
6. What is molal an
elevation
constant? ? What are
11.
Define
osmosis.
Under
what
conditions
does
osmosis
units?
(D.S.B. 1997)
take place ?
(Pb. Board 1997)
2.
1.
What are the colligative properties of a solution?

What is common in all these ?
How does relative lowering in vapour pressure help in
calculating the molar mass of a solute ?
3.100
Solutions
3.101
Solutions
12. When an egg without its outerhard surface is placed

(ii) 1 M potassium chloride
in pure water, it swells in size. When the same egg is
(Hi) 1 M ALUMINIUM CHLORIDE (Haryana Board
kept in NaCl solution, it shrinks. Assign reason.
2002)
(A.I.S.B. 1998)
23. Write two points of distinction between diffusion
13. What is the difference between osmosis and
AND OSMOSIS.
(Pb. Board 2002)
DIFFUSION ?
(J.K.
jjOSiBoard
Competitive
xcmu*tatiOHi
24. Why is calcium chloride used to clear snow in
1997)
COLD COUNTRIES ?
14. Give a method for determining the osmotic pressure
25. Explain as to why there is a rise in boiling point
of a solution.ofState
the Lowering
principle underlying
this
Measurement
Relative
in Vapour Pressure
when a non-volatile solid is dissolved in a liquid.
method.
Walker
Method)
15.(Ostwatd
How doesand
osmotic
pressure
depend upon
(D.S.B. 2003)
TEMPERATURE
?
(HaryanacanBoard
The
relative lowering
in vapour pressure
be measured
26. What
withtype
the help
of azeotrope
of this method.
is formedThe
by apparatus
mixing nitric
1996)
acid and
water
consists of two sets are glass bulbs (three in each
set). The three
bulbs
of ?the first set are filled with the
16. What
Vanthalf
Hoffof
equation
for dilute while
solutions
paper
2003)
solution
to is
about
their capacity
the? other three bulbs are filled with(C.B.S.E.
the puresample
solvent
to the
In what way is it helpful in calculating the osmotic
is osmotic
pressure both
? Explain
how the
same level. These sets of bulbs are weighed separately and27.
keptWhat
in a constant
temperature
(thermostat)
pressure of a solution ?
(D.S.B. 2000)
molecular
mass of
a non
volatile
can be
as16.
shown
Fig. solutions
These are
then happens
connected
with
weighed
glass
tubes
whichsolute
are filled
What in
arethe
isotonic
? What
when
suchthree U-shaped
determined
from
it can
? (Haryana
Board
2004)
with anhydrous
CaCI
to
absorb
the
water
vapours
{P4O10
or
even
cone.
H
S0
also
be
used).
These
are
2
4
solutions ane 2 separated by a semipermeable
Hints
and
Answers
also called
Guards
tubes
since
they
donot
allow
the
water
vapours
from
outside
to
enter
the
glass
bulbs.
membrane ?
(H.P. Board
^ upon the no. of soluteDry
air
particles.
1999) ___^1. All depend
18. Why are injectable medicines dissolved in saline 6. K kg mol"1 <K m'1),
water before being administered ?
15. Increases with rise in temperature.
19. In marshy places, the plants decay quite fast. Assign
18. Both become isotonic.
reason.
19. Plant roots burst because of extra intake of water
20. What happens when R.B.C, are placed in 0-1% NaCl
20. Their size will increase,
solution ?
21. Due to osmosis which increases with rise in
21. When fruits and vegetables that have been dried are
temeprature.
placed in water, they swell in size and regain their
original form. Why ? Would a temperature increase
22. I M urea solution.
accelerate this process ?
26. Maximum boiling azeotrope is formed.
22. Out of the following solutions which has the
maximum freezing point and why ?
(i) 1 M urea
A current of pure dry air is led into glass bulbs one by one. It first gets saturated with the water vapours
present on the surface of the solution and the amount of vapours absorbed is proportional to the vapour
pressure on the surface of the solution. When bubbled through the bulbs containing the solvent, air absorbs
ABNORMAL
MOLECULAR
MASSES
additional water vapours because
the vapour pressure
on the surface
of the solvent is more than on the
surface
solution.
Thebyincrease
the mass of air is7.proportional
to
the
difference in the vapour
1.
Whatofdothe
you
understand
abnormalinmolecular
Explain giving examples the term colligative
pressure
ofofpure
solvent
(P^) and solution (P s). Finally, theproperty*.
air is passed
set of calcium
chloride
masses
solutes
?
Why through
do we sometimes
get abnormal
(Haryana
Board 1998,
A.I.S.B.
1996)
molecular
of the
substances
using
colligative
tubes which absorb
all the water
vapours
present
in the air and
dry airmasses
escapes
from
the outlet.
These
tubes
2.
Define Vant
factor.again
(Pb. Board
1998)
properties
the solution. to
(C.B.S.E.
Foreign value
2003)
are detached
andHoff
weighed
to find
out the increase in mass
whichofcorresponds
the maximum
3.
What is
Vant Hoff
factor ?pressure
How does
it help
in of 8.
Give (P
one
example each when Vant Hoff factor is
of vapour
pressure
I.E. vapour
on the
surface
solvent
A).
determining the degree of dissociation and
2
AND 1/2.
(Pb. Board 2003)
association
of a solute in solution ?
9. Explain with the helps of suitable examples in each
Calculations
(Pb. Board 2000)
case. Why the molar masses of some substances
Loss
in mass
in the
P5 is more
The
value
of Vant
Hoffsolution
factor forbulbs
a solution
determined with the help of colbgative properties
than
does
it signify
2(A.I.S.B.
are (i) higher (ii) lower than actual values.
Loss1.inWhat
mass
in the
solvent
bulbs X2000)
(p^- Ps)
What are degree of dissociation and degree of
(C.B.S.E. sample paper 2003)
Total loss of
in electrolytes
mass in both
set of
P{ + (P
association
? How
arebulbs
these Xrelated
to A - Ps) = PAHints
and
Answers
the
Van'tinHoff
factor
? 2 tubes)
(Gain
mass
of CaCl
4. Solute dissociates in solution
What happens toLoss
the colligative
when
in mass inproperties
solvent bulbs
solute associates in solution ? (H.P. Board 1999)
7. 5 8. (i) Less than 1 (ii) More than 1.
PA-P8.S i = 2 (KCI), i = 1/2 (C6H5COOH)
What is the expected Vant Hoff factor for
KThus,
dissociates
in
4[Fe(CN)jJ when
Gainitin completely
mass of CaCl
2 tubes
water?
(D.S.B. 1998)
4.
5.
6.
7.
3.102
Solutions
Thus, relative lowering in vapour pressure can be calculated with the help of the method.
The method is successful in case the solute is of non-volatile nature.
DETERMINATION OF MOLECULAR MASS OF THE SOLUTE. The molecular mass of the solute can also
be calculated with the help of Raoults Law. According to the law,
In case, the solution is dilute (WB/MB) can be neglected.

