Solutions Dinesh

Solutions
We know that substances exist in three phases i.e. solid, liquid and gaseous phases. We are also familiar
with the general characteristics of these phases. Let us study as to what will happen if the substances belonging
to the same or different phases are mixed 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 phase i.e. the
solution may be homogeneous or heterogeneous. For example, a mixture of oil and water is heterogeneous
while that of salt and water is normally homogeneous. Homogeneous mixture of two or more substances is
known as true solution cr simply a solution. The different constituents present in a true solution or solution lose
their physical identities and cannot be separated from each other by available methods like filtration, settling or
centrifugation etc. However, they must not chemically react with each other. Thus, a true 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. %
Solutions
T TABLE 3.1 Types of Solutions

—.— ............................ — ............................................... — ............... ......
Solute Solvent Example
Gas Gas Air (Mixture of many gases)
Gas Liquid Aerated drinks
Gas Solid Gases adsorbed over metal surface (occlusion). Gases dissolved in minerals.
Liquid Gas Humidity in air

Liquid Liquid * Mixture of miscible liquids (alcohol in water)
Liquid Solid Mercury in an amalgam, Hydrated salts
Solid Gas Iodine vapours in air
Solid Liquid Salts dissolved in water
Solid Solid Alloys of metals e.g. Interstitial solid solution.
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) (4g)
Strength = (250mL) 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.
Solutions • 3.3
If A and B are the two components of a binary solution,
WA X 100
Mass percent of A =
WA + WB
Mass percent of B = ------- Wb„, * 100

WA + 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 VA + V B X 100
VB
V
A + VB
Volume percent of B 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 ^ Volume of A 6
PPmA 'Mass of solution or
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 (ordm3) of the solution
Gram moles of the solute

Mathematically, Molarity (M)
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 :
4 -9g / 98g mol'1 (0-05 mol)

Molarity (M)
250 mL /1000 (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 M2, 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.
Gram formula mass of solute

Mathematically, Formality (F) =
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 :
(2-02g)/101g(formulamass)
Formality (F)= 0 04 Formula mass L"1 or 0-04 F
500mL/1000
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
Mathematically, Molality (m) = 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 :
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.
Gram equivalents of the solute
Mathematically, Normality (N) =
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
Molar mass of acid

Equivalent mass of acid
Basicity (No of replaceable H+ions present)
__________ Molar mass of base __________
Equivalent mass of base Acidity (No. of replaceable OH- ions present)
____ Molar mass of salt
Equivalent mass of salt Total positive charge on cation
Atomic mass of the element
Equivalent mass of element Valency of the element
Formula mass of the ion
Equivalent mass of ion
Charge on the ion
0 3.6 Solutions
• For example, the normality of a solution containing 0-74 g of Ca(OH)2 dissolved in 200 mL
of the solution can be calculated as follows : '•
_ ., c r. Molar mass 74
Equivalent mass ot Ca(UH)2 = = 37 = 37g equiv -i
Acidity
Normality of solution (N) = 0-74 g / 37 g equiv 1 _ 200 011 equiv./L (or 0-1 N)
mL /1000
Normality of solution on mixing two solutions. When volume V! of a solution of normality Nj is
mixed with the volume V2 of another solution of normality N2 then the normality N3 of the resulting solution
(volume = V[ + V2) is given by the equation.
N,V, + N2V2 = N3 (Vi + V2)
Mole Fraction (x)

Mole fraction may be defined as :
the ratio of the number of moles of one component to the total number of moles of all
the components present in the solution.
For a binary solution made up of components A and B.
Mole fraction of A (JCa) =

"A + «B
Mole fraction of B (xB) = "B

«A + "B
Sum of mole fractions (xA + xB) = nA 'B

+ =1
«A + «B «A + «B
Remember
• Mole fraction being a ratio has no units.
• Sum of the mole fractions of different components in a solution is always
equal to 1. _________________________________________________________
Mass Fraction
Mass fraction may be defined as :
the ratio of the mass of one component to the total mass of all the components present in the
solution.
For a binary solution containing two components A and B
W4
Mass fraction of A =
WA + W B
WB
Mass fraction of B =
wA + wB
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 • 3.7
^ Tools for Numerical Problems

Mass of component
Mass Percent ~ x 100
Mass of solution
Volume of component
Volume Percent Volume of solution x 100
Parts of component ^ 6
Parts per million (ppm) Parts of solution
Gram moles of solute ___
Molarity (M) Volume of solution in Litres
Gram moles of solute Molality (m) Mass of solvent ip Kg

Relation between Molarity and Molality
Molarity _ Mass of solvent in kg _ Mass of solution - Mass of solute Molality
Volume of solution in litres Volume of solution in litres
Density of solution x Volume of solution - Moles of solute x molar mass of solute
Gram equivalents of solute

Normality (N) =
Volume of solution in Litres
,, No of moles of component
Mole Fraction = ------- ———;—- ---- -- —- ---
Moles in the solution
Mass of component
Mass Fraction =
Mass of solution
Relation between molarity and density
_ % Strength x Density x 10
Molarity (M) Molar mass of solute
Relation between normality and density
% Strength x Density x 10
Normality (N)
Equivelent mass of solute
Normality of Acid = Molarity x Basicity
Normality of Base = Normality x Acidity
Molarity on mixing solutions : M]V, + M2V2 = M3 '(Vj + V2)
Normality on mixing solutions : N]Vj + N2V2 = N3 (V[ + V2)
• 3.8 Solutions
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 x 100
Mass of solution
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.
Mass of solute , m
Solution. 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
Mass (20g)
Volume of solution ^5T = 11-8 cm3
Density (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
Solutions • 3.9
££ 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)
Mass of NaOH / Molar mass of NaOH

Solution. Molarity (M) =
Volume of solution in Litres
Mass of NaOH = 4g. Molar mass of NaOH — 40 g mol-1,
200
Volume of solution = 200 mL = = 0-2L
1000
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 = -------- -- —; ------ =94-34 cm3
Density (i - uo g cm )
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
lOg / (74 • 5g mol-1)
Molarity (M) - (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)
• 3.10 Solutions
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) _
"Mj
(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)
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.
_ Mass of H2S04/MolarmassofH2S04
Molality (m)
Mass of water in kg
= 930 g ; Molar mass of H2S04 = 98 g mol'1
Mass of H2S04
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
Molality of solution (m)
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
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)
5-0 L of solution contain methanol = x (5-0L) = 9-22 mol.
(1-085L)
3 Example 3.11. Calculate the mole fraction of ethanol in a sample of spirit containing 92% ethanol by
mass. (H. P. Board 2002)
Solution. *C2H5OH -
n
C2H5OH + n\i20
Mass of C2H5OH = 92 g. Molar mass of C2H5OH = 46 g mol'1,
(92 g)
”C2H5OH (46gmor‘) = 2mo1
(8g)
Mass of H20 = 8g, Molar mass of H20 = 18 g mol'1 ; "H2O “ (i8g mol-1) = 0-44 mo1
_ (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
0- 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)
(tooog)
No of moles of H20 (ri|) moj-t ^ = 55-55 mol
Mote fraction of CH3OH (*CH30H) = 0-02

No of moles of CH3OH (n2) can be calculated as :
n2 _ n2
(XCH3OH) = 0-02
«! + /i2 55-55 +
n2 - 0-02 n2 = 55-55 x 0-02 = Mil
Mil
0-98 n2 = 1 • 111 or n2 = = 1*13 mol
0-98
• 3.12 Solutions
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 cnr

Density (0 ■ 994 g cm 3)
(1-13 mol) (1-13 x 1000 mol)
Molarity of solution (M) f 1042-4 , 3>| (1042-4 dm3)
dm
l-fMT1000 J
= 1-08 mol (dm3)'1 = 108 M
3 Find the molarity and molality of a 15% solution w/w of H 2S04 (density of
H2S04 = 1-02 g cm-*) ' (A.I.S.B. 1999. D.S.B. 1999)
Solution. 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 *)

Molality of solution (m)
Mass of water in kg (0 085kg)
= 1-8 (mol kg"1) = 1-8 m

Calculation of molarity of solution.
No of gram moles of H2S04
Molarity of solution (M)
Weight of solution 100 g ; Density of solution =
3
1Mass
-02 gofcm"
solution _ (100 g)
Volume of solution 98 0 cm3
Density (l-02gcm"^>
(15-0g)
No. of gram moles of H2S04 (98gmor1) =0-153 mol
(0-153 mol)
Molarity of solution (M) 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
= 49 0 g equiv.-1
Mass of H2S04 = 0-49 g ; Equivalent mass of H2S04 = Molar m— =
Basicity 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 *)
= 0-1 equiv. L-1 01 N
(01 L)
OExample 3.15. Calculate the number of molecules of oxalic acid (H2C2O4.2H2O) in 100 mL of
0- 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
Molar 0-2 equiv.
2x 1 +L'2 x 12 + 4x 16 + 2x 18 126
Equivalent mass of acid = Basicity ~ 2 2
1
= 63 g equiv.'
100
Volume of solution 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. L”1) 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
6-022 x 1023
1-26 g of oxalic acid has molecules - X (1-26 g) = 6-022 x 1021
(126 g)
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
(0-5 equiv. L-1) - (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
Volume of resulting solution = 600 mL = = 0-6 L

1000
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)
3
Solution. Volume of solution = 1000 cm
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
Molality of solution (m) ------ 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 H2S04 (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) _ 100
Volume of solution = mL
Density (1-218 g mL”1) 1218
100
1-218 mL of sample contains H2SO4 = 30 g
Solutions • 3.15
(30 g) x (V mL)
V mL of sample contains H2SO4 = (0-3654 V) g
(100/ 1-218 mL)
For 70% H2S04
Mass of H2S04 = 70 g ; Mass of solution = 100 g
Mass of solution (100 g) 100
Volume of solution = Density (l-OlOgmL1) 1610 mL
100 mL of sample contains H2SO4 = 70 g

1-610
(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) Volume of solution in litres
(1-4924 Vg)/(98 gmor1)

= 7-614 mol L-‘ = 7-614 M
(0 002 V)L
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)
= 1 mol L'1 = 1 M
(0-1 L)
• 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
0998 kg) = 1-002 mol/kg = 1-002 m
Step III. Calculation of mole fraction of NaOH

Mass of NaOH
(4 g)
No. of moles of NaOH ~ ^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
NaOH (0-1 mol)
Mole fraction of NaOH = = 0-018
n
NaOH H2o (0 ■ 1 mol) + (5 - 54 mol)
+n
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 of Na2S203 (474 g) iriA

mass Na2S203 = M . JJJ * 100 - 77100 = 37-
92
Mass of solution ' (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 mol
Molar mass (158 g mol" )
Mass of water _ (776 g) _ 43. j t
No. of moles of H20 = Molar mass (18 g mol-1) mol
Solutions Mole fraction of Na2S203 = 3.17
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)
...... (cn2.. No of moles of SiCK2- ions (3 mol) _ , „
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 =
Moles of H2S04
(11-5 mol L-1) =
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 *)
' 5
mot Kg ) - —rnwnj—rnvr:----------------
(l00O d - 1127)
kg
1000
• 3.18 Solutions
,0, , .. _ (11-5mol)
or (94-5 mol kg ) - jjoOOd - 1127)
1000 kg
/n„ , ,, . (1000 - 1127)

or (94-5 mol kg'1) x ---------- —--------- kg = (11-5 mol)
11-5 x 1000
or (lOOOd- 1127) =--------- —— ---- = 121 *7
94-5
121-7 + 1127 1248-7
d= = 1-2487
1000 1000
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 25°C 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
LiJ
Molarmass (158-0gmol )
Mass of water (95-0g)

No. of moles of water - w . ------------------- -rj— = 5-278mol
Molar mass (18-Og mol *)
Mass of solution = —(j.QQ'Qs) = 9 6 . 1 5 m L
Volume of solution = (1-04 g mL *)
Density
{a) Calculation of molarity of solution.
. ,.. .... Moles of Na2S203
Molarity of solution (M) = — --------------------- -- 1 3 -------
(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) = «B (0-0316 mol)

"B + «A (0-0316 mol + 5-278 mol)
(0-0316 mol)
= 5-95 X 10-3.
(5-3096 mol)
Solutions • 3.19
♦ 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,
• 3.20 Solutions
It is a common experience that the ionic solids differ in their solubility in water. For example, MgS04 is
highly 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.
2. 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 Glauber’s salt (Na2SO4.10H2O) in water is quite interesting. It initially increases
upto 32-3°C 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.
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.
Gas Water Ethanol Benzene

Hydrogen 0017 0080 0-060
Nitrogen 0015 0-130 0-104

Oxygen 0 028 0-130 0-165
Carbon dioxide 0-88 3-00 —
* For the detailed study of the concept of solubility product please consult unit Equilibrium-II from Companion
Chemistry for class XI.
Solutions • 3.21
Factors Influencing the solubility of a Gas

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).
2. Effect of temperature. In general, the solubility of a gas in a liquid decreases with the rise in
temperature. The process of dissolution is, exothermic because the gas contracts in volume and energy is
released during contraction. According to Lechatelier’s principle, the increase in temperature favours the
reverse process. Therefore, the solubility decreases with the increase in temperature.
Gas + Liquid ^ ^ Dissolved gas ; AH = -ve

(solution)
3. Effect of Pressure. This is a very important factor because the solubility of any gas in a particular
liquid increases when it is compressed or the pressure is increased. This exercise actually brings the molecules
closer and they liquefy to be a part of the solution. The relation between pressure and solubility is guided by
Henry’s 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
_____ Partial pressure of the gas ____

or
Mole fraction of the gas in the solution e
V
Here KH is known as Henry’s Law constant 3w
To illustrate this, a graph has been plotted between the i/i t
values of the partial pressures of HC1 (g) dissolved in -U
.21
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 Mole fraction of HC1
the same way. These are given in table 3.3. in cyclohexane
A FIGURE 3.1. Mole fraction
of HCI in solution.
• 3.22 Solutions
T TABLE 3.3. KH values of different gases in water

Gas Temperature (K) KH(Torr)
He 293 10-9 x 107

H2 293 5-2 x 107
N2 293 5 75 x 107
N2 303 6-68 x 107

02 293 2-95 x 107
02 303 3-52 x 107
298 1-24 x 106
co2
H2S 298 4-12 x 105
From the data collected, it is quite obvious that

(a) higher the value of KH for a gas, lesser will be its solubility in a given solvent. Thus, solubilities of
He, H2 and N2 in water at 293 K at the same pressure follow the order H2 > N2 > He.
(b) as the temperature increases the solubility of the gas tends to decrease. Thus, nitrogen is more
soluble in water at 293 K than at 303 K.
Remember
• Helium is employed to dilute the oxygen used as breathing gas during deep- sea diving
because it is the least soluble as compared to all the gases. This gives lesser bubbles in
the blood during decompression causing lesser discomfort to the divers.
• As the solubility of both oxygen and nitrogen in water decreases with increase in
temperature, aquatic species live more comfortably in cold water than in
_________________ warm water due to greater solubility of these gases in water.___________________
Applications of Henry's Law
The law is useful in many ways both in industry and in explaining biological phenomena. For example,
(i) In order to increase the solubility of C02 gas in soft drinks and soda water, the bottles are normally
sealed under high pressure.
(it) As pointed above, oxygen to be used by deep sea divers is generally diluted with helium inorder to
reduce or minimise the painful effects during decompression.
(Hi) As the partial pressure of oxygen in air is high, in lungs it combines with haemoglobin to form
oxyhaemoglobin. In tissues, the partial pressure of oxygen is comparatively low, threfore
oxyhaemoglobin releases oxygen in order to carry out cellular activities. Limitations of Henry's Law
Although Henery’s Law has vital applications, but if does suffer from some limitations as well. These are
listed :
(i) The law is applicable to gases only under ideal conditions i.e. under low pressure and high
temperature.
(ii) The molecules of the gas should not dissociate or associate in solution i.e. the gas has same
molecular state in the liquid as well as gaseous phases.
(iii) The gas should not react chemically with the solvent to form any compound. For example,
combines with water to form NH4OHfa^ which dissociates as follows :
NH3fol + H20(/> ------- > NH4OHfa^ ------- ± NH,f(aq) + OH~(aq)
Solutions • 3.23
3Example 3.23. If N2 8as >s bubbled through water at 20°C, how many millilitres (at STP) of N 2 would
dissolve in a litre of water ? Given that the partial pressure of N2 is equal to 742-5 torr and KH for nitrogen =
5-75 x 107 torr.
Solution, stop I. Calculation of no. of moles of N2.
According to Henry’s Law.
Partial pressure of N2 (742-5 torr)
Mole fraction of N2 (*N2 ) 1 29 x 10"5
KH for N2 (5-75 x 107 torr)
"N2 L.
Now, *N2 =
n
N2 + ,lH20 nH20
(rtN2 has been neglected in the above expression since the gas is very little soluble in water)
*N,2 = 1-29 x 10"5 ; "H2O = 2—( = 55-55 mol

(18 g mol-1)
«N2 = *N2 X «H2O = (I-29 x 10'3 x 55-55 mol) = 7-16 x 10"4 mol. Step II
Calculation of volume ofN2 at S.T.P.
1 mole of N2 at S.T.P. occupy = 22400 mL
7-16 x 10~4 mole of N2 at S.T.P, occupy = (22400 mL) ^ /7>1g x io~4mol) = 16-04 mL
(1 mol)
3Example 3.24. The Henry Law constant for oxygen dissolved in water is 4 34 X 104 atm at 25° C. It
partial pressure of oxygen in air is 0-2 atm. under ordinary atmospheric conditions, calculate the
concentration (in moles /lit re) of dissolved oxygen in water in equilibrium with air at 25° C.
(C.B.S.E. Sample Paper 2003)
Solution. According to Henry’s Law,
x Partial pressure of 07 - _________ 0_• 2 atm = 4 - 6 x 1 0 -6

Mole fraction of °2 (*02 ) = --------- - ^ -------------- - (4-34 ;x 10 atm)
KJJ for 0 2
”02 _ nQ2
Now, V 2
° ”02 H20 H20
+nn
(«o2 has been neglected in this expression since the gas is very little soluble in water)
(lOOOg)
*o2 = 4-6 x 10"* i nH2o (18gmol"1) “ 55 55 mo1’
rtQ2 = x0l x «H2O = (4-6 X 10"6) X (55-55 mol) = 2-55 x ltHmol.

OLxample 3.25. What is the ratio of the solubilities of N2 and 02 in H20 at 373 K, given that KH (N2) = 12-6
x 104 atm and KH (Of) = 7 01 X 10* atm. Assume that piNf = 0-80 atm and p(Of = 0-20 atm.
Solution.The ratio of the solubilities of the gases can be expressed in terms of their mole fractions.
According to Henry’s Law,
• 3.24 Solutions
*C2> » " (0-80 atm)

"-H(N2)
(12-6 x 104atm)
_ P(.02> _ (0-20 atm)
K
H(02)
l (0 2 )
(7-01 x 104 atm)
(0-80 atm)
•*(N2) = x (7-01 x 104atm) _
(12-6 x 104atm) (0-20 atm) ” 2'22
■^02)
Solid Solutions
The solid solution, as the name suggests, is formed by mixing two solid components in a suitable
manner. Such solutions are of two types :
1. Substitutional solid solutions. In the solutions, some atoms, molecules, or ions belonging to one
solid substance replace similar species belonging to the other solid in its crystal lattice as shown in the Fig.
3.2(a). The common examples of solid solutions are the alloys e.g., brass is an alloy of copper and zinc.
Similarly, coinage silver is an alloy of silver and copper.
OCDCÔO
0( X X XX)
VAÂ yv 3\ .A. J
©0cxa©o OO0OS0
Solvent (^) Solute ^ Solvent o Solute

(a) Substitutional solid (b) Interstitial
solution solid solution
▲ FIGURE 3.2, Types of Solid solutions.
Interstitial solid solutions. Solid solutions can also be formed when atoms of small size occupy the
voids or interstices that exist in the crystal lattices of certain metals. This leads to interstitial compounds.
For example, tungsten (W) has a face-centred cubic closed packed arrangement (f.c.c). In case carbon
atoms occupy the vacant or interstitial sites, tungsten carbide (W c) results which is extremely hard and is
employed for making grinding and cutting tools. The arrangement of components in such a solution has
been shown in Fig. 3.2(b).
jf^robleryiA <2ôr jf^ructice

3.1. A solution of naphthalene in benzene is 3% by mass of naphthalene. What is the mass percent of benzene
?
[Ans. 9796]
A solution contains 20 g sodium chloride in 95 cm3 solution. The density of solution is 1-25 g cm-3.
What is the mass percent of NaCl ? [Ans. 16-84 %)
‘ 3.3. A solution has been prepared by dissolving 60 g of methyl alcohol in 120 g of water. What is the mole
fraction of methyl alcohol and water ? (H.P. Board 1995) [Ans. (i) 0-220 (ii)
0-780]
■ 3.4. Calculate the molality of a sulphuric acid solution in which mole fraction of water is 0-85.
(A.I.S.B. 1999) [Arts. 9 8]
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 H2S04 by mass (density = 1-10 g mL*1).
Calculate : (/) Molarity (ii) Normality (Hi) Molality of solution. (A.I.S.B. 1999)
[Ans. (i) 1-68 M (ii) 3-36 N (Hi) 1-8 m]
• 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[
• 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
of water are mixed together. (Haryana Board 2003) [Ans. 0-09]
• 3.17. 6X10"3 g oxygen is dissolved in per kg of sea water. Calculate the ppm of oxygen in sea water.
(Pb. Board 2003 Supp. 2003) [Ans. 6 ppm)
• 3.18. 200-0 mL of calcium chloride solution contains 3-01 x 10 Cl* ions. Calculate the molarity of the solution
22
Assume that calcium chloride is completely ionised. (Pb. Board 2003 Supp.) [Ans. 0- 125M]
---------------------------------------------------------------------------------------------------------------- - - • • •
• 3.4 VAPOUR PRESSURE OF PURE LIQUID
We all know that the 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 molecules
present on the surface are being pulled inwards or downwards by the molecules present below 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 order to increase their free
movement also called randomness. In doing so, they take up certain energy from the rest 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 molecules in a liquid
experience.
In an open container, the evaporation of the liquid continues because the decrease in average kinetic
energy or the loss of energy is compensated by the surroundings. Ultimately, the entire liquid evaporates from
the container which becomes dry.
• 3.26 Solutions
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 Temperature
predicts the magnitude of the intermolecular forces. Higher
the vapour pressure of a particular liquid, lesser will be the ▲ FIGURE 3.4. Vapour pressure-
magnitude of these forces. temperature curves for some liquids.
Solutions • 3.27
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 and 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 Dalton’s 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
Raoult’s 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,
P°A = it x 1
Thus, PA = P^xA
[PA = Vapour pressure of the component when present in pure form]
The Raoult’s 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, Raoult’s 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 xA for
a volatile component in the solution will remain less than 1 simply because
X\ + xB = 1. Therefore, PA < P^ (VJCA < 1)
Solutions • 3.29
Thus the vapour pressure of the solution containing a non-volatile solute will be always less than the
vapour pressure of the pure solvent or there will be lowering in vapour pressure.
Mole Fraction of the Components in the Vapour Phase
The mole fraction of the volatile components in the vapour phase can be obtained with the help of
Dalton’s Law of partial pressures. Let the mole fraction of the two volatile components A and B in the
vapour phase of a solution be YA and YB respectively and PA and PB be their partial vapour pressures. Let
P be the total pressure in thr. vapour phase. Thus,
PA = YAP and PB = YBP (in vapour phase)
PA = *APA and PB = *BP°B (According to Raoult’s Law)
VAP - x.Pl »r VA - ^4- -
Y.P = *„Pi or Y„ . MS- = £
Thus, the mole fraction of each volatile component of binary solution is the ratio of its partial vapour
pressure and the total vapour pressure of the solution in the vapour phase.
Raoutt's Law as a special case of Henry's Law
We have studied that according to Raoult’s Law the vapour pressure of volatile component (A) in
a given solution is given as :
PA = PAjrA (According to Raoult’s Law)

In the solution of a gas in a liquid, the gaseous component is normally so volatile that it exists as a gas
and its solubility in the liquid is governed by Henry’s Law according to which
PA “ KH*A (According to Henry’s Law)
If we compare the two expressions, we find that in both the cases, the partial vapour of the volatile
component or gas is directly proportional to its mole fraction in the solution. However,
proportionality constants P^ and KH are different. Thus, Raoult’s Law may be regarded as a special
case of Henry’s Law in which KH becomes equal to P^.
♦ 3.7 IDEAL AND NON-IDEAL SOLUTIONS

The binary solutions of the volatile liquids can be classified into two types. These are : Ideal solutions
and Non-ideal solutions and are discussed as follows :
Ideal Solutions
A solution is said to be ideal
if it strickly obeys Raoult’s Law at all concentrations and temperatures.
Thus, if A and B are the two components of the solution, then
• 3.30 Solutions
It may be noted that in order that a solution may behave ideally, the solute and solvent must be of same
nature. Thus, if A and B are the two volatile components of the solution, there should not be any
change in the magnitude of the forces of interaction when the two are mixed. This means that A ............. B
interactions must be the same as A ............... A and B .............. B interactions. When such solutions are
prepared, there should not be any change in volume and the enthalpy change must be also zero. The
characteristics of an ideal solution are listed as follows :
(i) It must obey Raoult’s Law at all concentrations and temperatures.
(ii) There should not be any change in the magnitude of forces of interaction when the components are
mixed.
(iii) Both the components present in the solution must have similar structures and polarity.
(iv) Volume change on mixing must be zero.
AVmjXjng = zero or VSO|Vent +
(v) Enthalpy change on mixing must be zero, i.e. AHmixing is zero. * (ii) (iii) (iv)
Remember
It is very difficult to have an ideal solution. Under the conditions mentioned above,
the solutions tend to become ideal. Dilute solutions in which the concentration of
the solute does not exceed 5 percent are generally regarded as ideal solutions.
Examples of Ideal Solutions : It has been pointed out that the solutions become ideal in case
solute and solvent are of similar nature. A few examples of ideal solutions are :
(i)
Benzene and toluene
(ii) n-Hexane and n-heptane
(iii) Ethyl bromide and ethyl iodide
(iv) Bromobenzene and iodobenzene
Graphical Representation of the
Behaviour of Ideal Solution. According
to Raoult’s Law,
PA = Pi*A and PB = P^B
This means that the vapour pressures
of the components present in a solution
are the linear functions of their mole
fractions. Graphs showing the variation
between the partial vapour pressures and
the corresponding mole fractions for the
components A and B for a binary solution
are shown in the Fig. 3.6 ▲ FIGURE 3.6. Graphical representation of the
From the graph the following behaviour of ideal solution consisting of
generalisations can be made components A and B.
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
Solutions • 3.31
This means that the vapour pressure of liquid A is maximum when x A = 1 and is zero when *A = 0.
2. Straight line (II) also indicated by dotted line represents the variation in vapour pressure with change
in mole fraction for liquid B.
When xB = 1 (liquid is pure), then PB = PgXB = Pg
When xB = 0 (liquid B is absent) then PB = PgXB = 0
This means that the vapour pressure of the liquid B is maximum when x B - 1 and is zero when *B = 0
3. The total vapour pressure P of the solution as indicated by the normal line (III) is the linear sum of the
partial vapour pressures of the volatile components A and B present in the solution.
p = pA + pB = p;*A + PB*B
It also indicates that the vapour pressure of the ideal solution at any stage lies in between the vapour
pressures P^ and Pg
Non-Ideal Solutions
Solutions which fail to fulfil the characteristics of an ideal solution are known as non-ideal solutions. For
such solutions,
(i) Raoult’s Law is not obeyed i.e. PA * P^JCA and PB * PgXB
(if) A ...... B interactions are different from A ............ A and B ........ B interactions.
(Hi) There is a change in volume when the two components are mixed i.e. AVmixing * zero.
(iv) There is a change in enthalpy when the two components are mixed i.e. AHmixing * zero.
The important characteristics of the ideal and non-ideal solutions are compared in the table 3.2
▼ TABLK 3.2 Comparison of the characteristics of ideal and non-ideal solutions

Ideal solution Non-ideal solution
1. The forces of interaction of the components in the The forces of interaction of the components in 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.
2. There is no change in volume on mixing the There is a 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
components i.e. AHmjxing = 0 i,&, AHmixing £ 0.
4. Components obey Raouit’s Law at all temperatures Components deviate from Raoult’s Law i.e.
and concentrations i.e.
PA * PA** ’ Pfi * PB*8'
PA = PA*A. PB = PB*B
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 Raoult’s Law.
• Solutions showing negative deviations from Raoult’s Law.
• 3.32 Solutions
Non-ideal solutions showing positive deviations from Raoulfs Law

Non-ideal solutions show positive deviations from Raoult’s Law in case on mixing the two
volatile components of the solution, the magnitude of forces of interaction decrease i.e. A ........................ B
interaction is less than the A ......... A and B .......... B interactions. As a result, the partial vapour pressure
of each component and the total pressure of the solution will be greater as compared to an ideal solution.
PA > P°A*A and pB > P VB
▲ FIGURE 3.7. Graphical representation of non-ideal solution having +ve deviation

from Raoult’s 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 Raoult’s 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 Raoult’s
Law are :
(i) Ethyl alcohol and cyclohexane
(ii) Acetone and carbon disulphide
(iii) Acetone and benzene
(iv) Carbon tetrachloride and chloroform
(v) Ethyl alcohol and water
(vi) Acetone and ethyl alcohol
Solutions • 3.33
Explanation. Let us analyse the behaviour of the solution when ethyl alcohol and cyclohexane are
mixed. In ethyl alcohol molecules, strong intermolecular hydrogen bonding is present because of their polar
nature. The presence of cyclohexane molecules will naturally reduce the hydrogen bonding and thus the
escaping tendency of the alcohol molecules will increase. Same thing will happen for the molecules of
cyclohexane because the presence of alcohol molecules in the in-between space will reduce the attractive
forces which are mainly van der Waal’s 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 as a whole will be more than that of an ideal solution.
6+ 6- S+ 5' S+ 6 * 5+ 5‘
H-O ------- H-0 -------- H-0 ........... H-O-
i
i C2H5
C2H
^6 ^1 2 C fc Hj5j C 6 H,2
Non-ideal solutions showing negative deviations from Raoult's Law.
Non-ideal solutions show negative deviations from Raoult’s Law in case on mixing the volatile
components of the solution, the forces of interaction increase i.e. A.... B interactions become more
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, the behaviour of such a solution has also been represented in the Fig. 3.8. As expected, it is
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.
• 3.34 Solutions
(ii) AHmixing is negative. Energy is expected to be released because of the increase in the forces
of interaction. Therefore, the process of mixing is exothermic in nature or AH mixing is negative.
In case the solute is a solid, its solubility in the solution is expected to decrease with rise in
temperature.
Examples of solutions. A few examples of the solutions responsible for negative deviations from
the Raoult’s Law are listed.
(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 f
components present in the solution. As a result, they will have lesser /CH3
tendency to escape out of the liquid mixture than when they were present Cl—C—H ........ Q=C
alone in their respective containers. This will, quite obviously, decrease 'CH3
Cl Acetone
the vapour pressure of each component in the solution and also that of the
Chloroform
solution as a whole.
The important characteristics of the non-ideal solutions which exhibit positive and negative deviations
from Raoult’s Law are compared below in the Table. 3.3
▼ TABLE 3.3 Comparison of the characteristics of non-ideal solutions showing positive and
negative deviations from Raoult’s Law
Solutions with + ve deviations Solutions with -ve deviations
1. A ..... B interactions are less than A .............. A and