PA - Ps _ WB x MA P;
MB x WA
If all the other values are known, MB (molar mass of the solute) can be calculated,
3F SAMPLE. A current of dry air was bubbled through a bulb containing 26 66g of an organic
compound in 200g of water and through a bulb at the same temperature containing water and finally
through anhydrous CaCli tube. The loss in mass in bulb containing water was 0-087g and the gain in mass
of the calcium chloride tube was 2 036g. Calculate the molecular mass of the organic substance.
Solution :
PA ~ Ps _ Loss in mass of solvent bulb

PA Gain in mass of CaCl2 tube
(Q-087g)
(2-036g) = 0 0427
According to Raoults Law
WB/MB
+ WA/MA
26-66
MB
p _ p
77- - -200
wr = = . s = 0-0427
1A
26 66-------fs.
MB 18 ** 77~
26-66 x 18 x MB
MB
26-66 x 18 + 200 XMB
PA
= 0-0427 or
26-66 x 18
26-66 x 18 + 200 x MB
= 0-0427
479-88
479-88 + 200 x M8 0*0427 or 479-88 - 479-88 X 0-0427 + 200 x 0 0427 x Me
3.103
Solutions
479.88 = 20-49 + 8-54 x MB or 8-54 MB = 479-88 - 20-49

459-39
= 53-8.
8-54
MR =
Note. The number of moles of solute (W/MB) are not neglected in this case because the solution is not
dilute as the concentration of solute in the solution is more than 10%.
Measurement of Vapour Pressure of a Liquid with Temperature
The measurement is given with the help of Clausis Clapyron s equation.
Ji = _^Ll3L_
6
P, 2-303R
Iog
T - Ti
T, x T 2 J
Here PL and P2 are the vapour pressures at temperatures T[ and T2 respectively while AHvap is the molar
enthalpy of vaporisation.
SEXUMP The boiling point of CCl4 is 77C and its heat of vaporisation is about 31 kJ mot1. Calculate the
vapour pressure in atmospheres at 25 C.
Solution
log A = AHvaP P, 2-303 T2-Tt

R
T, x T- 2 J
P2 = 1 atm (because 77C is b.p. of liquid CC14) lvap =
31 kJ mol'1 = 31 X 103 J mol'1 ; R = 8-314 J T2 = 77 +
273 = 350 K ; T( = 25 + 273 = 298 K
(31 x 10J J mor)x (52 K)
log
2- 303 x (8-314 J K'1 mol'l)x (298 K) x (252 K)

= 0-807
M
= Antilog (0-807) = 6-41

__
Pi =
(1 atm)
6-41
6-41
= 0-156 atm.
Calculation of Osmotic Pressure from Relative Lowering of Vapour Pressure
Osmotic pressure (n) of a solution is related to the relative lowering in vapour pressure as :
P
A ~ Ps _
RpT
3.104
Solutions
SOME NOTEWORTHY POINTS

>
>
>
>
>
>
>
>
>
>
Solubility is the maximum of the solute in 100 g of the solvent in a saturated solution.
ppm is used to express the concentration of the solutions in which solute is present in very
small amount.
Molality and Mole fraction are independent of temperature whereas molaritv and normality
are not.
1 Molar solution is normally more concentrated than 1 molal solution.
For solutions with non-volatile solutes, the vapour pressure of the solution is always less
than that of the solvent.
Ideal solutions strictly obey Raoults Law at all temperatures aqd all concentrations.
Non-ideal solutions may show either positive deviations or negative deviations from
Raoults Law.
All Colligative Properties depend upon the number of the solute particles in a given
amount of the solvent.
Relative Lowering in vapour pressure can be measured by Ostwald and Walker Method.
Addition of non-volatile solute to a liquid raises its boiling point and lowers its freezing
point.
Ethylene glycol is used as Antifreeze for car radiators.
Molecular masses of proteins and polymers can be best determined with the help of
osmotic pressure.
Dilute solutions behave in same way as ideal gases and obey Vant Hoff equation.
Solutions with same osmotic pressure are called Isotonic Solutions or isotonic solutions
Osmosis always takes place from hypotonic into hypertonic solution separated by
semipermeable membrane.
Abnormal molecular masse are noticed for the solutes which undergo either dissociation
or association in the solve .
Important Relationships :
No. of moles of solute
_ No. of moles of solute
Molarity (M) Volume of solution in litres
No. of equivalents of solute
Normality (N)
Henrys Law : M P (At constant temperature)
Partial V. P. of the gas
Henrys Law constant : KH =*
Mole fraction of gas in solution
Raoults Law
P = PA-tA + PB XB (For ideal solutions)
Molality (M) =
P. -Ps
* SL
P* - Ps
KXW X1000
Elevation in b.p. B:
(For ideal solutino)
= JfiL
"A (For non-ideal solution)
AT/, = K/, x M = 2------------MBXWA
3.105
Solutions
Solutions
Solutions
* 3.107
Q.2. Vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non-volatile nonilihiiitillliiiii
electrolyte solid weighing 2-175g is added to MR(T
39-0g of benzene. The vapour pressure of solution is 600 mm
S
TEP
II.
Calculation
of
vapour
pressure
of
the
solution
2
Hg, What is the molecular mass of solid substance ?
(I.l.T.
^)
1990)
ACCORDING
10 RAOUIT
'S LAW :KJ, Molal Elevation
Constant
--- -77;
Solution : Step I. Calculation of no.b of
moles
of vap
solute
1000
X AH
^solution ~ Pbenzene x ^benzene
MR(T }
vap _ 600
_ ^solution2_ (600mm)
)
K
^benzene
r X WB x 1000
Pbenzene (640mm)
ATy = K/ x m =
Depression in f.p. :
^benzene 640
Moles of benzene + Moles of solute
1
Pi _
600 : 1S (39g)/(78gmol~
) T, - T, 0-5
Clausius Clapyrons equation
1
P, 2-303RLT|xT
2
640
39g/(78gmor
J+
0-5 + NWIM
0 5 + iw =0-5
x|CRT
= 0 533
it =
= - 7V
pressure
RT
RISOIUIE = 0-533 - 0-5
v = 0 033
MOL
Normal molecular mass
Vant Hoff factor :
Step 11 Calculation of molecular1 mass
of solute
Observed
molecular mass
Osmotic
PA-PS
Ps
iMass
- 1 of solute _
(2-175g)
Degree of association
: massa ~ ^No.
^ j of moles of solute (0 033 mol) ~ 65-9g1-1
Molecular
moli - 1
. =FB_ =B
( .- SOLUTION
IS DILUTE
Q.3. Calculate the number of molecules of oxalic
acid in lOOmL
of 0-02N oxalic
acid )solution.
Degree of dissociation :
a=
IXW
B XM
A
Solution
: Step
1. Calculation
P;-PS
Ps
n - 1
(Roorkee 1991)
(SOLUTION
)
of no. of moles of oxalic acid per litre
of the solution.
No. of moles of oxalic acid

G<mp&tdive'X&Mi*uM<HU
CALCIUM
of solution
litre NITRATE)
PA = 760MM, I = 2-4, WB = 7-0G, MB =Volume
164 G MOL
'1 = (FORin
MBmx WA
Molarity =
WA LOOG, MA = 18G MOL"1
Q.l. The vapour pressure of

a dilute
aqueous
solution
mm of mercury at
,1 No.
of moles
of oxalic
acidof glucose (C^lluOt) is 750
N 0-02
( M = = -(I.I.T.
= 0-1M)
19S9)
S
TE
760
(164GMOR
*)No.
X Calculation
(100
)
ofGmoles
=ofO-Oi
SOLUTION
:- P
molemol.
fraction of glucose.
Step
II
Calculation
of
no.
of
molecules
of
acid
per 100- mL750
of solution.
, , , - 0 0184 X 760 P\ oxalic
- P
760
s
760 - PS = 0-0184 OR PS =N760
10
= 0-0132
According
to Raoult
Law, xBcontains
= e
mL of oxalic
acidssolution
moles= = 0-01
760 1000
760
760
760 - 13-98 -- 746-02 MM.
Ps =-----------------------------------------------------Step CALCULATION OF MOLALITY OF SOLUTION 0 0 1
x 100 = 0 001 mol
100 mL of oxalic
acid solution
contains
moles
Mole fraction
of solute
= 0-0132
100
L
01GMOR
mol (L'
- - --------------------------760 - PS 373K.2-4
X (7-0(GI)(0
Xmolality
(18
Calculate
II)) )mole
fraction ofthe
solute.
Molecules of oxalic acid = 0-001BX NQ.0