A.... B interactions are more than A ........ A and B....B
B.... B interactions.
interactions.
2- PA > P°A*A and PB > P^B
PA < P A*A and PB < P°BXB AVmixing is negative AHmixing is
3- AVmjxing is positive
negative
4. AHmijing is positive
Solubility of solute (if solid) will decrease with rise in
5. Solubility of solute (if solid) will increase with rise in temperature.
temperature
♦ 3.8 CONSTANT BOILING LIQUID MIXTURES (AZEOTROPES)

We have studied that in solutions which show positive deviations from Raoult’s 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.
Solutions • 3.35
Types of Azeotropic Mixtures

Azeotropic liquid mixtures present in binary solutions are cf two types. These are known as minimum
boiling azeotropes and maximum boiling azeotropes.
Minimum Boiling Azeotropes. These are formed in case of binary liquid mixtures showing positive
deviations from Raoult’s Law. For examle, a liquid mixture having 95 57 mass percent of ethyl alcohol and
4-43 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
T TABLF. 3.4. Minimum Boiling Azeotropes
Components Mass % of B Boiling points (K)

A B in the azeotrope A B Azeotrope
Water, H20 Ethanol, C2H5OH 95-57 373 351-3 351-1

Chloroform, CHCI3 Ethanol, C2H5OH 67 00 334 351-3 332-3
Benzene, CfiHe Ethanol, C2HJOH 32-40 353-2 351-3 341-2
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
Components Boiling points (K)

Mass % of B in ________ ___ i— ______ _____
A B the azeotrope A B Azeotrope
Water, M20 Hydrogen chloride, HC1 20-20 373 188 383

Chloroform, CHCI3 Acetone, (C^^CO 20-00 334 329-25 347-7
Chloroform, CHCI3 Methyl acetate, CH3COOCH3 23 00 334 330 347-8
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 been
illustrated in Fig. 3.9 by taking the example of ethanol and water. How ever, in case of maximum boiling
azeotrope, the trend is the reverse. Hence, the boiling point of the
• 3.36 Solutions
mixture is more than the boiling point of any of the two components in pure slate. This has been shown
in Fig. 3.10.
▲ FIGURE 3.9. Boiling point diagram for A FIGURE 3.10. Boiling point diagram for
ethanol-water mixture leading to minimum HCI-Water mixture leading to maximum
boiling azeotrope boiling azeotrope.
Separation of the components from a binary Azeotropic Mixture
Wc have learnt that an azeotrope is a constant boiling mixture and it is not possible to separate the
components from the mixture by fractional distillation. However in some cases, the separation is needed. For
example, rectified spirit is a mixture of 95-5% alcohol and 4-5% water. It is an azeotropic mixture. Completely
pure alcohol, also known as absolute alcohol is needed for certain experiments in the laboratory and also for
some other purposes. In order to achieve it, rectified spirit is mixed a suitable amount of benzene and is
subjected to fractional distillation known as azeotropic distillation. Three fractions at different temperatures are
collected
(i) The fraction at 331’8 K is a ternary azeotrope (constant boiling mixture), containing 7-4% water,
74-1% benzene and 18 5% alcohol.
(ii) The second fraction obtained at 341-2 K is a binary azeotrope in which benzene and alcohol are
present in the ratio of 67-7% and 32-2% by mass respectively.
(iii) The last fraction collected at 351 K pure ethyl alcohol or 100% alcohol also called absolute
alcohol.
Tools for Numerical Problems
For binary solutions containing volatile components
PA = PA*A '• = Partial V.P. of component A
PA = V.P. of pure component A jrA =
Mole fraction of component A
PB = PBxB r PB = Partial V.P. of component B
Pg = V.P. of pure component B xB =
Mole fraction of component B
P = PA + PB : For ideal solution.
In the vapour phase :
PA (Partial V, P. of A in vapour phase)

Mole fraction of A :
P(TotalV.P )
PB (Partial V. P. of B in vapour phase)
Mole fraction of B : P (Total V.P.)
Solutions * 3 37
The vapour pressure of ethanol and methanol are 44-5 mm and 88-7 mm of Hg
respectively. A solution is prepared by mixing 60g of ethanol and 40g of methanol. Assuming the solution to
be ideal, calculate the vapour pressure of the solution. (H.P. Board 2002)
Solution :
Mass of CHÔH (40 g)

No. of moles of methanol («g) ~ Gram molar mass (32gmol ’) = 1 - 25 mol
Mass of CjH.OH (60g)

No. of moles of ethanol (nA) = Gram molar mass (46g mol 1) = 1-30 mol
«B (1-25 mol)
Mole fraction of methanol (XB) = n + n (1-25 mol + 1-30 mol) = 0-49
B A
Mole fraction of ethanol (xA) = «A (1-30 mol) = 0-51

nA + nB (1-25 mol + 1-30 mol)
Vapour pressure of pure mathanol (P B) = 88 7 mm
Vapour pressure of pure ethanol(P^) = 44-5 mm Partial vapour pressure of methanol (Pg)
= Pg-^B ~ (88-7 mm x 0-49) = 43-46 mm Partial vapour pressure of ethanol (PA) = PA*A = (44-5
mm x 0-51) = 22-70 mm Since the solution is ideal in nature,
Total vapour pressure of solution (P) = PA + PB = (22-70 + 43-46) = 66-16 mm.
CT sample 3.27. j}xe vapour pressure of an aqueous solution of glucose is 750 mm of mercury at 100°C.
Calculate the molality and mole fraction of solute. (Haryana Board 2001f
Solution : Calculation of mole fraction of solute
Vapour pressure of pure water at 373K (PA) = 760 mm Hg Vapour
pressure of aqueous solution at 373K (P) = 750 mm Hg
* P
According to Raoult’s Law, P = p. JCA or xA = —r-
PA
xA = (75° mm Hg) = 0-987 (760 mm
Hg)
Mole fraction of solute (JCb) = 1 - xA = 1 - 0-987 = 0-013.
Step 1 Calculation of molality of solution.
According to available information,
1 mole of the solution contains 0-013 mole of solute (glucose) and 0-987 mole of solvent (water) Mass
of 0-987 mole of water = 0-987 mol X (18 g mol-1) = 17-766 g = 17-766 x 10"3 kg
No. of moles of glucose Molality of solution (m) ~
Mass of solvent in kg“
(0-013 mol) 0-73 mol kg'1 0-73m.

(17-766 x 10-3kg)
Solutions
Example 3.28. Two liquids X and Y on mixing form an ideal solution. The vapour pressure of the
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 mixed,
the vapour pressure of solution thus formed is 560 mm Hg. What will be the vapour pressure of the pure X 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 P Y respectively.
In first solution :
Mole fraction of X = 3 = 0-75

«x + «Y 3+1 4
Mole fraction of Y = »Y . 1 J_ = 0-25

«X + «Y 3+1 4
According to Raoult’s Law,
P°x x 0-75 + P°y x 0-25 = 550 mm ...d)
In second solution :
n
Mole fraction of X = x 4 4 = 0-8
nx + nY 4+1 5
ny 1
Mole fraction of Y = _ J_ = 0-2
nx + nY 4+1 5
According to Raoult’s Law
P°x x 0 8 + P°Y x 0 2 = 560 mm ...(H)
Multiply equation (i) by 4 and equation (ii) by 5
3P°x + p Y = 550 x 4 = 2200 mm 4P°x + P°Y ...(Hi)
= 560 x 5 = 2800 mm Subtract - P°x = (2200 - 2800) = - 600 ...(iv)
mm
P°x = 600 mm
Substitute the value of Px in equation (Hi)
3 x (600 mm) + P°y = 2200 mm or P°y = 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.
_______ Mass of ethanol _______ (46g)

Solution : Moles of ethanol (nB) Molar mass of ethanol (C2HJOH) = 1 mol
(46 g mol"1)
______ Mass of methanol ______ 64 g

Moles of methanol («A) Molar mass of methanol (CH3OH) C32 g mol"1) = 2 mol
Solutions • 3.39
«B (lmol) 1
Mole fraction of ethanol (xB) = nA + nB (1 mol+ 2 mol) 3
Mole fraction of methanol (xA) = «A (2 mol) _2

nA + «B U mo1 + 2 mo1) 3
Vapour pressure of ethanol in mixture (PB) = PB x jrB — (4-5 x 104 Nm 2) x

= 1-5 X 104 Nm'2
2
Vapour pressure of methanol in mixture (PA) = PA x = (8'1 * 104 Nm'2) x —
5-4 x 104 Nm'2.

(1-5 x 104 + 5 4 x 104) = 6-9 x 104 Nm'2
Total vapour pressure of mixture
(1-5 x 104 Nm2J_ x ]00 _ 21.74%
Percentage of ethanol in mixture (6-9 x 104 Nm-2)
(5-4 x 104 Nm 2 ) x 10Q = 7g.26% (6 9 x 104

Percentage of methanol in mixture
Nm-2)
O Example 3.30. The vapour pressures of benzene and toluene at 293 K are 75 mm and 22 mm Hg
respectively. 23-4g of benzene and 64-4g of toluene are mixed. If the two form an ideal solution, calculate the
mole fraction of benzene in the vapour phase assuming that the vapours are in equilibrium with the liquid
mixture at this temperature. (D.S.B. 1999)
Solution : Step I. Calculation of the total vapour pressure
______Mass of benzene _____ (23-4g)
Moles of benzene (nB) 0-3 mol
Molar mass of benzene (C6H6) (78g mol-1)
Mass of toluene (92 g mol )

Moles of toluene («A) = TT~,--------------------- 771
-------------------------------------------------------------- 777TTT
Molar mass of toluene(C
(0-3 mol) 7Hg)
Mole fraction of benzene (rB) "B = 0-3
nA + nB (0-3 mol + 0-7 mol)
Mole fraction of toluene (xA) = —^— =--------------- (0 7 mol) ------- = 0*7

nA + nB (0-3 mol + 0-7 mol)
Vapour pressure of benzene in solution (PB) = PB x JCB = (75 mm) x 0-3 = 22-5 mm
Vapour pressure of toluene in solution (P A) = PA x xA = (22 mm) X 0-7 = 15*4 mm Total
vapour pressure of solution = PB + A=

P
22-5 + 15 4 = 37‘9 mm.
3.40 Solutions
W1HWKWIKMI
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.
3 Example 3.31. The vapour pressure of ethyl acetate and ethyl propionate are 72-8 mm and 27-7 mm of
Hg respectively. A solution is prepared by mixing 25g of ethyl acetate and 50g of ethyl propionate. Assuming
the solution to be ideal, calculate its vapour pressure. (Pb. Board 2002)
Mass of CH3COOC2H3
Solution : No. of moles of CH3COOC2H5 (nB) ~
Molar mass
(25g)
= 0-284 mol
(88gmol ')
Mass of C2H5COOC2H,
No. of moles of C2H3COOC2H5 (nA) ---- ---------- ^~ss
(50g)
= 0-49 mol
(102gm or ’)
Mole fraction of ethyl acetate (xg) = — ______ (0 284 mol) _____

nA + nB (0-284 mol + 0-49 mol)
= 0-37
(0 • 49 mol) ____
Mole fraction of ethyl propionate (JCa) = —^— = —
nA + nB (0-284 mol +0-49 mol)
= 0-63
Vapour pressure of ethyl acetate (P^) = 72-8 mm
Vapour pressure of ethyl propionate (P^) =27-7 mm
Vapour pressure of ethyl acetate in solution (PB) = P°B*B = (72-8 mm) x 0-37 = 26-94 mm
a
Vapour pressure of ethyl propionate in solution (P A) = P°A*A = (27-7 mm) x 0-63 = 17-45 mm
Total vapour pressure of solution = PB + PA
= 26-94 mm + 17-45 mm = 44-39 mm.
Solutions • 3.41
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)

No. of moles of water (nA) Molecular mass (18 g mol’1) _ ^ 55 mol
nB (1 mol)
Mole fraction of solute (JCb) n
«B + * (1 mol + 55-55 mol)
1
= 0-0177
56-55
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 (C6Hn06) 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 _ (10g)

= 0 • 056 mol
Moles of glucose (nB) Molar mass of glucose (180g moF1)
Mass of water (90g)

= 5 mol
Moles of water (nA) = Mole Molar mass of water (18g mol ')
n. (5 mol)
= 0-9889
fraction of water (jtA) = + (5 mol + 0-056 mol) 5-056
«A "B
Vapour pressure of pure water (P A) = 32-8 mm

Vapour pressure of solution (PA) = P°A x JCA
= (32-8 mm) x (0-9889) =
32-44 mm.
• 3.42 Solutions
voblervid <L^'or f^ructice
Calculate the partial vapour pressure of C2H4Br2 at 85°C for an ideal solution with mole fraction of 0-25.
Vapour pressure of pure C2H4Br2 at 85°C is 170 mm Hg. [Ans. 42-5 mm Hg]
At 40°C, 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 Raoult’s 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 25°C ? At 25°C, the vapour pressure of water is
20 mm and the density is lg/mL. [Ans. 19-884 mm]
At 25°C, 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 mL’ 1. [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 20°C, 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.
Solutions • 3.43
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 Raoult’s Law, the vapour pressure of the solution (P s 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 ,
Ps = P;(1-*B) o r !-*B
p^ - Ps = Lowering in vapour pressure of the solution
PA-
= 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 (xB) 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 -
" *B (Here JTB = Mole fraction of solute)
"B WB/MB
But *B =
«B + «A WB / MB + WA / MA
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, nB < < < 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 nA.
The relation may be derived as follows :
-
P
A *s _ T _ nB PA «B +
«A
PA . »a + «A , . "A
or --------------- - 1 + —
PA - PS «B «B
or = _EA _____ i = p;-(p;-ps) = _ps

"B p; - Ps p; - Ps PA - Ps
PA - Ps=J}B_ = B MA °
W x r
Ps «A MB x WA
If all other values are known, MB 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.
For ideal or dilute solution :

PA ~ ps = "ft. = B *
W
MA
P A " A MB x W A
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 20°C 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 Raoult’s
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)

Ps (342g mol-1) x (lOOOg) ” 0 0036
17-5mm - 1 = 0 0036 or = 1 0036

Ps
(17-5mm)
or Ps 17-44 mm.
1-0036
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 Raoult’s Law,
P^-Ps _ «B W B x MA
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 (iSgmor1)
(0-75atm) (eOgmol-1) * (50g)
025
WB = 0-75 55-55 g
• 3.46 Solutions
Step II, Calculation of the molality of solution.
(55-55 g)
No. of moles of urea _ (60 g moP^T
Molality of solution (m) 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 50°C 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 Raoult’s 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) " M„x(100g)
(2-0 g) x (76-0 g mol"1) x (854 torr)

MB 254-52 g mol"1.
(5-1 torr) x (lOOg)
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
8
(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 Raoult’s 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) V
or
”B ' Ps MA
(0-02 atm) . (1000 g)

(0-98atm) X (lSgmor1) = l‘134rao1 = 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 Raoult’s Law,
p;-ps ..^^3 p; «A MB WA
(760mm - 745mm) 5 g x (18g mol ')

(760 mm) MB x (95g)
15 5g x (18g mol ')

760 MB x (95g)
(5 g) :< (18gmol~‘) x 760

or Ms (95g)x 15
48 g mol-1
r!
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.
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
Relative lowering of vapour pressure = Mole fraction of solute (B)
As the solution is dilute, we can use the formula.

Pi - Ps ”B _ wB ;; MA
Pi «A MB WA
(195 mm - 192 5 mm) _ (l-Og)x (58 g mol-1) (195
mm) MBx(100g)
00128 =
MB X (100 g)
(1-0 g) x (58 g mol ‘)

M8 =
0- 0128 x (100 g)
— 45-31 g mol 1
PM practice
ervt6
• 3.31. The vapour pressure of a solution containing 108-24 g of a non-volatile solute dissolved in lOOOg ot
water at 293 K is 17-354 mm Hg. The vapour pressure of water at 293K is 17-54 mm Hg. Assuming the
solution to be ideal, calculate the molar mass of the solute. |Ans. 181-78 g mol 1
• 3.32. The vapour pressure of 21% of an aqueous solution of a non volatile solute at 373 K is 755 mm Hg.
Calculate the molecular mass of the solute. [Ans. 58-68 g moi-1]
• 3.33. A solution containing 6g of benzoic acid, C6HjCOOH in 50g of diethyl ether, C2H50C2H5, has a vapour
pressure of 410 mm Hg at 293K. Calculate the molar mass of the benzoic acid. Vapour pressure of
diethyl ether at 293 K is 442 mm Hg. [Ans, 113-8 g mol ']
• 3.34. The vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non volatile solute
weighing 2-175 g is added to 39-0 g of benzene. The vapour pressure of solution is 600 mm Hg. What is the
molar mass of the solute ? (I.l.T. 1990) [Ans. 69-6 g mol *]
• 3.35. The vapour pressure of pure benzene at a certain temperature is 200 mm Hg. At the same temperature
the vapour pressure of a solution containing 2g of a nonvolatile, non electrolytic solid in 78 g of benzene is 195
mm Hg. What is the molecular mass of the solid ? (M.L.N.R. 1992) [Ans. 80 g mol ']
• 3.36. The vapour pressure of pure water at 30°C is 31-80 mm of Hg. How many grams of urea (molecular
mass = 60) should be dissolved in lOOOg of water to lower the vapour pressure by 0-25 mm of Hg ?
(Pb. Board 2001) [Ans. 26-2 g]
• 3.11. ELEVATION IN BOILING POINT TEMPERATURE

The boiling point of a liquid is the temperature at which it boils or the pressure on the surface of the
liquid becomes equal to the external pressure. If the external pressure is one atmosphere, the boiling point
temperature of the liquid is called normal boiling point temperature. If a small amount of
Solutions • 3.49
a non-volatile solute is added to a volatile solvent (e.g. water), the vapour pressure of the solution tormed will
decrease. This means that the solution will have to be heated to a higher temperature in order that its vapour
pressure is equal to the atmospheric pressure. Thus, the boiling point temperature
(T*) of the solution will be more than that of the pure solvent (T h) and there will be elevation or rise
in the boiling point temperature. Mathematically,
Elevation in b.p. temperature (AT*)=(T* - T*).
The variation of the vapour pressure with
rise in temperature can also be expressed
graphically by plotting curves between the
temperature and the corresponding vapour
pressure of pure liquid (solvent) and also its
dilute solution. The curve for the pure solvent
is indicated as AB while for the solution is
represented as CD. The vapour pressure curve
CD for solution lies below the curve for the
pure solvent AB. This is quite expected also
because the vapour pressure of the solution is
less than that of the pure solvent. If P represents
the atmospheric pressure, then the corresponding
temperatures T* and T* are the boiling point
temperatures of the pure solvent and solution.
For a small range of concentration, the rise 4. FIGURE 3.11. Plot for variation In vapour
in temperature (AT*) is directly proportional to pressure and elevation of boiling point,
the decrease in vapour pressure (AP). Since for
a dilute solution, the decrease in vapour pressure is proportional to the molality (m) of the solution, therefore,
AT* is also related to the molality in the same way. Thus,
AT* x m or AT* = K* m
Here K* is a constant called molal elevation constant or molal ebullioscopic constant.
Derivation of the relation AT* = K* x m
It has been pointed out above that the rise in boiling point temperature (AT*) is directly proportional
to decrease in vapour pressure (AP). But according to Raoult’s Law,
Decrease in vapour pressure (AP) x Mole fraction of solute (x B)
AT* x xB or AT* = k xB (Here k = constant of proportionality)
But JCB = —2a ------ /. AT* = k —Os—
nA + n B nA + nB
Since ideal solution is also dilute, nB < < < nA and can be neglected.
AT* =- kIrUi_ „
kn n k x MA x n ii
or AT* =
"A W A / M. wl
If nB moles of the solute are dissolved in lOOOg of solvent (W A = lOOOg or kg) then nB/WA
represents molality (m) of the solution.
AT* = kMA x m.
The molar mass of solvent (MA) is constant. Therefore, k x MA = constant (K*) where K* is molal
elevation constant.
Thus, AT* = K* X m
* 3.50 Solutions
Elevation in boiling point- Colligative Property

From the above relation, it is evident that elevation in boiling point (AT*) is directly proportional to the
molality (m) of the solution since K* is constant. Since AT* is related to molality or number of moles of the
solute per kg of the solvent, it is therefore, a colligative property.
Molal Elevation constant or Ebullioscopic constant
The elevation or rise in boiling point temperature is related to the molality of solution as :
AT* = K*m or AT* = K* (if m = 1)
Molal elevation constant (AT*) may be defined as :
Elevation in boiling point temperature for one molal solution i.e. the solution in which one mole
of the solute is dissolved in one kg of the solvent.
Molal elevation constant (K*) for a particular solvent has also been calculated from the thermodynamic
relationship.
K MKT;2
b
(1000 x AHvap)
Here M = Molar mass of solvent ; R = Gas constant
T* = Boiling point of solvent;
AHvap = Molar enthalpy of vaporisation of the solvent.
Units of K* : K/m or K kg mol'1
It may be noted that the value of K* depends upon the nature of the solvent only and is quite independent
of the nature of the solute. The K* values of some common solvents are listed.
▼ 1 \BI I 3.6. Molal elevation constants of some solvents
Solvent B.P. (K)

Molal elevation constant (K*) (K kg mol"1)
Water 373 0-52
Ethyl alcohol 351-5 1-20
Benzene 353 3 2-53
Chloroform 334-4 3-63
Carbon tetrachloride 350 0 503
Ether 307-8 2-02
Cyclohexane 353-5 2-79
Determination of Observed Molar Mass of Solute

We know that, AT* = K* x m
WB / MB _ WR x 1000 m
(Molality) - , 1000 ~ MB x WA
Kh x WB x 1000
AT* = Kt> * m =
MB X W A
Kfc x WB x 1000
AT* x WA '
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
Kfc *
ATh
~ MB X W A
K MRT;2
1000 X AH. ,„
h
— ____________ _________ . — ■ — ... _____________________________________ _

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 (Kb) for water is
0-52 K kg mob1. (A.I.S.B. 1997)
K, x WB
Solution : MB 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)
_ K, xWB
MB
Solution : AT, X WA
WB = 50 g ; WA = 1 kg ; AT, = 0-5 K ;
K, = 2-53 km'1 or 2-53 K kg mol'1
M = <2 ■53Kkgmorl)x (50 g)
B
(0-5 K) x (1 kg)
= 253 g mol"1.
• 3.52 Solutions
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 (Kb) 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
MB AT, x WA
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 W B b MB x
WA
Mass of camphor (WB) = 0 456 g Mass of acetone

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

Mola 1000
l
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)
Solutions • 3.53
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 100 g of benzene raises its
boiling point by 1 °C. What is the molecular mass of the solute ?
(Kb for benzene = 2-53 K kg mol'1)
(Pb. Board 2000)
_ KtxW„
Solution : MB x ^
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)

MB 253 g mol'1
(1 K) x (0-1 kg)
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 0-25°C. If the molecular mass of the non-electrolyte is 103 0 g mot1, calculate the molal
elevation constant for benzene. (D.S.B. 2003)
_ AT,, x MB x WA
Solution: Kfr w
*B
WB = 0-90 g ; WA = 87-9 g = 0 0879 kg ; MB = 103-0 g mol'1 ; ATfc = 0-25 K

_ (0-25 K) x (103-0 g mol'1) x (0 0879 kg)
Kb
~ (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
non-volatile and non-electrolyte solute increases the boiling point of water by 0104 K.
(H.P. Board 2003)
ATfr
Solution :
AT„ =Kj Km or Kj, =
m = 0-2 m ; ATj, = 0-104 K

(0-104 K)
Kb 0-52 Km'1 or 0-52 K kg mol'1
(0-2 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) ” 5’02K 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.
.. MR(T;)2
Solution : Kb
1000 x (AHvap)
(vap) = 40-585 kJ mol'1 = 40585 J mol'1
AH
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

2
1000 x (40585 J mol'1)
= 0-5l3 Kkg mol'1 = 0-513 K/m.
• 3.55
Solutions
. A solution of 7g of a non-volatile solute in 250g of water boils at 100-26°C. Find the molecular mass of
the solute K„ for water is 0-52 K kg mol'1. lAns- 56S m01 1
. A solution containing 0-45 g of urea in 22-50g of 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'
[Ans. 0-51 K kg mol"1]
The boiling point of ethanol is 78'C and its molal boiling point elevation constant per lOOOg is 115 K. A
solution of 1'12 g of camphor in 32g of ethanol has a boiling point of 78-28°C. Calculate the molecular mass of
camphor. (A.LS.B. 1996) [Ans. 143-75 g mol"1]
A solution containing 0*90g of a non-volatile solute in 100 mL of benzene has density 0-88 g mL at 298 K, and
it boils at a temperature 0-25° higher than benzene. Calculate the molecular mass of solute. Molal boiling point
elevation constant for benzene is 2-52 K kg mol [Ans. 103' 1 g mol ]
A solution of 12-5g of an unknown solute in 170g water gave a boiling point elevation of 0-63K. Calculate the
molar mass of the solute. (K^ = 0-53 K kg mol'1).
(Pb. Board 1991, D.S.B. 1997, A.l.S.B. 1997, H.S.B. 1997 S) [Ans. 61 -85g mol'1]
Calculate the boiling point of a solution containing l-8g of a non-volatile solute dissolved in 90g of benzene.
The boiling point of pure benzene is 353-23 K, Kj, = 2-53 K kg mol 1. [Molecular mass of solute = 58g mol'*]
(A.l.S.B. 1994) [Ans. 354-1 K]
. s 4 The boiling point of water is 100°C and it becomes 100-52°C if 3g of a non-volatile solute is dissolved in 20 mL of
it. Calculate the molecular weight of the solute. (K6 for water is 0-52 K kg mol 1 density of water = 1 g mol'1).
(D.S.B. 1992 Supp.) [Ans. 150 g mol'1]
Calculate the molecular mass of a substance, 1-0 gram of which when dissolved in 100 gram of solvent gave an
elevation of 0-307K in the boiling point. (Molar elevation constant = 1 -84 K kg mol ).
[Ans. 59-93 g mol'1]
. t.4? The boiling point of water becomes 100-52°C if 1 -5g of a non-volatile solute is dissolved in 100 mL of it. Calculate
the molecular weight of the solute. (K* for water = 0-6 K kg mol '). (density of water =
1 g mL'1) (H P- Board 1994) [Arts. 17-31 g mol'1]
The boiling point of 5% solution (W/W) of non-volatile solute in water is 100-45°C. The boiling point of pure
water is 100°C. Calculate the molar mass of the solute (Kt for water = 0-52 K kg mol'1)
[Ans. 60-8 g mol'1]
_________________________________________
♦ 3.12. DEPRESSION IN FREEZING POINT TEMPERATURE
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).
• 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 obtained by adding a non-volatile
solute are shown in the Fig. 3.12.
The temperatures corresponding to the points
where these states meet represent the freezing
points of pure solvent (Ty) and that of the
y,
solution Cl/). Since T/is lower than T there
is lowering or depression‘in the freezing point
(AT/).
Just as in case of elevation in boiling point
temperature, the depression is freezing point
temperature is also proportional to the molality
(m) of the solution. Thus,
AT/QC m or AT/ = K/ X m
Here K/ is the molal depression constant
and is also known as molal cryoscopic constant. A FIGURE 3.12. Plot for variation in vapour
pressure and freezing point.
If m = 1 molal, AT/ = K/.
Thus, molal depression constant may be defined as :
*
Depression or lowering in freezing point temperature for 1 molal solution i.e. the solution in
which one mole of the solute is dissolved in kg of the solvent.
The molal depression constant (K/) can also be calculated from the thermodynamic relationship.
MR(T})2
Kf
~ 1000 x AH~
Here M = Molar mass of solvent, R = constant
T} = Freezing point of solvent, AH^,, = Molar enthalpy of fusion of the solvent
Units of K/: KJm or K kg mol'1.
Just like molal elevation constant, the value of K/ also depends upon the nature of the solvent and is quite
independent for the nature of the solute. The K/ values of some solvents are listed.
▼ TABLE 3.7. Molal depression constants of some solvents.