23
20
+
*B= 103 x 6-022
B nA x 10 = 6-022 x 10 molecules.
of dissociation
Ca(NOj) 2 in
in dilute
solution
solution
7-0g of the solute
per of
lOOg
If H|1Q.4.The
molesdegree
of the
solute be of
dissolved
lOOOg
of theaqueous
solvent,
thencontaining
B will represent
molality
theofsolution.
water at 100C is 70 percent. If the vapour pressure of water at 100C is 760mm, calculate the vapour pressure of the solution.
(100 S)
xB - 0-0132 ; nA (jggmor1)
= 55-55 mol
Solution : Step I Calculation
of the Van't Hoff factorB(i)

B
.xB or
. cccc 0 0132
Calcium nitrate dissociates
solution
71g in
+ Naqueous
A
B +as : J-*
2
xN
55-55 x 0 0132
B +
Ca(N03)2 /t^B =Ca0-0132
+(AQ) +
2N0
3 (AQ) l-l
0-9868 nB = 55-55 x 0-0132

55-55 x 0-0132
l-l
a - --------7 or 0-7 = ----7 or L = 0-7 X 2 + 1 = 2-4

= 0-74
"B N - 1
0-9868 3-1
(I.l.T. 1991)
3.108
Solutions
Vapour pressure of solution (PA) =
- l / 4PA) = 3/4 pA
For the' solution,
PA*A - PA X
(100 g) :
A
3/4 P
(18 g mol-1)
A = PA
3_
3^
*A
rtA + ns
100 mol;
18
(100/18 mol)
= (WB g)
(60 g mol )
_ Wg_ mol.
60
(100 /18mol) +(W /60 mol)

100
18
100 x 60 + W x 18
18 x 60
6000
6000 + I8W
10
0
18 x 60
6000 x 18 W
18
or 6000 + 18W = 6000 X = 8000.

2000
18W = 8000 - 6000 or W =

18 = 1 1 1 1 .
Q.5. A solution of urea in water boils at 100-18C. Calculate the freezing point of the same solution. Molal
Mass of
l l l 1-86
g and 0-512 K m'1 respectively.
constants
K,urea
and =
K,l are
Solution
:
= K, x m and AT, = K, X m
Sup I I Calculation of molarityATy
of solution.
Mass of urea
AT>
(llllg)
Molarity of solution (M) ==
Molar mass
ill-1
(60 g moH)
AT, K,
m o l k-Ig
Mass
of
watering/1000
(kg)
kg) 6 0 x 0 - 1
AT* = 100- 18C - 100 0 - 0 18C = 0-18K(100/1000
K,
= 18-52 mol kg'1 = 18-52 m.
= 1-86 K m-, K, = 0-512 K nr1
Q.8.Calculate the freezing point of a non-electrolyte aqueous solution having osmotic pressure of 2-0 atm
(1861C
-y~|- x 0-18K = 0-654K = 0-654C 1 K, 0 (Roorkee 1993)
at 300 K (Ky = 1-86 K kg mol'1). AT, -Ll x AT, =
(0-512K m_l)
SOLUTION : STEP I Calculation of the molar concentration of the solution
Freezing point of solution = 0C - 0-654C = - 0-654C.
Q.6. Addition of 0-643g of a compoundnto=50
mLorofCbenzene
(density = 0-879 g/mL) lowers the freezing point from 5CRT
51 C to 5-03C. If K,for benzene RT
is 5-12, calculate the molar mass of compound. (I.I.T. 1992)
2'Oatm)
Solution : Mass of benzene (WA) = V x d = (50 mL(X
0-879 g/mL) = 43-95g = 0-04395 kg WB1 =
C=
= 0-0812 mol L'
1
(0-0821
atmkg
K_mol-*
mot~^) x (300K)
0-643g, AT, = 5-51 - 5-03 = 0-48C = 0-48K
Kf =litre
5-12K
K, x WB
STEP 11. Calculation of freezing point of the solution
Molar mass of compound (MB)_ A-jy x v/A
It is assumed that the molarity (concentration) of the solution is the same as molality.
m = 0-0812
mol kg'1
= (5-12 K kg mor^x (0-6436)1 =
mol-t.
1
.
ATy = Kf x m
= (1-86
K kg mol'
) x (0 0812 mol kg'1) = 0151K.
(0-48K)
x (0-04395
kg)
Freezingpoint of solution (Ty) = Ty- ATy = 273K - 0 1 5 1K = 272-849 K.
Q.7. What mass of2 a non-volatile solute urea (NH2CONH2) need to be dissolved
in l00g of water in order to
J
Q.9.
8-0575
10' kg ofofGlauber's
in water
obtain of
1 dm
of a solution of density 1077-2 kg m'3.
decrease the
vapourx pressure
water by salt
25%is?dissolved
Also calculate
the to
molality
the solution.
Calculate the molarity, molality and mole fraction of Na 2S04 in the solution. (/./. T. 1994)
(I.I.T. 1993)
Solution : Molecular mass of Glaubers salt (Na2S04.10H2O)
= 2 x 23 + 32 + 4 x 16 + 10 x 18 = 322 a.m.u.
= 322 gmol'1
Now
Mass of Glaubers salt = 8 0575 x 10"2 kg = 80-575 g

SOLUTION : STEP 1 Calculation of mass of urea
Vapour pressure of water = PA
Solutions
3.109
Mass________(80575 g)
Moles of Glaubers salt
Molar mass (322gmoTr)

Volume of the solution = 1 dm3 = 1L = 1000 mL
= 0 25 mol
Density of solution - 1077 2 kg nT3 = 1 0772 g m'3 = 1 0772 g mL'1 Mass

of 1000 mL of solution = 1000 x L0772 = 1077-2g
Mass of water = (1077-2 - 80-575) = 996-625g
Moles of solute
0 25 mol
2508 m
Molality of solution <) = Massof
jn kg = Îsg /1000) = O'

ir
996-625g ..
Moles of water =----------------= 55 -37 mol
(18gmol *)
Mole fraction of solute
(0 25 mol)
(0-25 mol)
= 0-00045
(0-25 mol) + (55-37 mol) (55-62 mol)
............................................ Moles of solute

(0-25 mol)
Molarity of solution (M) - TT-!-----------;:: -------------------------Volume of solution in litres
1L
= 0-25 mol Ll = 0-25M.
Q.10. The freezing point of a solution containing 0-2g of acetic acid in 20-0g of benzene is lowered by 0-45C.
Calculate the degree of association of acetic acid in benzene (K/ for benzene = 5-12 K kg mol -1).
(Roorkee 1994)
SOLUTION : STEP I. Calculation of observed molecular mass of acetic acid
Kf x WB x 1000
MR =
ATb x WA
WB = 0-2g, WA = 20-0g. ATF = 0-45C = 0-45K, KF = 5-12 K kg MOL1
(512 kg K MOL-1) x (0-2g)x 1000

MB
(0-45K) x (20g)
= 113-78 g mol I-I
STEP 11. Calculation of Van't Hoff factor (i)

_ Normal molar mass _ (60gmol *)
Observed molar mass (113 -78 g mol-1)
STEP III. Calculation of degree of association (a)

2CH3COOH ^^ (CH3COOH)2
i-1
0-527 -1
(1/n-l)
(1/2-1)
0-473
0-50
= 0-946
Degree of association (a) = 0-946 X 100 = 94-6%.

Q.ll. 0-85 g aqueous solution of NaN03 is approximately 90% dissociated at 27C. Calculate the osmotic pressure
(R = 0-0821 L atm K'1 mol'1).
(Roorkee 1996)
SOLUTION : Calculation of Van't Hoff factor
NaNOj . Na+ (aq) + N03" (aq)
i-1 n
-1
or 0-9 =
i-I
or 1 1 = 0-9 + 1 = 1-9
Solutions
3.110
Calculation of osmotic pressure Initial
(0-85g)
no. of moles of NaN03 (nB) =
(85 g mol !)
0 01 mol
/ nBRT
Osmotic pressure (it) = (CRT -
19 x (0 01 mol) x (0 0821 Latin K~* mol-1) x 300 K -------
- -=4-68 atm.
ToTlV)
Q.12.A very small amount of non-volatile solute (that does not dissociate) is dissolved in 5<-8 cm 3 of benzene
(density = 0-889 g cm-3). At room temperature, vapour pressure of the solution is 98-88 mm Hg while that of benzene is
100 mm. Find the molality of the solution. If the freezing point temperature of the solution is 0-73 degree lower than that
of benzene, what is the value of Ky for benzene.
<1.1. T. 1997)
SOLUTION : STEP I. Calculation of molality of solution
Mass of benzene = V x d = 56-8 cm3 x 0-889 g cm3 = 50-5g *= 0 0505 kg
No. of moles of benzene (A)
(50 -5g)
Mass of benzene
Molar mass of benzene (78-0gmol
= 0-65 mol
According to Raoults Law,
PA ~PS
PA
100 - 98-88
( . Solution is dilute)
"A
B
0 -65 mol
100
1-12
B
100
x (0-65 mol) = 0-0073 mol
No. of moles of solute _ 0 - 0073 mol _ 0 145 m

0 0505 kg 0-0505 kg
MASS OF SOLVENT IN
= 0-145 mol kg 1
KG
STEP II. Calculation ofmolal depression constant (Kj)

m = 0145m, ATy = 0-73
AT = 0-73K
/
ATy = Ky x m or Ky =
Vm
(0-73K)
= 5-034 K m'1.
Kr =
V(0145m)
Q.13.A solution of non-volatile solute in water freezes at -0-30C. The vapour pressure of pure water at 298K is 2351 mm Hg and Kr for water is 1-86 degree/molal. Calculate the vapour pressure of the solution at 298 K. (I.I.T.1998)
SOLUTION : STEP 1. Calculation of molality of solution
AT,
K y x m or m
AT,
K,
ATy = 0 - (- 0-30C) = 0-30C = 0-30K, Ky = 1-86 K m"

(0-30K)
(1-86K mol-1)
= 0-16 m
SOLUTE
X
Solutions
ROILING POINT <C)

K*
0-68
100
Y
27
0-53
mole fraction (x &) of the solute
Z STEP II. Calculation of 253
0-98
0- 16m solution means that 0-16 mole of the solute is dissolved in 1 kg of the solvent (water)
s.m J
016
B
= 0-00287
0 16 + 1000 (18
"B +
A
STEP III. Calculation of vapour pressure of solution APA
JfB
Mole fraction of solvent (xA) = I - JCB = 1 - 0-00287 = 0-99713 Vapour pressure of

solution = PAxA = (23-51 mm) x 0-99713 = 23-4425 mm.
Q.14. To 500 cm' of water 3-0 x 10 3 kg of acetic acid is added, 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 enr' respectively. (1.1.T.
2000)
SOLUTION : STEP I. Calculation ofVan't Hoff factor (i)
(aq)
CH3COOH ------^ CH3COO- + H+
-1
(-1
n- 1
2-1
a - ------------ - or 0-23 = -- -- - -r or i = 1 23
STEP II. Calculation of molality of solution (m)
No. of moles of acetic acid
Molality (m)
Mass of acetic acid

Normal molar mass (CH3COOH)
(30g)
(60g mol1)
= 0 05 mol
No .of moles of CH3COOH

Mass of water in kg
(0 05 mol)
500 x 0-997
1000
kg
0-05 x 1000
= 0-lm
500 x 0-997
STEP III. Calculation of depression in freezing point (ATf) of the solution

4 T / = / X K / X m = 1-23 x (1-86 Km"1) x (0-1 m) = 0-229K. Q.15.
(a) Calculate the molarity of water if its density is 1000 kg/m 3.
(b) Match the following if the molecular weights of x, y and z are the same.
Solutions
3.112
Solutions
w
, Wl _ No, of moles of water (1000 g / 18g mol'1)

o arity ( ) Volume of water in litre
IL
55-56 mol L"
= 55-56 M.
1. Which of ihe following 0-1 M aqueous solution will
(b)have
Higher
value ofpoint
the solvent
implies its higher polarity and thus, higher boiling point as well since the boiling
lowestK,freezing
?
point is linked with intermolecular forces. Thus, greater the K, value, higher will be the boiling point of the
solvent. This means that the matching is correct.
Q.16. 1-22 g of benzoic acid is dissolved in (i) 100 g of acetone (K, for acetone = 1-7 K kg mol'1) and fit) 00 g of
benzene (K, for benzene = 2-6 K kg mol"1). The elevation in boiling point are 0-17C and 0-13C respectively.
(a) What are the molecular masses cf benzoic acid in both the cases ?
(b) What do you deduce out of it in terms of structure of benzoic acid ?
Solution : (a) Molecular mass of benzoic acid in acetone solvent
(A) POTASSIUM SULPHATE SODIUM CHLORIDE

)
(C) (UBREA
(D) GLUCOSE.
(// T. 2004)
Kj, x WB x 1000
MR =
(M.L.N.R. 1990)
AT, x WA
2. MOLALITY IS EXPRESSED IN
1
(1-7K kg moP
x (l-22g)
x 1000
(A) GRAMS/LITRE
(B) L)ITRES
/MOLES
(C) MOLES/LITRE
. I22
(017K)
x (100
(D) MOLES
/KG.g)
(C.B.S.E.
MED. 1990)
Molecular mass of benzoic
acid in benzene
solvent
3. THE FREEZING POINT OF EQUIMOLAR AQUEOUS
WILL SOLUTION BE HIGHEST FOR
(A) C6HjNH3d
(B) CA(NO 3)2
K, x WB x 1000
MR
(D) C6HI206.
3
(C) LA(N03)(2-6
K kg moP1) x (122g)x 1000
(0-13K) x (lOOg)
AT,, x WA
= 244 g mol'
(b) The normal molar mass of benzoic acid (C6HJCOOH)

7x 12+2 + 1 6 x 6 + 1 = 122 g mol"1
This shows that benzoic acid behaves normally in acetone while it dimersies in benzene solvent because of
intermolecular hydrogen bonding.
C6H5
o=c-o
Solution : (a) Density of water = 1000 kg/m3