Solvent F.P. (K)
Molal depression constant (K/) (K kg mol'1)

Water 273'0 1 86
Ethyl alcohol 155-7 1 -99
Benzene 278-6 5-12
Chloroform 209-6 4-70
Carbon tetrachloride 250-5 31-8
Ether 156-9 1 79
Cyclohexane 279-5 20-2
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
1
In severe cold, the temperature usually falls below 0°C. 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 (HO—CH2—CH2—OH). It is popularly
known as coolant. A mixture of ethylene glycol and water in equal proportion by volume freezes at
-36°C. 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
"(Molal,l),> ■ " MBX WA
K7 X WB X 1000
AT>- MB x W A
Kf x WB x 1000 MB
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 mp h 3 1 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 o fK 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,
MB
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 mot1, what is the molar mass of the unknown substance ?
(A.I.S.B. 1997)
K ] x Wn
Solution : MB = 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)
MB
-------------(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 -6°C (K ffo r water = 1-85 K kg mot'). (Roorkee 1992)
MB x AT- x WA
Solution : WB ~ ----------7} ------------
K
f
Molar mass of ethylene glycol (OHCH2CH2OH), MB = 62 g mol'1
Depression in freezing point (ATy) = 06 - (-6°C) = 6°C = 6K
Molar depression constant (Kj) = T85 K kg mol'1 Mass of water (WA) =
4 kg
f62g mol 1) x (6K) x (4 kg)

W
*=' ~ (T-85 K kg mol'1) « 8-
OF sample 3 Calculate the amount of ice which will separate on cooling a solution containing 50g of ethylene
glycol in 200g of water to - 9-3°C. (K ffo r water = 1-86 K kg mol'1) (Roorkee 1995)
Solution : Stt p I Calculation of the amount of water present in the antifreeze solution.
Mass of ethylene glycol (WB) = 50g Molar mass of ethylene glycol
(MB) = 62g mol"1 Depression in freezing point (ATy) = 0 - (- 9-3°C) =
9-3°C = 9-3K
• 3.59
Solutions
Molar depression constair K,) = 1-86 K kg mol'1
WB x K, _ (5Qg) x (1-86K kg mol'1)
Mass of water (WA) “ MB x AT, " (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 Sex. When 3-26g of selenium is dissolved in 226 g of benzene, the
observed freezing point is 0-112°C 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,) = 0-112°C = 0-112K
Molar depression constant (K,) = 4-9 K kg mol"1
(4-9 K kg mol *)x (3-26 g)

631-08 g moT1
(0-112 K) x (0-226 kg)
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. *
K = MR< V
Solution :
(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/~ (6024-6J

mol"1)
= 1-85K kg mol"1 = 1-85 K m"1
• 3.60 Solutions
The freezing point of a solution containing 18g of a non-volatile solute dissolved in 200g of water decreases by
0-93. Find the molecular mass of solute, for water is 1-86 K/m. [Ans. 180 g mol'1]
• 3.48 A solution of l-25g of a certain non-electrolyte in 20 0 g of water freezes at 271-94 K. Calculate the
molecular mass of the solute. Kf for water is 1-86 K/m. (Haryana Board 1996) [Ans. 109-67 g mol'1]
A solution containing 62-5g of non-volatile solute per lOOOg of water has a freezing point 1 06°C less than that
of water. Calculate the molecular mass of the solute. (K^ = 1 -86 K kg mol'1).
[Ans. 109-67 g mol'1]
* -S-M. A solution of sucrose (molar mass = 342g/mol) is prepared by dissolving 68-4g in lOOOg of water. What 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 0-40°C. Calculate the molecular mass of the non-volatile substance. Ky-for benzene is
5-12 Km'1. (Himachal Board 2000 S) (Ans. 133-33 g mol'1]
" 3.52. A solution containing 25-6g of sulphur dissolved in lOOOg of naphthalene whose melting point is 80-l°C,
gave a freezing point lowering of O^C. Calculate the formula of sulphur. Kf for naphthalene is 6-8
K/m- [Ans. Sg]
• 3.53. A solution containing 18g of a non-volatile solute in 200g of water freezes at 272-07 K. Calculate the
• 3.54. molecular mass of the solute.(Given K/ = 1-86 K/m) (D.S.B. 1993) [Ans. 180 g mol"1]
Normal freezing point of a solvent is 150°C. A 0-5 molal solution of urea in the this solvent causes a
freezing point depression of two degrees. Calculate the molal depression constant.
(Haryana Board 1998) [Ans. 4 Km'1]
• 3.55. The freezing point of cyclohexane is 279-65K. A solution of 14-75g of a solute in 500g of cyclohexane has a
freezing point of 277-33 K. Calculate the molar mass of the solute. (Given Kf = 20-2 K kg mol-1).
(Haryana Board 1996) [Ans. 256-85 g mol'1]
Addition of 0-643 g of a compound to 50mL of benzene (density 0-879g/mL) lowers the freezing point from
5-51°C to 5-03°C. If Ky = 5-12 km"1, calculate the molecular mass of the compound.
(Haryana Board 2001) [Ans. 156g mol'1]
' ----------------------------------------- - ----- -- ------------------------------------------------ — ------------------------------- • • •

♦ 3.13. OSMOSIS AND OSMOTIC PRESSURE
Osmosis
In order to understand the phenomenon of osmosis, let us take an inverted thistle funnel with mouth tied
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 funnel starts rising. It is quite obviously due to the flow of solvent (water) into the solution through the
semipermeable membrane. This is known as osmosis (In Greek, Osmos = to push). This was observed for the
first time by Abbe Nollet in 1748.
Osmosis can also take place when the two solutions with different concentration of the same solute are
placed in contact and are separated by a semipermeable membrane. It will occur from the dilute solution into
the concentrated solution or from the solution with lesser solute concentration into the solution with higher
concentration of the solute. Osmosis may be defined as :
Solutions • 3.61
A FIGURE 3.13. Process of osmosis through semipermeable membrane

The spontaneous movement of the solvent molecules either from pure solvent into the solution or
from dilute solution into the concentrated solution through a semipermeable membrane.
________________
Semipermeable Membranes
These are the membranes which allow only the movement of the solvent molecules through them.
These may be either naturally occurring such as parchment, cellophone, bladder of goat or pig and some
other cell membranes. However, these are not perfect for measurements in the laboratory.
Semipermeable membranes have also been prepared chemically. For example, when aqueous solutions
of potassium ferrocyanide and copper sulphate are mixed in a porous pot, the gelatinous precipitate of
copper ferrocyanide fills in the pores of the porous pot and acts as semipermeable membrane.
2CUS04 + K4[Fe(CN)6] -------- * Cu2lFe(CN)6] + 2K2S04
In addition to this, a variety of polymer membranes such as polymer cellulose acetate are also available.
_____________________________
In order to demonstrate the osmosis, remove outer shells of two eggs of the same size by placing them-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 will
shrink in size. In the first case, water enters the egg which contains a concentrated fluid through the egg walls
acting as semipermeable membrane. In the second case, water present in the fluid comes out of it as a result of
osmosis and passes into sodium chloride solution which is more concentrated. Thus, swelling takes place in
the first case while shrinkage occurs in the second case.
1 ►
.^ — “ — “ _“ _'
Pure _ Brine (NaCl)
water solution
▲ FIGURE 3.14. Demonstration of the phenomenon of osmosis (Normal lines represent size
before osmosis and dotted lines represent size after osmosis).
• 3.62 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
ions) of different substances and no semipermeable membrane is needed for the same. Osmosis is rather
selective in the sense that only the particles of the solvent can diffuse and that too through a semipermeable
membrane. Moreover, osmosis can be reversed or even stopped by applying pressure on the solution but this
is not possible in diffusion. The major points of distinction between osmosis and diffusion are listed in the
Table 3.8.
▼ TABLE 3.S. Difference between osmosis and diffusion
Osmosis Diffusion
1. The process of osmosis takes place through a semipermeable In diffusion, no semipermeable membrane is required.
membrane.
2. The process of osmosis involves the movement of the solvent In diffusion both the solute and the solvent molecules can
molecules in one direction only. move but in opposite direction.
In diffusion, the molecules (solute and solvent) move from a
3. In osmosis, molecules of solvent move from a region of lower region of higher concentration into a region of lower
concentration of solute into a region of higher concentration. concentration.
It cannot be prevented or stopped.
4. Osmosis can be stopped or reversed by applying additional
pressure on the side of higher concentration.
5. The process of osmosis is common in liquids only. The process of diffusion is common in liquids as well
as in gases.
Osmotic Pressure
In order to understand osmotic pressure, deposit the
artificial semipermeable membrane of copper ferrocyanide
in a porous pot fitted with a long glass tube with the help of
rubber stopper. Fill the porous pot with aqueous sugar
solution and place them in water taken in a beaker as
shown in Fig. 3.15.
Osmosis will occur and the level of the solution will
slowly rise in the glass tube. After a few days, the level
will become stationary and no further osmosis will occur.
Actually hydrostatic pressure called osmotic pressure develops
on the surface of solution which stops osmosis. The osmotic
pressure may be defined as :
the excess hydrostatic pressure that develops
due to osmosis at a particular temperature.
Alternate definition of osmotic pressure. Osmotic
pressure can also be defined in an alternate manner. To
understand it, consider a glass vessel divided into two
compartments with the help of a semipermeable membrane ▲ FIGURE 3.15. Representation of
as shown in Fig. 3.16. osmotic pressure.
Solutions • 3.63
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 K in order to distinguish it from atmospheric pressure which is
represented as P.
Remember
A solution of its own has only vapour pressure. It will develop osmotic pressure only when
osmosis takes place by placing it in contact with a solvent or less concentrated solution
through a semipermeable membrane. ______________________________________
Reverse Osmosis and its Application
It is interesting to note that if external pressure higher than the osmotic pressure is applied on the
solution, the solvent will start flowing from the solution into the pure solvent and the level of solvent in the
smaller tube will start rising. This process is known as reverse 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
dissolved salts into pure water. Sea water is taken in a tank provided with a rigid semipermeable membrane of
cellulose acetate. The membrane, in fact, is permeable to water but impermeable to the impurities as well as
ions present in sea water. Pressure more than osmotic pressure is applied on it. Reverse osmosis occurs and
pure water forces it way out of the semipermeable membrane because of reverse osmosis. This is quite good for
drinking purposes. Many countries have employed desalination plants to meet the requirement of drinking
water.
Experimental Determination of Osmotic Pressure
A number of methods are available to determine the osmotic pressure of a solution. These are :
• Pfeffer’s method
• Berkley-Hartley’s method
• de Vries plasmolytic method
• Morse-Frazer method
• Townsend’s reverse osmosis method.

The commonly used method is by Berkley and Hartley’s. 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 Hartley’s Method
pressure gauge gives the osmotic pressure. for 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
Van’t 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-Van’t 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 0°C (273K) is 224 atm.
2, Gay Lussac Van’t 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
V
Solutions • 3.65
As osmotic pressure is also denoted by the sign P, therefore,

PV = nRT
This equation is known as Van’t 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 Van’t Hoff equation : trV = nRT But
_ WB
n = WB/MB «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.

(it) The solution is dilute i.e., the concentration of the solution is not more than 5%.
(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 Van’t 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.

Van’t Hoff Equation : KV = nRT
« = — RT = CRT V
WB x R x T WB x R x T
n or MB =
MB x V nxV
JI Osmotic pressure in atmospheres Volume of
V solution in litres Solution constant (0-0821 L
R atm K"1 mol1)
r^RT n2RT
For Isotonic Solutions : ”t n2 or Vi “ v2
Solutions • 3 67
jmtteeeHtiwaws
#*
OExample 3.55. Calculate the osmotic pressure of 5% solution of canesugar (sucrose) at 15°C.
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- = 0-1L
1000
Solution constant (R) = 0 0821 L-atm K 1 mol 1
Temperature (T) = 15°C = 15 + 273
288
K
■ 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
rt
n= = 4-82 atm, V = 1L, R = 0 0821 L atm K'1 =mol*
0-21mol.
(0■ 0821 Latm K' mol ) x (293K)
1 -1
T = 293K
Step II, Calculation of the molality of solution.
(4-82atm) x (1L)
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---------------------------------
(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) (Pb. Board 2000 Supp.)
Solution : Step I. Calculation of the osmotic pressure of solution containing urea.
WjxRxT
n
'~ MB x V
l
• 3.68 Solutions
WB = 4-5g, MB = 60g mol-1, T = 300K

R = 0 0821 L atm K"1 mol'1. V = (100 + 100) = -2°°™L- = 0-2L
1UUU
(4-5g) x (0 0821 Latm K-1 mol-1) x (300K) _ „
•• TCt — " - -■ ■■ ■ ■ - , ------------------—— — mil)
(60 g mol *) x (0-2L)
Step II. Calculation of the osmotic pressure of solution containing sucrose.
WB = 3-42g, MB = 342 g mol-', T = 300K
R = 0-0821 L atm K'1 mol-1, V = (100 + 100) = = 0-2L

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

Total osmotic 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%
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 X R X T
^{glycerine) MB x V
WB 10-2g, V = 1L
= (10'2g) x R x T 71
(glycerine) MB x (1L)
WB X R X T
17 (glucose)
Mn x V
WB = 2g, MB = (180 g mol'1), V = 100 mL = O IL
= (2g)x R x T
%'ucose) (180g mol-1) x (0■ 1L) ...(it)
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)
(10-2g) x (180g mol-1) x (0-1L) (lL)«(2g)

w
= 91-8 g mol-1 Molar mass of glycerine =

91-8 g mol-1.
\
Solutions
Êxample 3.59. At what concentration of solute 'P' the solution will be isotonic with a 5 percent
solution of urea ? (Molar mass of ‘P‘ = 342 g mol~*) (Pb. Board 2003)
Solution : Since solutions are isotonic, rc(Solute) = 7t(„rea)
WB x R x T
"(urea) ~ MB x V
WB = 5g ; MB = (60 g mol'1) ;V = 01L
_ (5g)x R x T
"(urea) ( wi . m n r h x m , m •••w
1
(60 g mol" ) x (0-1L)
WB x R x T
MB x V
(342 g mol-1) ; V = 0-1 1

WjxR x T ...(H)
^(solute) (342 g mol-*) x (0-1 L)
Equating (i) and (ii)
(5g)x R x T
W„xR x T
(342 g mol-1) x (O IL)
(5g)x (342 g mol-1)

or WB =
(60 g mol -1) "
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 37°C ? (A.I.S.B. 1999 Supp.)
Solution : ft = CRT
or C
RT
7i = 7-2 atm,
R = 0-0821 L atm K"1 mol"1,
T = 37°C = 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 CI2H220II 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.
n
• 3.70 Solutions
At the equilibrium, the mole fractions of sucrose in the two solutions are the same and are represented as
:
(0-010 mol) (0- 020mol)
(0 010 mol + lOOg / 18g moF1) - n(H20) (0-020 mol + lOOg / 18g mol'1) + nH20
(0-010 mol) (0- 020 mol)
(5-56mol) - n(H20) (5-57mol) + nH20
or 0-0557 mol + (0-010 mol) n (HzO) = 0-1112 mol - (0 020 mol) nH20 0-030 n (H20)
= (0-1112 - 0-0557) mol = 0-0555 mol.
_ (0-0555 mol)
1-85 mol
(0-030)
Concentration of sucrose in resulting solution.
(O-OlOmol) 0-010
= 0 00269
(5-56mol) - (l-85mol) 3-71
ProLL <
2~ôr jf^ractice
• 3.5 Osmotic pressure of blood is 8-21 atm at 37°C. How much glucose should be used per litre for an
intravenous injection that is isotonic with blood ? (Pb. Board 1999) [Ans. 58-068g]
• ■ How much glucose, QHÔg must be dissolved per litre of the solution that yields osmotic pressure of
2- 72 atmospheres at
298 K ? R = 0-0821 L atm K"1 mol"1. [Ans. 20-0116 g]
• ■. 3-0g of non-volatile solute when dissolved in 1 litre water, shows as osmotic pressure of 2 atmosphere at
300 K. Calculate the molecular mass of the solute. (R = 0-082 litre atm K"1 mol"1). (H.P. Board 1996)
[Ans. 36-9 g mol"1]
• 3.60. The osmotic pressure of a solution containing 1 -0g protein in 200 mL of aqueous solution at 27°C has
been
found to be 2-0 x 10"1 atm. Calculate the molecular mass of protein. (R = 0-082 L atm mol"1 K"1).
(A.I.S.B. 1990) [Ans. 615-7 g mol"1]
Osmotic pressure of a solution containing 2g dissolved protein per 300 cm3 of solution is 20 mm of Hg at
27°C. Calculate the molecular mass of protein. (R = 0 0821 L atm K"1 mol"1).
(D.S.B. 1992) [Ans. 6238-6 g mol"1]
• 3.62. Osmotic pressure of a solution containing 7g of a protein per 100 mL of solution is 25 mm Hg at 310 K.
Calculate the molecular mass of the protein. (R = 0-0821 L atm K"1 mol"1),
(A.I.S.B. 1993) [Ans. 54159-3]
• 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 the molecular mass of the compound.
(Pb. Board 1994 Supp.) [Ans. 189-94 g mol"1]
• 3.64 A 5% solution of sucrose (Ci2H220n) is isotonic with 0-877% solution of urea. Calculate the molecular
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
• 3.66. 1 atmosphere at 0°C ? (A.I.S.B. 1998 Supp.) [Ans. 22-4L]
Find the osmotic pressure of M/20 solution of urea at 27°C (R = 0-0821 L atm K"1 mol"1).
[Ans. 1-2315 atm]
Solutions • 3.71
♦ 3.14. ABNORMAL MOLECULAR MASSES

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
the colligative property is inversely proportional to the molecular mass of the solute. Accurate values of
the molecular masses can be obtained provided the solutes are non-electrolytes and donot undergo either
dissociation or association in solution. But in many cases, the solutes are electrolytes i.e., acids, bases
and salts. When these are dissolved in solvents they are likely to undergo either dissociation or
association leading to change in the number of the particles. Since the colligative properties are
dependent upon the number of the solute particles, these are also likely to be affected. Molecular masses
of the solutes which are inversely proportional to the colligative properties must have different values
from their normal values. In other words, these are abnormal in nature and are also called observed
molecular masses. Let us briefly study some examples of association and dissociation.
Association of Solute Particles
In certain solvents (generally non-polar) the particles of the solute undergo association i.e., two
or more molecules of a solute combine to form a bigger molecule. As a result, the total number of
nA (A)„
(Single molecules) (Associated molecule)
solute molecules in the solution will decrease. The colligative properties are expected to decrease
while the molecular masses of the solutes involved are expected to increase. It is quite expected also
since the molecular mass, as stated above, varies inversely as the colligative property.
For example, in benzene solvent, both acetic acid and benzoic acid exist as dimers because of the
presence of intermolecular hydrogen bonding
2CH3COOH --- --- ^ (CH3COOH)2 ; 2C6H5COOH ------------ --- ^ (C6H5COOH)2
C6H5
,0 = C-(X
CH3 H ,H
I
.o=c-o\ \o-c=oy‘
H ,H
I
\ 0-C=0'
C6H5
Benzoic acid
The normal molecular massI of acetic acid is 60 amu. and its observed molecular mass is expected
CH3
to be 120 amu in case all the molecules undergo association in benzene. Similarly, the normal
molecular mass of benzoicAcetic
acid isacid
122 amu. and its observed molecular mass must be 244 amu. in
case of complete association. However, in most of the cases the association is not hundred percent or
complete which means that all the molecules of both the solutes mentioned above donot get associated.
Dissociation of Solute Particles
Solute particles in case of electrolytes are expected to undergo dissociation in polar solvents like
water as follows :
AB -- ---A+ + B'
As a result, the number of the ions (or particles) formed will increase. The colligative properties
in turn, are also likely to increase and the observed molecular masses of the solute must decrease
•i
* 3.72 Solutions
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)
Van’t Hoff has introduced a factor known as Van’t 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
Van’t 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.
The value of t predicts the nature of the solute in solution.

• 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 Van't Hoff Factor and Extent of Association or Dissociation of the
Electrolytes in solutions.
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
Degree of association Total no. of moles of the electrolyte
No. of moles of the electrolyte dissociated
Degree of dissociation Let us Total no . of moles of the electrolyte
Van’t Hoff factor (i) both in association and dissociation.
try to co-relate a and
J
Solutions • 3.73
Relation between a and i in Association

Let us suppose that n molecules of the electrolyte ‘A’ get associated to form bigger molecule (A)„
i.e. nA v. s (A)„
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)
i= or i -l = a (1/n - 1)
1
i-1
a (For association)
1/n-1
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)
No. of moles of the electrolyte after dissociation _____
i=
No. of moles of electrolyte without considering any dissociation
1 - a + na
i= or i - 1 = a (n - 1)
1
i-1n-
a (For dissociation)
1
Note. The value of Van’t 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

Observed colligative property _ Normal molar mass
Van't Hoff factor (0 =
Normal colligative property Observed molar mass
• 3.74 Solutions
In associatioh/riissociation :
ATft = /K^m; ATy = /Kym; n = /CRT.
i-I
(For association) : a=
1 In - 1
(For dissociation) : a= /-1

n-1
• I sample 3 62. Assuming complete dissociation, calculate the expected freezing point of a
solution prepared by dissolving 6 0g of Glauber's salt. Na 2S04,10H2O in 0-1 kg of water. (Given
value of Kf — 186 K kg mol'1). (D.S.B. 1998)
Solution : Na2S04 .IOH2O dissociates in aqueous solution as :
Na2S04 .IOKJO -------» 2Na+ + S042' + (10H2O)
2 +1„
„ . .. .... - „ ... No. of particles after dissociation
Van t Hoff factor (1) =------------- -------------------------------- 1
No. of particles originally present
(IOHJO molecules are not considered as these are the part of the solvent)
ATy = i x K y x m = r x Kwny x
MB x W A
i = 3, WB = 6 0 g, WA = 0-1 kg, Kf = 1*86 K kg mol"1 MB(Na2S04.10H2O)
= (2 X 23) + 32 + (4 x 16) + (10 x 18) = 322 g mol'1
3 x (1 86K kg mol"1) x (6g) = 1-04K 1

=
(322gmol ’)x(O-lkg)
Freezing point of solution (Ty) = Ty° - ATy = 273K - 104K = 271-96K.
Calculate the amount of sodium chloride which must 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).
(A.I.S.B. 1997)
Solution : Sodium chloride (NaCl) dissociates as :
NaCl ------> Na+ + Cl'
factor (/) - N° ■ of particles after dissociation _ 1 + 1 _ j

Van’t Hoff:
No. of particles originally present
ATy x MB x WA
WR = »x K,
i = 2, WA =
1 kg, ATy = 3K, Ky =
1-86 K kg mol'1 MB (NaCl)
_ (3K) x (58-5g mol-1) x (1 kg)1
= 23 + 35-5
WB = 58-5 g mol'
~ 2 x (1-86K kg mol-1) =
47-2 g.
Solutions • 3.75
SExample 3.64. Solution A contains 6g of urea in 100 inL of it at 27°C while solution B has 6g of acetic
acid in 100 mL of the solution at the same temperature. Are the two solutions equimolar as well as isotonic ?
(Ticklish Problem)
Solution. Comparing the molarities of the two solutions.
x. , ■ ,XMX Mass of urea / Molar mass of urea
For solution A Molarity (M) =-----------------------------------------------
(egmeogmor1)
---------- oTE --------- = 1 mol L 1 = 1 M
Mass of acetic acid / Molar mass of acetic acid
For solution B Molarity (M) =
_ (6g) / (60 g moF1)
= 1 mol L -i _ 1 M
0 -1 L
Solution A and B are equimolar.
Comparing the osmotic pressures of the two solutions.
For solution A *. n = i'CRT=lx(l mol L~')x(0-0821 L atm K"1 mol_1)x300 K
= 24*63 atm.
For solution B : Acetic acid ionises in aqueous solution as :
CH3COOH + H20 ---- ----- ^ CH3COO- (aq) + H30+(aq)
In this case, Van’t Hoff factor (i) > 1
n = /CRT > 24-63 atm.
Since the two solutions have different osmotic pressures, these are not isotonic.
SExample 3.65 The freezing point of a solution containing 0 3g of acetic acid in 30g of benzene is lowered by
0 45°. Calculate Van't Hoff factor. (Kffor benzene = 512 K kg mol' 1) (A.I.S.B. 2001)
Solution : step 1. Calculation of observed molar mass of acetic acid (CH3COOH).
K f x WB
M
B AJf x WA
WB = 0-3g, WA = 30-0g, = 0-03 kg AT/ = 0 45° = 0-45K K/ =

5-12K kg mol‘l
(5-12K kgmor1) x (0-3g)

MB = = 113-8 g mol’1
(0-45K) x (0-03 kg)
Step II. Calculation of Van't Hoff factor Normal molar mass of CH3COOH
=12 + 3x1 + 12 + 2 x 1 6 + 1
= 12 + 3 + 12 + 32 + 1 = 60 g mol-1
Normal molar mass _ (60-0 g mol-1) _ ,,
Observed molar (113-8 g mol-1)
Solutions
Dfxample 3.66. A solution contains 0-8960g of K2S04 in 500 mL. Its osmotic pressure is found to be 0-69
atm at 27°C. 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
500
WB = 0-8960g, V = 1000 = 0-5L, T = 27°C = 300K
R = 0 0821 L atm K*1 mol*1, n = 0-69 atm.
(0-8960g)x (0 0821 LatmK~ 1mol~1) x (300K)
=
“
MB
(0-69atm) x (0-5L) =63-97g mol*1
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
Normal molar mass _ (174 g mol ‘) = 2>

Van’t Hoff factor O') = 72.
Observed molar mass (63-97 g mol-1)
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 100-0832°C. 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.
_ K, x WB
MB =
AT, x WA
WB = 1 -248g ; WA = 100 g = 0-1 kg ; AT* = 0-0832°C
or 0 0832 K ; K, = 0 52 K kg mol*1
- (0 - 52 K kg mol"1) x (1 ■ 248 g)
MB
(0 0832 K) x (01 kg) -788mo1'
Step II. Calculation of Van’t 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
(i-'l) (2-67-1) 1-67
Degree of dissociation (a) - ^ ^ ^ ^ -------- — = 0-825
Degree of dissociation of barium chloride is 0-835 or its percentage dissociation = 0-835 x 100
= 83-5%
Solutions
OExample 3.68. Calculate the boiling point of one molar aqueous solution (density = 104 g
mL'1) of potassium chloride ( Kf , — 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% K2SOJ solution at 27°C 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 KI„rm 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 = 71K2SO4 or 2 x R x T = i x R x T or t = 2 Step

III. Calculation of degree of ionisation of K2SO4.
For K2S04 ; a = -^7 = = | = 0-5

n — 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
= K/ x WB
M B = 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 g
(0-025 kg)x (1-62K)
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) _ ___

Van’t 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)
0-992
° 1/n - 1 1 / 2 - 1 ~ (-0-50)
.-. Percentage association of acid = 0-992 x 100 = 99-2%.
Solutions * 3.79
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 5 5 °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
a
~l/«-l or 08 (1/3-1) or 1
~ 0-467
Calculation of depression in freezing point (AT})
ATy = i x Kj - x m
i = 0-467, Kf = 5-12 km'1, m = 0-25 rnolal ATy = (0-467) x
(5-12 km' ) x (0-25m) = 0-6K = 0:6°C -'Hi) Calculation of freezing point of solution
1 5
Freezing point of solution (Ty) = Ty° - ATy = 5-5°C - 0-6°C = 4*9°C.
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 -8°C.
-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 0-45°C.
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 BaCl2 in 250g of water boils at lOO-OSS'C. Calculate the ratio of the Van’t Hoff
factor and molality of BaClj in this solution. (Kft for water = 0-52 K nr*. Molar mass of BaCl2 = 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 27°C. Calculate Van’t
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]
•5 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 Van’t 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]
• 3.80 Solutions
Problems with Solutions

♦PROBLEM 1 At 40°C, the average osmotic pressure of blood is 8-8 atm. Find the total
concentration of the various constituents in the blood. Assuming that the concentration is the same as
the molality, find the freezing point of the solution. (Kyfor water = 1 86, K Kg mol'1)
Solution. Step I. Calculation of concentration of the solution
According to van’t Hoff equation.
= CRT or C =
RT
it = 8-8 atm, T = 40°C = 40+ 273 = 313 K,
R = 0 0821 litre-atm K'1 mol"1.
(8-8atm)
C=
(0.0821 L - atm K^moP1) x (313 K)
= 0-34 mol L' (M)
1
Step II. Calculation of freezing point of the solution

Depression in freezing point of solution (ATy) = Ky x m
m =0-34 mol kg'1 (same as molarity as given)
Ky = 1 -86 K kg mol'1
ATy = (1-86 K kg mol'1) x (0 34 mol kg'1) = 0-63 K = 0-63°C
Freezing point of solution = 0 - (0-63°C) = - 0-63°C
♦ PROBI When 18 g of a solute having empirical formula CH 20 is dissolved in 300 g
of water, the solution freezes at - 0-93°C. What is the molecular formula of the solute ? (K<- for
water = 1-86 K kg mol-1)
Solution Step l.Calculation of molar mass of the solute.
_ *V
MB = ATy X WA
WB * 18 g ; WA = 300 g = 0-3 kg ; ATy = 0 - (- 0-93°C) = 0-93°C
= 0-93 K.
Ky = 1-86 K kg mol'1
(1-86K kg mol *) x (18g)
= = 120g mol
(0-93K) x (0*3 kg)
Step II. Calculation of the molecular formula of the solute.
Empirical formula mass of solute (CH20) = 12 + 2x 1 + 16 = 30 g Molecular
mass of solute — 120 g mol'1 = 120 g
Molecular mass of solute _ (120 g) _ Empirical
n~
formula mass of solute (30 g)
Molecular formula of solute = 4 (CH20) = C4H804
• 3.81
Solutions
♦ PROBLEM 3 2 g of urea when dissolved in 200 g of certain solvent decreases the freezing
point by 0*2°C. 3*2 g of an unknown substance when dissolved in 160 g of same solvent depresses the
freezing point by 0*36°C. Calculate the molar mass of unknown substance.
K , x WB
Solution. MB AT, x WA
Value of K, will remain the same as the solvent is the same.
For Urea : MB = 60 g mol"1 ; WB = 2 g : WA = 200 g = 0 2 kg
AT, = 0-2°C = 0-2 K
K, x (2g)
(60 g mol"1) - ■ ■■«)
(0-2K) x (0 2kg)
For Unknown Substance WB = 3-2 g; WA = 160 g = 0-16 kg
AT, = 0-36°C = 0-36 K
K, x (3- 2g)
Ma = ■ (H)
(0-36K) x (0-16kg)
Divide eqn. (ii) by eqn, (i)
MF K, x (3*2g) . (0-2K) x (0-2 kg) _ j n

-1
(60g mol ) (0-36K) x (0-16kg) * K,x (2 g)
MB - 111 x (60 mol'1) = 66*67 g mol' 1
♦ PROBLEM 4. Ethylene glycol is used as antifreeze. What relative proportions of ethylene

glycol and water (by weight) should be mixed to form an antifreeze solution that will not start
freezing until the temperature reaches - 37°C (K,for water = 1*86 kg mol"1) ?
Solution. According to van’t Hoff theory of dilute solution
AT,
AT, = iK, m or m iK f
Since ethylene glycol (HO—CH2—CH2—OH) is a covalent compound, the value of van’t Hoff
factor i' - 1.
AT, = 0 - (- 37°C) = 37°C = 37 K ; K, = 1*86 K kg mol'1
37 K
m= -^y- = 20mol kg'*
1 x 1-86K kg mol
This value of m shows that 20 moles of ethylene glycol are dissolved per 1000 g (kg) of water.
Molar mass of HO—H2C—CH2—OH = 62 g mol'1
Mass of 20 moles of HO-CH2-CH2-OH * (62 g mol"1) x (20 mol) = 1240 g.
The relative proportions in which ethylene glycol and water must be mixed
= 1240 : 1000 = 1*24 : 1*00.
• 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 :
Mass of KMn04
Molar mass of KMn04
Molarity (M) =
Volume of solution
(0-416 g)
(158 g moL1)
(0-05 mol L'1) =
Volume of solution
Volume of solution = 0-416g = 0-527 L = 52-7 mL

(158 g mol1) x (0-05 mol L“‘)
♦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 mL’1) = 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) = P AxA = (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

Solutions • 3.83
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) (120g)/(60gmol )
Molality of solution (m) = ~ (900/1000 kg)
120x 1000 (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. 4
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
(KMn04) (Oxalate)
x (15 0 mL) = N2 x (10 0 mL)
(15 mL)
N, =
20 x (10 mL) 40
Strength of oxalate ions per litre of the solution
= Normality X Equivalent mass of oxalate ions
3 88 Eq. mass of C204 - 88