1 Litre of water = i kg = 1000 g
o-c=o
1
C6H5
H
(l.l.r. 2003)
Solutions
3.114
(A) 0-1 M UREA
F<> 0-1 TN SUCROSE
30.
A
A vapour
solution
of) cane
sugar
mass
FC 0-15.
LM ACETIC
ACID pressure
()D
0-1 of
MC
C(molar
L2The
aAsolution
of 5g=of342)
nonisisotonic within1 lOOg
% solution
of a substance
X. The
)
electrolyte
of water
at a particular
molar mass ofisX2985
is Nm'2. The vapour pressure of
temperature
pure
is 43000 Nm" 2. The
(a> water
171-2 at this temperature
(b) 68
molecular mass of solute is :
fc) 34-2
(a) 180
(b) 90
(c) 270
fd)
136-2.
(C.B.S.E.(I.I.T.
Med. 1993)
1998)
(d) 200.
16.
31. A
The
sugar
molal
syrup
freezing
of weight
point214-2
for water
g contains
is 1-86
34-2g
C/m.
of
Therefore,
sugar. The molal
tne concentration
freezing point
of solution
ofOlm
is : NaCI
solution
be :
fa) 0-55in water is expected
(b) to5-5
(a) -(c)
1-86C
(B(d)
) -001.186C (U.T. 1998)
55
(C) - 0-372C
(D) + 0-372C.
32. Which has highest boiling point at 1 atm pressure ?
(a) 0-1 M NaCl
(b)
(M.L.N.R. 1994)
0-1 M Sucrose
17. Vant Hoff factor for 0-1 M ideal solution is :
fc) 0-1
0-1 M BaCh
(d) 10-1 M Glucose.
(a)
(b)
(C) 0 01
(D) None(M.P.P.M.T.
of these. 1998)
33. An aqueous solution freezes at -0186C (Ky = 1-86,
(M.L.N.R. 1994)
K;, = 0-512). What is the elevation in boiling point'?
18. At 25C, the highest osmotic pressure is expected
(a)OT0-186
by
M solution of : (b) 0-512
(c) CaCI
0-86 2
(a)
(C) Glucose
<d) KC1
0-0512.
(b)
(d) Urea.
F.M.P.P.M.T. 1998)
(C.B.S.E.
Med.
1994)
(l.l.T.
1990)
Which pressure
of the following
salts will
have the
4.19.Osmotic
of a solution
is 0-0821
atmsame
at
value
of Van't
Hoff factor
(f)
as thatatof27C
K 4solution
[Fe(CN)
34. temperature
The
osmotic
of 1M
solution
is
ofpressure
300K.
The
concentration
of
in(,|
moles/litre
will be
(a)
2-46 atm
(b) 24-6 atm
(,A)
AI2(S04)3 (B)
NaCI
(a) 0-33 (b)
0-066
1-21 atm
(d)
12-1
atm.
((c)
C) A1(N0
)
{
D
)
Na
S0
.
3 3
2
4
2
(c) 0-3 x lO'
(d)
3.(Roorkee
1990)
(C.P.M.T.
1999)
(C.B.S.E.
Med. 1994)
5.20.
is not
a is
colligative
property
? of0water
35.Which
The of
Vant
factor for
0-1M
Ba(N
12g
ureaHoff
dissolved
in
1 litre
and 683)2 solution
is 2-74.
The degree
of dissociation
4g
of
is also
dissolved
inis1: litre of water.
(a) ATyfb)sucrose
n
The
lowering
in the vapour
pressure
of first case
(a)
9
1
3
%
(b)
87%
(c) AJ
K*.
b {d)
is
(c) 100%
(d) 74%.
(U.T. 1999)
(Pb.
1991)
(a)
B) not
greater
than
second
36. equal
Whichtoof the second
following(does
showC.E.T.
positive
6. The
in ?vapour
pressure
fromlowering
Raoults Law
(deviation
C)relative
less than
second
(d)
double the
second.is
proportional
to the ratio between the number of
fa) Benzene-chloroform
(a)
molecules
to solvent(E.A.M.C.E.T.
molecules 1995)
(b) solute
Benzene-acetone
Isotonic solutions
have same
(b)
molecules
to the total number of
121. solute
molecules
in solution
(a)
Molar
concentration
(c) Benzene-ethanol
solvent molecules to the total number of
(b) (c)
Molality
r
f (d) Benzene-carbon
- (M.P.P.M.T. 2000)
molecules intetrachloride.
solution
(c) Normality
i(d)
solvent molecules to the total number of ions
(d)
these.
(A.F.M.C.
1995)
37. None
Depression
in freezing
point(C.B.S.E.
for 1M
urea,
IN of
SOLUTION
.
Med.1M
1991)
When
mango
placed
intheaqueous
solutionionof
glucose
andpaste
1MisNaCl
are inhas
ratio. fluoride
7.22.500g
tooth
sample
0-2g
hydrochloric
acid, itis the(b)concentration
concentration.
(a) 1 : 2 : 3What
3 : 2 : 2 of fluoride
(a) inShriks
terms of ppm level ? (b) Swells
(c) 1 : 1 : 2
(d) None of these.
fa)
(C)250
Bursts
(fb)
D) 200
Nothing happens.
(Haryana C.E.E.T. 2000)
(c) 400 (d) 1000.
(A.l.I.M.S.
(C.P.M.T.1991)
1995)
* 3.115
Solutions
23.
in b.p.ofofthe
a solution
of lOgofofcolloids,
solute
38. An
For elevation
determination
molar mass
(molar
mass
100) in which
100 g of
water is property
AT*. Theis
polymers
and=proteins
coiligative
ebullioscopic
constant for water is :
used ?
A) 10
) 10AT pressure ft)
(a) (Diffusion
pressure (b)(BAtmospheric
Molal depression constant depends upon

(Osmotic
C) AT* pressure (d) Turgor
(D) AV10.
pressure.
(a) nature of the solute
(C.B.S.E.Med.
Med.2OOO)
1995)
(C.B.S.E.
(b)
the3 solvent
24.
A
molal
aqueous
acid acid
(HX)is
39. nature
To0-2
500of
cm
of
water, solution
3 0 X 10of
3 akgweak
of acetic
isadded
20 pressure
percent
ionised.
freezing
pointwhat
of this
If 23% of
acetic The
acid is
dissociated
will
(c) vapour
solution
1
solution
is (Given
= 1-86C
kg? mol"
for
water)
be
depression
in
freezing
point
K
[
for
water
is
1-86
(d) heat of solution.
(Pb.
C.E.T.
'1 and density of
is 0-997 g cm'3.
(KAkg
) -mol
0-45C
(Bwater
) - 0-90C
1991)
fn) -00-31C
186K
(b) -0-53C.
0-228K
(c)
(d)
9. Mole
CJH0-556K.
J(OH>3 in solution
fc) fraction
0-372Kof glycerine(d)
(U.T. 2000)
containing
36gm
of
water
and
46 gm (L
ofcm
glycerine
IT.
3 1995)
40. The volume of water to be added to 100
of 0-5N
25. is0-1
M 4NaCI
01M CH
3COOH
H2SO
to getand
decinormal
solution
is :solutions are
kept (b)
in separate
containers.
If their osmotic
(a) 0-46
0-40
3
fa) 100 cm
450 cm3 then what
pressures
P(b)
respectively
2 (C.P.M
(c) 0-20
(d) are P[ and0-36
T.1991)
3
will
(c) molecular
be
500
thecm
correct
statement
(d) sodium
400
? cm3.chloride as
10. The
mass
of
determined
osmotic pressure
is :
(A) P, > Pby
(B) P,method
= P2 (K.C.E.T.
2
2001)
(a)41. equal
Depression
is =directly
(C) to
P| 58-5
< P2in freezing point
(D) P|
P2 = 0 proportional
atm.
to
(b) greater
than 58-5
(C.P.M.T. 1996)
fa)than
mole58-5
fraction of the solution
(c)
less
26. Azeotropic mixture of HC1 and H20 has
molarity
the solutionis correct.
(d)(b) none
of theofinformation
(A) 48% HCI

(B) 82-2% HC!
fc) molality of the solution
(Haryana
C.E.T.
(C) 36% HCI
(D)sample
20-2% Paper
HCI. 1992)
fd) molality of the solvent.
11. The molarity of pure water is
(A.F.M.C. 1997)
(Tamil Nadu C.E.T. 2001)
(a)
55-6 (b)
27.
by50
temperature
? will have
42. Which
Which is
of not
the affected
following
aqueous
solutions
(c) 100
<d)
18.
(K.
C.E.T.
1993)
(feezing point ? (B) Molality
(least
A) Normality
12. Which of the following liquid pairs will show
(c) Molarity
(d) Formality.
positive deviation from Raoults Law ?
(A.I.l.M.S. 1997)
(a) Water-hydrochloric acid
28. If all the following four compounds were sold at
(b) Water-nitric
acid which would be the cheapest for
the same price,
preparing antifreeze solution for a car radiator ?
(c) Acetone-chloroform
CH-3METHANOL
OH
(B) C2H1993)
5OH
(D) B(a)
EN2ENE
. (M.P.C.E.E.
13. The
states
that (d)
the mass
a gas3 dissolved
(c)lawCwhich
C3Hof
2H4(OH)
2
5(OH)
in given mass of the solvent at any (A.M.U.
temperature
is
1997)
directly proportional to the pressure of the gas
29. The vapour pressure of a solvent decreases by 10
above the solution is:
mm mercury when a non-volatile solute is added
(a) Joules
(b) Boyles
to the law
solvent. The mole
fractionlaw
of the solute in
the
solution
is
0-2.
What
should
(c) Henrys law
(d) Charles law.be the mole
fraction of
solvent if
decrease
in vapour
14. Increasing
thethe
temperature
of the
an aqueous
solution
pressure
will
cause is to be 20mm of mercury ?
fo)
0-8 in molarity (b) 0-6
(a) decrease
0-4 in molality (d) 0-4.
(b)(c)decrease
(c) decrease in mole fraction (C.B.S.E. Med. 1998)
(d) decrease in % (w/w).
(l.l.T. 1993)
(E) 0-1 M NACL

(KERALA E.E.E. 2001)
SEPARATED
SOLUTE
3.116 ---->
MOLECULES
(II) PURE
(HI) SEPARATED SOLVENT AND SOLUTE
45. Colligative properties of the solutions are those
MOLECULES ; AH SOLUTION ON FORMED WILL BE
properties which depend on the
AHJ *+* AH2 + AH3
IDEAL IF
(a) shapes of the particles

AH, + AH; - AH3
(b) nature of the solvent
(T) AHSO( ^ -ÂH3 - AH, -AH2
(c) nature of the particles only
(D) AHSO,
AH3 - AH| - AHJ
(d) number of the particles only
(e) volume of the solution. (KERALA P.M.T. 2002)
46. Colligative properties are used for the
determination of
(a) molar mass
(b) equivalent mass
(c) arrangement of molecules
(d) melting and boiling points
(E) BOTH (a) AND (bj . (Kerala C.E.T. 2002)
47. 2-5 litre of 1M NaOH solution is mixed with a
3- 0 litres of 0-5 M NaOH solution. The molarity
of the resulting solution is :
(A) 0-80 M
(B) 1 -0 M
(c) 0-73 M
(D) 0-50 M.
(C.B.S.E. Med. 2002)
48. What is the Vant Hoff factor when benzene
vapour pressure falls from 165mm to 162 mm
on addition of 6g of CH3COOH to 3 moles of
benzene ?
(A) 0-56
(B) 0-325
(c) 2
(d) 0-07
(U.P.S.E.A.T. 2002)
49. If liquids A and B form an ideal solution,
(a) the free energy of mixing is zero.
(b) the free energy as well as the entropy of
mixing are each zero.
(c) the enthalpy of mixing is zero.
(d) the entropy of mixing is zero.
(A.I.E.E.E. 2003)
50. In a 0-2 molal aqueous solution of a weak acid
HX, the degree of ionisation is 0-3. Taking KF
for water as 1-85, the freezing point of the
solution will be nearest to
(A) - 0-260C
(B) +0-180<C
(C) - 0-480C
(D) -0-360C
(A.I.E.E.E. 2003)
51. Formation of solution from two components
can be considered as :
(I) Pure solvent---->
Separated
solvent
molecules
; AH,
Solutions
(B) AHSOL^_
43. An aqueous solution of 6-3g oxalic acid dihydrate is
made upto 250mL. The volume of 0-1 N NaOH

required to completely neutralise 10 mL of this
solution is :
fa) 40 mL
(b) 20 ml.
fc) 10 mL
fd) 4 mL. (l.I.T. 2001)
44. 250 ml. of Na2C03 solution contains 2-65 grams of
the carbonate. If 10 mL of the solution is diluted to
one litre, what is the concentration of the resultant
solution ? (Molar mass of Na2C03 = 106).
fa) 0-1 M
(b) 0-001 M
fc)
0-01 M
(d)
10"4 M.
(E. A.M. C.E.T. 2001)
(A)
'2.
1.
(D)
A)
12 (D)
11. (Solutions
.22 (B)
21. (A)
57. The .average osmotic pressure of benzoic acid is 7-8
bar at 37C. What is the concentration of aqueous

KCt solution that could be used in blood stream ?
(a) 0-16 mol
L1
(b) 0-32 mol L_l
l
(c) 0-60 mol L~
(d) 0-45 mol L"1.
(A.I.I.M.S2004)
58. After adding a solute, the freezing point of a solution
decreases to - 0186. Which is the correct value of

TAi> if kf - 1-86 and kt, = 0-512 ?
(a) 0-521
(b) 0 0521
(c) 1-86
(c) 00186.
(Orissa J.E.E. 2004)
59. Relative lowering in vapour pressure of solution
containing non-volatile
solute
is
directly
proportional to mole fraction of solute. Above
statement is :
(a) Henry Law
(b) Dulong and Petit Law
3.117
(c) Raoult's Law (d) Le-chatelicr principle.
(A.F.M.C. 2004)
60. Which of the following colligative properties can
provide molar mass of proteins polymers or
colloids) with greater precision ?
(a) Relative lowering in vapour pressure
(b) Elevation of boiling point
(c) Depression in freezing point
(d) Osmotic pressure
(C.B.S.E. Med. 2003)

(E) RASTS METHOD.
(Kerala P.M.T. 2004)
52. What is the effect of the addition of sugar on the
61. A 0 004 M solution of Na 2S04 is isotonic with a 0 01
boiling and freezing points of water ?
M
of glucose
at the same
temperature.
(a)solution
Both boiling
and freezing
points
increase The
apparent
ofand
dissociation
of Na2S0
4
(b) Bothdegree
boiling
freezing points
decrease
is
(c): Boiling point decreases and freezing point
increases.
(a) 25%
(b) 50%
(d) 75%
Boiling point increases
and freezing point
(c)
(d) 85%.
decreases.
(l.l.T.
Screening
(e) Boiling point increases and
freezing
point2004)
is
NOT AFFECTED.
(Kerala C.E.T. 2003)
53. The volume of water to be added to N/2 HC1 to
prepare 500 cm
jA^nsivers
of N/10 solution is :
(b) 400 cm3
(d) 100 cm3
(Kamatka C.E.T. 2003)
54. During depression in freezing point in a solution, the
following are in equilibrium.
(a) liquid solvent and solid solvent
(b) liquid solvent and solid solute
(c) liquid solute and solid solute. (l.l.T. 2003)
55. Mixture of X = 0-02 mol of [Co(NH 3)jS04]Br and
0-02 mol of [Co(NH3)5Br]S04 was prepared in 2
litre of solution.
1 litre of mixture X + excess of AgNC>3---- Y
1 litre of mixture X + excess of BaCl2--------- Z
No. of moles of Y and Z are :
(a) 0 01,0-01
(b) 0-02,0 01
(c) 0-01,0-02
(d) 0-02,0-02
(l.l.T. 2003)
56. Which of the following statements is true ?
(a) The relative lowering in vapour pressure of a
solution is equal to the mole fraction of the
solute.
(b) Passage of solute molecules towards solution
side through semipermeable membrane is
osmosis.
(c) Boiling point of solution is always lower than
that of the solvent.
(d) Boiling point a liquid is the temeprature at
which its vapour pressure becomes equal to 200
mm.
(Orissa J.E.E. 2003)
(a) 45 cm
(c) 450 cm3
3
31. (A)
41. (O
51. <A)
61. (C)
32 (C)
.42
(D)
.52 (D)
.
3.
13.
23.
33.
(D)
(C)
(C)
<D)
4. (C)
14. (A)
24. (A)
34. (B)
43.
53.
5.
15.
25.
(A)
(B)
(D)
(A)
(A)
35.
45.
55.
7.
17.
27.
(B)
(D)
(A)
(C)
(B)
(B)
37. (C)
47. (C)
44. (B)
54. (A)
6. (B)
16. (C)
26. (D)
36. (A)
46. (A)
56. (A)
8. (B)
18. (A)
28. (A)
38. (C)
48. (A)
57. (B)
58. (B)
9.
19.
29.
39.
(O
(A)
(B)
(B)
10. <0
20. (A)
30. (B)
40. ID)
49. (C)
59. (<)
50. (C)
60. (D)
1 .()
2 -(d)
3. (d)
4 -(c)
K2S04 WILL FORM MAXIMUM IONS IN SOLUTION