X 2
~ 40 2 =
3-3 g/L
33
Amount of oxalate ions per 100 mL of the solution = — 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 = x 100
Amount of sample
0-33
x 100 = 66%
0-50
• 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 ?
[Ans. (i) 15-7 M (ii) 12-7 mL]
2. 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 25°C 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 25°C 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 nonvolatile, find
out its physical state in the two solutions. Give PH2O = 23-756 and PC6H6 = 72-5 torr at 25°C. [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 - 10°C.
(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 100°C at 760 mm pressure and the heat of vaporisation is 40-7 kJ
mol'1. Find out the vapour pressure of water at 85°C. [Ans. 438-52 mm]
12. The elevation in boiling point of a solution of non-electrolyte in CCI4 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 Van’t 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
14 Phenol (C6H5OH) gets associated in water to form double molecules. 0-6677 g of phenol dissolved in 35-5 g
of water depresses the freezing point of water by 0-215. (K,for water = 1-86 K kg'1 mol-1). Calculate
(i) Observed molar mass of phenol
(ii) Degree of association of phenol. [Ans. 162-47 g mol-1 ; 0-842]
15. The osmotic pressure of a urea solution is 500 mm of Hg at 10°C. The solution is diluted and its temeprature
is raised to 25°C. It is now found that the osmotic pressure of the solution is reduced to 105-3 mm.
Determine the extent of dilution of the solution. [Ans. 5 times]
Text Book Questions with Answers
Define the term solution. What kinds of solutions are possible ? Write briefly about each
type of solution with an example.
Ans. For answer, consult text-part. >
••2. Suppose a solid solution is formed between two substances, one whose particles are very large and the
other whose particles are very small. What type of solid solution is this likely to be ?
Ans. The solution likely to be formed is interstitial solution. For further details, consult text-part. ••3. Define
the following terms :
(i) Mole fraction (ii) Molality fill) Molarity (iv ) Mass percentage.
For answer, consult text-part.
Ans. Concentrated nitric acid used in the laboratory work is 68% nitric acid by mass in ••4. aqueous
solution. What should be the molarity of such a sample of acid if the density of the solution is 1*504 g mL"1
?
Mass of HN03 in solution = 68 g ^ns-
Molar mass of HNO3 = 63 g mol-1
Mass of solution = 100 g Density of
solution = 1-504 g mL-1
Mass of solution
Volume of solution - Density 0f solution
qoog) = 66 -5 mL = 0 0665 L
(1-504 g mL-1)
Mass of HN03 / Molar mass of HNQ3

Molarity of solution (M) Volume of solution in Litres
(68g/63gmol ’)
= 16-23 mol L-1 = 16-23 M.
(0-0665 L)
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*2 g mL'1, then what should be the molarity of the solution ?
Ans. Step I. Calculation of molality of solution.
Mass of glucose in solution = 10 g
Mass of solution = 100 g
Mass of water in solution = (100 - 10) = 90 g = 0 09 kg
Molar mass of glucose (C6H1206) = 6 x 12 + 12 x 1 + 6 x 16 = 180 g mol'1
Molality of solution (m ) = Mass of giucose ' MoJa-L™ss of glucose
10g/(180gmol *)
= 0-617 mol/kg = 0-617 m.
(0 09 kg)
Step II. Calculation of mole fraction of each component in solution.
Mass of glucose <18 g)
No. of moles of glucose = Molar mass (180 g mol-*) - = 0-055 mol
No. of moles of water = Mass of glucose (90 g)

Molar mass (18 g mol-1) = 50 mol
Mole fraction of glucose = c«H12o6

n
(0-055 mol) = 0-01
"C6H,2O6 + nH20 (0-055 mol) + (5-0 mol)
Mole fraction of water = 1 - 0-01 = 0-99
olution.
100 g
1-2 g m L'1
Volume of solution = Mass of solution 000 g) — ml
St'X.'l'l
Density -1
(1 - 2 g mL ) O J J J 111 Li
= 0 08333 L.
Mass of glucose / Molar mass of glucose
Molarity of solution (M) =
(10 g)/ (180 g mol)
(0-08333 L) = 0-67 mol L'1 = 0-67 M
How many mL of a 0-1 M HC1 are required to react completely with lg mixture of Na CC>3 and
••6. 2
NaHC0 containing equimolar amounts of two ?

3
Step I. Calculation of mass of constituents in the mixture.

Mass of the mixture = 1-0 g Let the mass of Na2C03 = jr g
MassofNaHC03 = (1 — jc)g
Solutions • 3.87
**#H666beK; S x-x-
Mass of Na2C03 (JC g) x

Moles of Na2C03 = —— ----------- 1 ---- 1 = ■ ■ ‘ = ~r^7 mol
2
Molar mass (106 g mol ) 106
Mass of NaHCO 3 . (1 ~ x ) g 1 - x 84
Moles of NaHCC>3 Molar mass 11101
(84 g moP1)
According to available data :
Moles of Na2C03 = Moles of NaHCC>3
(T56 “") * (-1 -X

84“ mol
106
or 84* = 106 - 106* or * = -y^- = 0-557g
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 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
Total mass of HCl required = (0-384 + 0-192) = 0-576g Step
III. Calculation of volume of HCl required.
Mass of HCl required = 0-576 g
Molarity of HCl solution = 0-1 M
Mass of HCl / Molar mass of HCl
Molarity of solution (M) Volume of solution (V)
(0-576 g) / (36-5 g/mol)
01 mol L"1 V V
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.
(300 g)x 25
Ans. Mass of one component (A) in solution = 75g
100
(400g)x 40
Mass of other component (B) in solution 100 = 160g
Mass of A
Mass per cent of component (A) x 100
Mass of solution
(75g)
x 100 = 32%
(235g)
Mass of B
Mass per cent of component (B) - Mass of solution X 100
(160 g)
X 100 - 68%
(235g)
**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) = Mass of solvent in kg
_ (222-6 g) / (62 g mol-1) 0-2

kg — 17-95 mol kg ,-t
= 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
(422-6 g)
Volume of solution = = 394-2 mL
Density of solution (1-072 grnL*1)
= 0-3942 L.
Solutions • 3.89
Mass of ethylene glycol / Molar mass

Molarity of solution (M)
(222-6 g) / (62 g mol-1)

9-10 mol L‘l= 9*10 M.
(0-3942 L)
••9. 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
Ans.
= 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 °l—L
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 the solution
••10. but it is comparatively less than both alcohol and water. As a result, the magnitude of attractive forces
Ans. tends to decrease and the solution shows positive deviation from Raoult’s 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 Henry’s 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
2
bar. If the solution contains 5*0 x 10' g of ethane, what shall be the partial pressure of the gas ?
2
According to Henry’s law,

The mass of the gas (m) dissolved in solution Partial pressure (/?) (At constant temperature)
•• 12.
Ans.
••13.
Ans.
Solutions
(6'56 x 10 2 g) oc 1 bar
(5-0 x 10~2 g) <x p
= ( 5 - O x 10 g ) ^ ba _ 0.762 bar
or
(6-56 x 10~2g)
••14. What is meant by positive and negative deviations from Raoult’s law and how is the sign of AHS0|
related to positive and negative deviations from Raoult’s 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 Raoult’s Law
PA ~ Ps = xB = nB _ _ W B x MA
B
Pi ("A + «B) "A MB * WA
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) - 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
••16. g of heptane and 35-09 of octane ?
Mass of heptane (C7H16) _ (25 g)

A ns. No. of moles of heptane (nB) y— — 0-25 mol
Gram molar mass (100 g mol ‘)
Mass of octane (C8H18) (35 g)
No. of moles of octane (nA) = 0-307 mol
Gram molar mass (114 g mol-1)
Mole traction of heptane (jcB) nB _ _________ (0-25 mol)

= 0-449
«B + «A (0-25 mol + 0-307 mol)
Mole fraction of octane (JCa) _____ (0-307 mol)

- 0-551
% + nA (0 ■ 25 mol + 0-307 mol)
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) = P A + PB = (47-23 + 25-79) = 73-02 kPa.
Solutions • 3.91
WMM5KSWKB5WIK4 jJl
••17. The vapour pressure of water is 12-3 k Pa at 300 K. Calculate the vapour pressure of
1 molal solution in it.
Ans. 1 molal solution implies one mole of the solute dissolved in lOOOg <1 kg) of solvent i.e.
water.
No. of moles of solute («B) “ 1 m°l
Mass of water (lOOOg) = 55 55 mol

No. of moles of water (nA)
Molar mass (18 g mol-1)
nB ___ ______ (1 mol) _____

Mole fraction of solute (xB) fifj + nA (1 mol + 55-55 mol)
_J __
56-55 0-0177
Vapour pressure solution (PA) = PAxA = PA(1 - xB) = 12-3 kPa x (1 - 0-0177)
= 12-3 ka xO-9823 = 12-08 kPa.
••18. Calculate the mass of a non-volatile solute (molecular mass 40) which should be dissolved in 114 g
of octane to reduce its pressure to 80%.
Ans. The solution is assumed to be non-ideal. According to Raoult’s Law,
P
A - PS = _ _Wg_ x MA_
Ps nA MB WA
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.
(P; - Ps) MB x WA ps
WB
MA
(0-2 atm) (40g mol ‘) x (114g) (0-8
atm) (114gmor‘)
••19. 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.
Ans. Solution. Step I. Calculation of molecular mass of solute.
In the first case :
Mass of solute (30 g) — mol
No. of moles of solute (nB) - TT^ i T ~ /u ,-u M
Molecular mass (Mg mol ) 5 mol
Mass of solute _ (90 g)
-1
No. of moles ot water (nA) Molecular mass (18 g mol )
• 3.92 Solutions
wsa
Mole fraction of water (JCa) = (5 mol)

nA +% ^5 mol + mol j (5 +
Vapour pressure of solution (PA) = 2-8 kPa

According to Raoult’s Law P A = PAJCA
(2-8 kPa) = Pi ...fti

FU
In the second case :
30 ,
No. of moles of solute (ha) — mol M
No. of moles of water (nA) — Mass of ~—

water (108 g) ,
| o mol
,
Molecular mass (18 g mol- )
(6 mol)
Mole fraction of water (JCa) =
6 mol + — moi .
«A + «B
M Ft)
Vapour pressure of solution (PA) = 2-9 kPa
According to Raoult’s Law, P A = pA,*A
(2 9 kPa) = PA ...(H)
FIJ
Dividing eqn. (i) by eqn. (ii)
(2-8 kPa) 5 x (6M + 30)
6 x (5M + 30)
(2-9 kPa)
28 6 16-8
6M + 30
or
5M + 30 ~ TF * T ” 74
or 1-159 (5M + 30) = 6M + 30
or 5-795 M + 34-77 = 6M + 30
4-77
or 0-205 M = 4-77 or M = - 0-205 = 23-27
Molar mass of solute « 23-27 g mol-1

Step II. Calculation ofvapur pressure of water
According to Raoult's Law,
pA = P>A or <2'S kPa) = PA

5+B
M
Solutions
- P° ^ - p° —5—
A
or (2-8 kPa) = PA 5+ 1 29 A 6-29
f5+-*U
l 23-27 )
or = (2-8 kPa^) x 6- 29 = 3.52 kPa
• •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
Ans. / MB x W A
For cane sugar solution : 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) ________
2-15K ■ (342gmorr)x (0-095 kg) ...Q)
For glucose solution :

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) ...(H)
Divide eqn. (ii) by eqn. (i) ( K / ) x (5g)

AT/ (342 g mol ])x (0-095 kg)
(2 • 15 K) (180 g mol'1 )x (0-095 kg^ (K/)x(5g)
(342gmoF1) ,,
AT, ~ nen --------- Frrx2‘15K = 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 AB 2 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.
Calculate atomic mass of A and B. (A.l.S.B. 2004)
K / x WB
M
Ans. B AT/ x WA
Step I. Calculation of the molecular masses of the two compounds.
For the compound AB2 :
WB = 1 g ; WA = 20 g = 0 02 kg ; AT/ = 2-3 K ; K/ = 5-1
K kg mol'1
1
M _ (5-1 K kg mol" ) x ( l g ) = j 10.87 g mol-t (2-3 K)x
(0-02 kg)
* 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
...a)
Subtract eqn. (i) from (iij
:(ii )
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
At 300 K, 36 g glucose present per litre in its solution has osmotic pressure of 4-98 bar
•22,
If the osmotic pressure of the solution is 1*52 bar, at the same temperature, what would
be its concentration ?
CRT
V
Ans.
n=
W,'B _ (36 g)
1st case n = 4-98 bar ; C _ -0-2 mol
MB (180 g mol ')
T = 300 K ; V = 1 L
( 0 - 2 mol) x R x (300 K)
(4 -98 bar) =
(1 L) ...(i)
Ilnd case : n = 1*52 bar ; T = 300 K, V = 1 L
= C x R x (300 K)
( 1 5 2 bar) =
1L ... (H )
Divide eqn. (ii) by eqn. (i)
(1-52 bar)
(4-98 bar) 0 • 2 mol
(1-52 bar)
C=
(4 ■ 98 bar) X (0-2mol) = 0-061 mol
= 0-061 mol L'1 - 0-061 M.
• 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.
Ans. (a) IF the density of solvent is lg/mL. In aqueous solution, the density of water is normally
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 (Ci2H220n)
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, AV tmix)
Ans.
will be negative and solution will show negative deviation as CH3. .-Cl
^C=0 ....... H—CCf
compared to ideal solution.
Outer hard shell of two eggs are removed by placing them in dilute HC1.“3 If one is kept in
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 (nB) 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.
• 3.97
Solutions
□ □ Plants grown in marshy lands generally decay after sometime. Assign reason.
Ans. Plants that are grown in marshy lands have developed high osmotic pressure because of the presence of
extra salt particles in the cell saps. Therefore, they may absorb excess of water from the soil which
will lead to the bursting of root hair. The plants will therefore, slowly decay.
□ □ Calcium chloride is used to clear snow in cold countries. Explain.
Ans. When calcium chloride is added to snow which is ice, the freezing point of water gets lowered because
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 (NH 2CONH2)
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
How does pressure influence the solubility of a gas in