(3)
IS THE CORRECT ANSWER.
EXCEPT GLUCOSE ALL OTHER WILL FORM IONS IN
SOLUTION.
JT = CRT
8. (b)
9.(0
MOLE FRACTION --------------------------GLYCERINE-----------^GLYCERINE + ATWATER
Hints & Explanations46
92 0-5
46 36 0-5 + 2-0
92 18
RT 0-0821
RT 0 0821X 300
= 0.33X 10~2 MOL L-1
= 0-2.
10. (O SINCE NACI DISSOCIATES IN SOLUTION, THE
5 -(d) K6 (MOLAL
ELEVATION CONSTANT) IS NOT A

COLLIGATIVE PROPERLY.
6 .(b)
MOLECULAR MASS IS EXPECTED TO DECREASE.
11 .(a)
MOLARITY (M) = ^77 = 55-55 MOL.

(L8GMOL-1 J
= 55-6
7.(0
PPM = J'29J X 10S =400. (500G)
Solutions
12, (d) Addition of benzene will reduce H-bonding

:v in CH3OH molecules resulting in increase
in the vapour pressure.
13, (it) Conceptual problem.
14, (a) Molarity decreases upon increasing the
temperature as volume increases.
, , pA - Ps .. WB
5 ()
- PA
MA
' MB
WA
Freezing point of solution

= 0C - 45rC = - 45"C.
25. (a) Since NaCI is a stronger electrolyte than
CH3COOH, it will dissociate to greater
extent. Therefore P, > P2
26. (d) is the correct answer.
27. (b) Molality is not affected.
1
28. (a) AT/cc
3000 - 2985 = (59)

(189)
3000
WB
(100g)
MB =180 (by calculation)
16. (c)
ATf = iKfm = 2 x 1 -86cC/m x 0-1 m
= 0372CC
F.P = 0 - 0-372C = - 0-372C
(b) For ideal solution,
AT/will be maximum in case of CH3OH

because its molar mass is the least.
29. (b)
_Ap
_
*B
Ap'
Ap'
i = 1.
17. (a) CaCI^ will give maximum no. of ions (3) in

solution.
18. (a) Both will give same no of ions in aqueous
30. (b)
4K++ [Fe(CN)6]-
K4[Fe(CN)6]
20.
AI2(S04)3 - ------^ 2AI3* + 3S042

(a) Both have same lowering in V.P as they have
same no. of moles.
Urea =
68-4g
342 g
Sucrose
or
=
0-2.
21. (a) Isotonic solutions have same molar

22. (b)
concentration
It swells due to osmosis
10 1000
23. (c) AJb=Kbx
100 100
MB =
342
= 68.4
31. (a) Weight of water (W A)

= 214-2- 34-2 = 180g
.. . ... WB 1000
Molality = x -----------Mg WA
(34-2g)
a = -ror 02 = \
1000
1
(342 g mol ) (
24 (a) HX ionises in solution

HX
^H+ + X
I-1
_ WB x R x T
MB X V
R, T and V are constants for isotonic
solutions
71 =
1 = _5_
MB 342
12g
60^ = 02
100
/-I
n-
/ = 1 -2
ATr = ix K/x m
= 1 2 x (1 -86C mol'1) x (0-2 m)

= 0-45C
=q 4
Mole fraction of solvent.

= 1 - 0 4 = 0 6.
solution.
19.
20
*s ^*B*~ = 0-2 X
180
9)
= 0-55m,
180
32. (c) 0-1 M BaClg because it will form maximum
ions (3) in solution
33. (d) For the same solution.
ATfr _ AT/
Ke -'K,
3.119
Solutions
waiakiMj
AT,
or AT6 ~ -j- x Kb
1-86(0-186 C)
41.
42.
x 0-512.
= 0 0512C.
it = CRT
34. (b)
= (1 mol L-1) x (0-0821 L atm
K"1 mor1) x 300 K
= 24 6 atm.
43.
= 500 cm3
Volume of water to be added = 500 - 100
= 400 cm3
(c) Conceptual problem
(d) 0-1 m CaCI2 because it will give maximum
ions in solution.
(a) Equivalent mass of oxalic acid
=
Normality of oxalic acid
35. (b) Ba(N03)2 - 3a2t + 2 N03_ j1
36.
37.
38.
39.
6-3
= 0-87.
Degree of dissociation = 0-87 x 100

= 87 %.
(a) Benzene - chloroform shows negative
deviation from Raoults Law because
attractive forces will increase.
(c) 1 M urea and 1 M glucose have same AT,
value but the value is double for NaCI
solution. The ratio is 1:1:2.
(c) Conceptual problem
(b) CH3COOH dissociates in water as :
CH3COOH - - ----^CH3COQ- + H+
/ -1
a
n-1
or 0-23 =
i-1
2-1
/ = 1 + 0-23 = 1 -23
250
(oxalic acid) (NaOH)
N,V, =NZV2
0-4 x 10 =0-1
V2 =x V2
(60g)
44. (b) Molarity of solution (M)

_ 2 65
1000
106
250 = 0-1 M
(Concentrated) (Diluted)
M- i Vi = M 2 V 2
0-1 X 10 = M2 x 1000
0-1x 10
M? =
1000
= 0-001 M
45. (d) Conceptual problem

46. (a) Conceptual problem
47. (c) M,V, + M2V2 = M3(V1 + V2)
M^V^ + MZV2
M3 = ---------------
(V, + v2)
1000
M3 =
(500x 0-997)
(3g)x 1000
(60g) x (498-5g) =0'1
AT, = /'x K,x m
= 1-23x 1-86x0-1 =0-228 K.
40. (d)
= N2V2
(0-5 N) x (100 cm3) s (0-1N) x V2
(0-5N)x (100cm3)
V, =
= 40 mL
01
WR 1000
Molality (m) = x
MB W A
(3g)
0-4N
63
2-74-1
a = n -3 1
- 1
1-74
= 63
(0-1N)
3- 0
4- 5
1 X 2-5 + 0-5 x 3
2- 5+3
= 0.73M
48. (a) Observed molar mass of CH3COOH :

P
A ~ Ps _ ^
PA " A
6 1
165 MB 3
3.121
Solutions
Solutions
M0
165 x 6
3x3
For
S0 +QUESTIONS
BaCI * BaS0
Type
2
(2)
(0-01 mol) (0-01 mo!)
I.I.T./A.M.M.S. Examinations
56. (a) Conceptual problem.
ASSERTION-REASON
110
Normal molar
mass
The questions
given
below consist of Assertion (A) and Reason (R). Use the following
57. (b) it= CRT or C =
Observed
molar
mass
key to select the correct answer.
(a ) If both assertion and reason are correct and reason is correct explanation for assertion.
60
Q _correct
___________
(7-7 atm)
(b) If both assertion
=
= 0and
explanation
for__________
55 reason are correct bat reason is not
(close to 0-56)
~
7o-0821Latm
IC'morV
31 OK = 0-31
assertion,
49. (c) Conceptual problem.
+
-1
50.(c) (c)
+ X-but
; nreason
= 2 is incorrect.
If HX
assertion isH
correct
mol L .
58.
(b) We know that AT = K x m
&
6
(d) If assertion is- incorrect but
is correct.
nnreason
/-I
and ATf = Kf x m
or 0 3
- Tîr
(e) If assertion and
reason*both are inccorrect.
I - 1-3
ATf
= ~ or ofAT
= K
Molality
concentration
the6solution.
ATf si
xK/ x mis preferred to molarity for expressing the
ATfj
c
b
=Molality
1-3 x 1 85
0 2determined
= 0canx be
more easily than molarity.
AT V
Kf
481 .. Freezing pt. of solution = (0 - 0Vant Hoff factor for benzoic acid is less than 1 in ATf,
benzene. 0-186 x
f
= 0-0521 K.
0 521
(A) For an idea!Benzoic
solution,acid associates in benzene. 59. (c) is the correct answer.
1-86
AH soi = AH
^ + AH
2 - t- donot
AH 3show any osmosis when placed side by side.
Isotonic
solutions
60. (d) is the correct answer.
52. (d) Conceptual problem.
Isotonic solutions have same solute concentration.
53. (B) V x 0-5 N = 500 cm3 x 0-1 N
61. (c) Since the solutions are isotonic, they have
theazeotrope.
same osmotic pressure also.
alcohol
w (500cm3) Ethyl
X (0-1N)
and water 3form maximum boiling
v
l ,00cm
*ioifi)
Attractive forces in solution tend to increase. ^ NajS04 Volume of water added = 500 - 100
In an ideal solution, AH mixing is zero.
^glucose /x 0-004
= 400 cm3
A............B interactions are the same as A.................
and0B
B interactions.
RT =A0-01
- 0...............
1RT
54. (a) Conceptual problem.
/ 0-004
2-5
Addition
of
ethyl
alcohol
lowers
the
freezing
point
of
water.
55. (a) Concentration of tons in 1 litre of the
Na2S04 ~
solution after
mixing will
be reduced
to half
Impurities
always
lower the
freezing point of a solvent.
2Na+ + S042"
H
i.e. 0-01 mol.
v
Out of various colligative properties, only osmotic pressure is used to determine
Br + AgN03-------> AgBr(Y)
i - 1 = 2-5-1
1-5
the molecular
masses of polymers.
a
(001 mol) Polymer (solutions
0-01 mol)
2
donot possess a constant boiling point nor-1freezing3point.
-1
481 )C = - 0-481C
51.
75%.
Greater the molal depression constant of the solvent used0-75
less or
is the
freezing point
of the solution.
Depression in freezing point depends upon the nature of the solvent.
1. Assertion
Reason
2.
3.
4.
Assertion
Reason
Assertion
Reason
Assertion
Reason
5. Assertion
Reason
6. Assertion
Reason
Molarity of the solution changes with temperature.

Molarity is a colligative property.
01 M NaCl solution boils at higher temperature than 0-1 M BaCl2 solution.
Elevation in boiling point depends upon the number of solute particles in the
solution. 1
7. Assertion
8.
Reason
Assertion
Reason
9. Assertion
Reason
10. Assertion
Reason
Solutions
Hints & Explanations

1. (C) Molality does not change with temperature while molarity changes.
2.
(A) Reason is the correct explanation for assertion.
3.
(C) Isotonic solutions have same molar concentration of the solute.
4.
(E) Assertion. Ethyl alcohol and water form minimum boiling azeotrope.
Reason. Attractive forces in solution tend to decrease.
5.
(A)
Reason is the correct explanation for assertion.
6.
(A)
Reason is the correct explanation for assertion.
7.
(C) Polymer solutions have very small elevation in ooiling point and depression in freezing point.
8.
(A) Reason is the correct explanation for assertion.
9.
(C) Molarity depends upon volume which changes with change in temperature.
10. (D) 01 M NaCl solution boils at lower temperature than 0-1 M BaCl2 solution.
jQ-tis-wers
1. (C)
2. (a)
3, (c)
4. (e) S. (a)
6. (a)
7. (cf 8. fa) 9. (c)
10. (d)

Solutions Dinesh

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Solutions

T TABLE 3.1 Types of Solutions

.............................. ................................................ .......................

Strength of a solution may be defined as :

The units of concentration are gL"1 or g dm'3.

Mass percent of a solution may be defined as :

If A and B are the two components of a binary solution,

Mass percent of B =-------Wb, * 100

Volume percent of a solution may be defined as :

Concentrations can also be expressed in terms of weight/volume (i.e. WA/).

Parts per Million (ppm).

Molarity of a solution may be defined as :

Gram moles of the solute

Mass of solute in grams / molar mass

4 -9g / 98g mol'1

= 0-2 mol L'1 (OR 0-2 M)

Gram formula mass of solute

UNITS of FORMALITY : Gram formula mass/Litre.

0 04 Formula mass L"1 or 0-04 F

Molality of a solution may be defined as :

Gram equivalents of the solute

Mass of solute in gram / equivalent mass

Equivalent mass of acid

Molar mass of acid

Equivalent mass of base

____________Molar mass of base____________

Equivalent mass of salt

______Molar mass of salt

Equivalent mass of ion

Charge on the ion

of the solution can be calculated as follows :

Mole fraction of B (xB) =

Volume of solution in litres

Mass fraction of A =Normality of Acid = Molarity x Basicity

Normality on mixing solutions : N]Vj + N2V2 = N3 (V[ + V2)

GJ Problems on Mass Percent/Volume Percent/ppm

Mass of urea = 5g, Mass of water = 95g

Mass of water = 250 - 62-5 = 187-5 G

Problems on Molarity/Molalrty/Mole Fraction

Mass of NaOH / Molar mass of NaOH

Volume of solution = 200 mL =

STEP II. Calculation of molarity of solution

lOg / (74 5g mol-1)

Molarity of solution can also be obtained by applying the formula :

According to available data :

Solution. STEP L. Calculation of the mass of solvent (water)

Molality (M) = (930g/(98gmol *) = 10.43 mo, kg-i = 10.43 m (0-91 kg)

Step 11. CALCULATION OF MOLALITY OF OH' IONS

Ba2* (AQ) + 20H' (AQ)

5-0 L of solution contain methanol =

Mass of C2H5OH = 92 g. Molar mass of C2H5OH = 46 g mol'1,

j-t ^ = 55-55 mol

Mote fraction of CH3OH (*CH30H) = 0-02

0-02 N2 = 55-55 x 0-02 = Mil

Molality of CH3OH solution = 1*13 molal

Molarity of solution (M)

Weight of H2S04 in 100 g solution = 15 0 g

No of gram moles of H2SQ4 _ 15g/(98gmol *)

Calculation of molarity of solution.

No of gram moles of H 2S04

1-56 mol (dm3)"1 = 1-56 M

No of gram equivalents of HjSO*

Volume of solution = 100 mL - "[QQQ" = 01 L

= 0-1 equiv. L-1

Molar mass of base

Partial pressure of the gas