1. Define a solution. 6.
a liquid ? State the law which governs it.
2. Give an example of a solution in which solute is a solid 7. The solubility of C02 in water increases with increase
while solvent is a liquid. in pressure but decreases with the increase in
3. Does the solution of oil and water represent a true temperature ? Explain.
solution ? What is a saturated solution ? What happens if the
temperature of the saturated solution is increased ?
4. Define solubility. How is it expressed ? 8. Why are ionic solids soluble in water but insoluble in
5.
The solubility of NaCl in water increases with rise in polar solvents ?
temperature while that of CUSO4 decreases. 9.
Why ?
>
• 3.96 Solutions
10. Carbon tetrachloride and water are immiscible 4. Units of solubility = g/IOOg of the solvent.
whereas ethyl alcohol and water are miscible in all 6. Solubility increases with rise in pressure according to
proportions. Explain, Henry’s law.
11. Give the example of a solution which has liquid as 8. It becomes unsaturated.
the solute and solid as the solvent. 10. Ethyl alcohol and water are both polar while CC14 is
Hints and Answers non-polar.
11. Hydrated salts.
2. Solution of soluble salts in water.
3. No. it is not a true solution.
CONCENTRATION OF SOLUTIONS
1. Define molality. What are its units ? 9. Define (i) normality (ii) molarity (iii) mole fraction.
(D.S.B. 1994; A.l.S.B. 1993)
(H.P. Board 1994)
10. Molality and mole fraction of the solutions are not
2. What is the effect of temperature on molarity of a affected by change in temperature while molarity
solution ?
and normality change. Explain.
3. What is molality of a solution ? How does it differ
11. Out of 1M H2SO4 and IN H2SO4 which is more
from molarity ?
concentrated and why ? (Pb. Board 2003 Supp.)
(D.S.B. 1994, Haryana Board 98 Supp.)
12. Why does molality (m) remain unchanged with
4. Out of molality and molarity which is better for
temperature but molarity (M) changes ?
expressing the concentration of a solution ?
(Pb. Board 2003)
5. Explain the terms mass fraction and mole fraction. 13. Why is 1 M solution more concentrated than 1m
(A. I. SB. 1994) solution ? (Pb. Board 2004)
6. Define molarity and mole fraction. Hints and Answers
(Haryana Board 2000)
7. Define normality of a solution.
1. Moles/kg.
8. Define the terms molarity and molality of a solution. 2. It changes.
How does the rise in temperature change molarity 4. Molality is better.
and molality values of the solutions. (D.S.B. 2001) 10.
Volume is not involved in case mole of molality and
fraction but is considered molarity for expressing
and normality.
11. 1M H2SO4 is more concentrated.
RAOULT’S LAW (IDEAL AND NON-IDEAL SOLUTIONS)
1. Define the vapour pressure of a liquid. What are the 5. Distinguish between ideal and non-ideal solutions.
factors which influence the vapour pressure of the (Haryana Board 1999, 2001)
liquid 7 6. Certain solutions show positive deviations from
2. Explain why the vapour pressure of a solvent gets Raoult’s Law while some show negative deviations.
lowered when a non-volatile solute is added to it. What does it signify ?
(D.S.B. 1993, H P. Board 1995) 7. Explain an azeotrope. Give one example each of
3. State Raoult’s Law. Derive its expression for a maximum boiling and minimum boiling azeotrope.
solution containing non-volatile solute in a volatile (H.P. Board 2000)
solvent. (Pb. Board 1996) 8. Rectified spirit is an azeotropic mixture. How will
4. What is an ideal solution ? What are the you prepare absolute alcohol from rectified spirit ?
characteristics for an ideal solution ?
Solutions • 3.99
9. Mention the characteristics of ideal solution. What proportions Co-relate the above behaviour with
causes deviation of non-ideal solutions from Raoult’s molecular structure of these compounds.
LaW 7 (Pb. Board 1999) (A.I.S.B. 2003)
10. Discuss the behaviour of the non-ideal solutions 18. What are non-ideal solutions ? Explain as to why
showing positive and negative deviation from non-ideal solutions deviate from Raoult's Law.
Raoult’s Law. (Haryana Board 2001) (D.S.B. 2003)
11. Carbon tetrachloride and water are immiscible while 19. State and derive Raoult’s Law for a solution
ethyl alcohol and water are miscible in all proportions. containing
Co-relate the above behaviour with structural nature (a) Volatile solutes (b) Non-volatile solutes.
of the molecules of these compounds. (D.S.B. 2001) (H P. Board 2003)
12. Give the main points of distinction between nonideal 20. Why is vapour pressure of solvent lowered on adding
solutions showing positive and negative deviations non-volatile solute to it ? (Pb. Board 2004)
from Raoult’s Law. 21. Mixing of acetone and chloroform occurs with
13. Draw a suitable labelled diagram to express the reduction in volume and is endothermic process.
relationship for ideal solutions of components A and B What change will occur in vapour pressure ? Explain
between vapour pressures and mole fractions of your answer. (Pb. Board 2004)
components at constant temperature ?
22. State Raoult’s Law for solution containing volatile
(D.S.B. 2002)
liquid maxture. (C.B.S.E. Foreign 2004)
14. What are ideal solutions ? Explain non-ideal
solutions showing negative deviation from Raoult’s 23. Ethanol and water form a solution showing positive
Law with diagram. (Haryana Board 2002) deviation from Raoult’s Law. Explain.
15. Explain the relation between mole fraction and (H.P. Board 2004)
Raoult’s Law for solutions having volatile solutes lints and Answers
with the help of diagram. (Haryana Board 2002) 7. Maximum boiling : 20-2% HC1 and 79-8% water
16. What is Raoult’s Law ? Why does a solution of ethanol by mass
and cyclohexane show positive deviations from ideal 21. Vapour pressure of the solution will decrease.
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. What are the colligative properties of a solution? What 7. How will you show that depression in freezing point
is common in all these ? temperature is a colligative property ?
(Pb. Board 2001)
2. How does relative lowering in vapour pressure help in
calculating the molar mass of a solute ? 8. Illustrate elevation in boiling point with the help
of vapour pressure temperature curve of a solution.
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)
9. Explain why freezing point of solution is lowered
4. How will you show that relative lowering in vapour when a non-volatile solute is present in it.
pressure is a colligative property ? (A.I.S.B. 2001)
(Pb. Board 2001)
10. Show graphically how the vapour pressure of a
solvent and solution change with temperature. Show
5. Define boiling point of a liquid. Why does the boiling on this graph the boiling points of the solvent and
point of a liquid rise when a non-volatile solute is solution. Which is higher and why ?
added to it ? (A.I.S.B. 2001)
6. What is molal elevation constant ? What are 11. Define osmosis. Under what conditions does osmosis
units? (D.S.B. 1997) take place ? (Pb. Board 1997)
• 3.100 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 2002)
kept in NaCl solution, it shrinks. Assign reason. 23. Write two points of distinction between diffusion
(A.I.S.B. 1998) and osmosis. (Pb. Board 2002)
13. What is the difference between osmosis and
diffusion ? 24. Why is calcium chloride used to clear snow in
(J.K. Board1997)
14. Give a method for determining the osmotic pressure of cold countries ? (Pb. Board 2003 Supp.)
a solution. State the principle underlying this method. 25. Explain as to why there is a rise in boiling point when
15. How does osmotic pressure depend upon a non-volatile solid is dissolved in a liquid.
temperature ? (Haryana Board1996) (D.S.B. 2003)
16. What is Van’t Hoff equation for dilute solutions ? 26. What type of azeotrope is formed by mixing nitric
In what way is it helpful in calculating the osmotic acid and water ?
pressure of a solution ? (D.S.B. 2000) (C.B.S.E. sample paper 2003)
16. What are isotonic solutions ? What happens when such 27. What is osmotic pressure ? Explain how the
solutions ane separated by a semipermeable molecular mass of a non volatile solute can be
membrane ?(H.P. Board determined from it ? (Haryana Board 2004)
1999)
18. Why are injectable medicines dissolved in saline water Hints and Answers
before being administered ? 1. All depend upon the no. of solute particles.
19. In marshy places, the plants decay quite fast. Assign 6. K kg mol"1 <K m'1),
reason.
20. What happens when R.B.C, are placed in 0-1% NaCl 15. Increases with rise in temperature.
solution ? 18. Both become isotonic.
21. When fruits and vegetables that have been dried are 19. Plant roots burst because of extra intake of water
placed in water, they swell in size and regain their 20. Their size will increase,
original form. Why ? Would a temperature increase 21. Due to osmosis which increases with rise in
accelerate this process ? temeprature.
22. Out of the following solutions which has the 22. I M urea solution.
maximum freezing point and why ? 26. Maximum boiling azeotrope is formed.
(i) 1 M urea
ABNORMAL MOLECULAR MASSES

1. What do you understand by abnormal molecular 8. Explain giving examples the term ‘colligative
masses of solutes ? property*. Why do we sometimes get abnormal
(Haryana Board 1998, A.I.S.B. 1996) molecular masses of the substances using colligative
2. Define Van’t Hoff factor. (Pb. Board 1998) properties of the solution. (C.B.S.E. Foreign 2003)
3. What is Van’t Hoff factor ? How does it help in 9. Give one example each when Van’t Hoff factor is
determining the degree of dissociation and 2 and 1/2. (Pb. Board 2003)
association of a solute in solution ? 10. Explain with the helps of suitable examples in each
(Pb. Board 2000) case. Why the molar masses of some substances
4. The value of Van’t Hoff factor for a solution is more determined with the help of colbgative properties are
than 1. What does it signify 2(A.I.S.B. 2000) (i) higher (ii) lower than actual values.
5. What are degree of dissociation and degree of (C.B.S.E. sample paper 2003)
association of electrolytes ? How are these related to
the Van't Hoff factor ? Hints and Answers
6. What happens to the colligative properties when 4. Solute dissociates in solution
solute associates in solution ? (H.P. Board 1999) 7. 5 8. (i) Less than 1 (ii) More than 1.
7. What is the expected Van’t Hoff factor for 9. i = 2 (KCI), i = 1/2 (C6H5COOH)
K4[Fe(CN)jJ when it completely dissociates in water?
(D.S.B. 1998)
t
Solutions • 3.101
jOSi Competitive £xcmu*tatiOHi
Measurement of Relative Lowering in Vapour Pressure

(Ostwatd and Walker Method)
The relative lowering in vapour pressure can be measured with the help of this method. The apparatus
consists of two sets are glass bulbs (three in each set). The three bulbs of the first set are filled with the
solution to about half of their capacity while the other three bulbs are filled with the pure solvent to the same
level. These sets of bulbs are weighed separately and kept in a constant temperature both (thermostat) as
shown in the Fig. These are then connected with three U-shaped weighed glass tubes which are filled with
anhydrous CaCI2 to absorb the water vapours {P4O10 or even cone. H2S04 can also be used). These are also
called Guards tubes since they donot allow the water vapours from outside to enter the glass bulbs.
_^ ^ Dry air
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
additional water vapours because the vapour pressure on the surface of the solvent is more than on the
surface of the solution. The increase in the mass of air is proportional to the difference in the vapour
pressure of pure solvent (P^) and solution (P s). Finally, the air is passed through set of calcium chloride
tubes which absorb all the water vapours present in the air and dry air escapes from the outlet. These tubes
are detached and weighed again to find out the increase in mass which corresponds to the maximum value
of vapour pressure i.e. vapour pressure on the surface of solvent (P A).
Calculations
Loss in mass in the solution bulbs « P5
Loss in mass in the solvent bulbs x (p^- Ps)
Total loss in mass in both set of bulbs x P{ + (PA - Ps) = PA-
(Gain in mass of CaCl2 tubes)
Loss in mass in solvent bulbs
PA-PS
Thus, Gain in mass of CaCl2 tubes
• 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 Raoult’s Law. According to the law,
In case, the solution is dilute (WB/MB) can be neglected.
PA - Ps _ WB x MA P;
MB x W A
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.
PA ~ Ps _ Loss in mass of solvent bulb

Solution :
PA Gain in mass of CaCl2 tube
(Q-087g)
(2-036g) = 0 0427
According to Raoult’s Law
WB/MB + WA/MA
26-66
MB p° _ p
77 -----200
26 66 1A
wr = —=. s = 0-0427
-------- fs.
** 77~ PA
MB 18
26-66 x 18 x MB
MB 26-66 x 18
= 0-0427 or = 0-0427
26-66 x 18 + 200 XMB 26-66 x 18 + 200 x MB
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
MR = = 53-8.
8-54
Note. The number of moles of solute (W„/M B) 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.
IogJi = _^Ll3L_ T» - Ti
6
P, 2-303R T, x T 2 J
Here PL and P2 are the vapour pressures at temperatures T[ and T 2 respectively while AHvap is the molar
enthalpy of vaporisation.
SExump The boiling point of CCl4 is 77°C and its heat of vaporisation is about 31 kJ mot 1. Calculate the
vapour pressure in atmospheres at 25 °C.
log A = AHvaP P, T2-Tt

Solution 2-303 R
T, x T- 2 J
P2 = 1 atm (because 77°C 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
log (31 x 10J J mor‘)x (52 K)

2- 303 x (8-314 J K'1 mol'l)x (298 K) x (252 K)
= 0-807
= Antilog (0-807) = 6-41

M
__
(1 atm)
Pi = = 0-156 atm.
6-41 6-41
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 Raoult’s Law at all temperatures aqd all concentrations.
Non-ideal solutions may show either positive deviations or negative deviations from
> Raoult’s 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 Van’t 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
Molality (m) =
_ No. of moles of solute
Molarity (M) Volume of solution in litres
No. of equivalents of solute
Normality (N) Volume of solution in litres
Henry’s Law : m « P (At constant temperature)
Partial V. P. of the gas
Henry’s Law constant : KH =*
Mole fraction of gas in solution
Raoult’s Law P = PA-tA + PB XB (For ideal solutions)
P. -Ps * «SL
(For ideal solutino)
«A
P* - Ps = JfiL
"A (For non-ideal solution)
„ K„XW X1000
Elevation in b.p. B: AT/, = K/, x m = —2 ----§ ---------
MBXWA
Solutions • 3.105
MR(T ^)2
Molal Elevation Constant :KJ, - -- --77;—
b
1000 X AHvap
MR(T })2
Molal Depression
r constant : Kf =J , —777
1000 x AH vap
r X WB x 1000
K
Depression in f.p. : ATy = K/ x m = —
Pi _ T, - T,
Clausius Clapyron’s equation : 1°S
P, 2-303RLT|xT 2
Osmotic pressure it = CRT = - 7V

RT
v
Normal molecular mass
Van’t Hoff factor :
1
Observed molecular mass
i-1
Degree of association : a~^^j
i-1
Degree of dissociation : a=
n-1
m
G<mp&tdive£'X&Mi*uM<HU
Q.l. The vapour pressure of a dilute aqueous solution of glucose (C^lluOt) is 750 mm of mercury at
373K. Calculate (i) molality (ii) mole fraction of the solute. (I.I.T. 19S9)
Solution: -SteP Calculation of mole fraction of glucose.
n,,, P\ - Ps 760 - 750
10
According to Raoult s Law, xB = —■ e—— =------------- = — = 0-0132
760 760
Step Calculation of molality of solution
Mole fraction of solute = 0-0132
«B
*B
”B + nA
If H|1 moles of the solute be dissolved in lOOOg of the solvent, then «B will represent molality of the solution.
(100 ° S) ,
= = 55-55 mol
xB - 0-0132 ; nA (jggmor1)
»B .xB or „
«B
. cccc 0 0132
71g + nA «B + J-*
/tB = 0-0132 x nB + 55-55 x 0 0132
0-9868 nB = 55-55 x 0-0132
55-55 x 0-0132
"B = 0-74
0-9868
Solutions
Q.2. Vapour pressure of pure benzene at a certain temperature is 640 mm Hg. A non-volatile non-
electrolyte solid weighing 2-175g is added to 39-0g of benzene. The vapour pressure of solution is 600 mm
Hg, What is the molecular mass of solid substance ? (I.l.T. 1990)
Solution : Step I. Calculation of no. of moles of solute
^solution ~ Pbenzene x ^benzene
_ ^solution _ (600mm) _ 600
■^benzene
Pbenzene (640mm)
6
40
■^benzene Moles of benzene + Moles of solute
Moles of benzene 1
600 (39g)/(78gmol~ ) 0-5
640 39g/(78gmor1 J + 0-5 + nwiM
0 5 + iw =0-5 x|£ = 0 533
risoiuie = 0-533 - 0-5 = 0 033
mol
Step 11 Calculation of molecular mass of solute
Mass of solute _ (2-175g)
Molecular mass No. of moles of solute (0 ■ 033 mol) ~ 65-9g1-1
mol
Q.3. Calculate the number of molecules of oxalic acid in lOOmL of 0-02N oxalic acid solution.
(Roorkee 1991)
Solution : Step 1. Calculationof no. of moles of oxalic acid per litre of the solution.
No. of moles of oxalic acid
Molarity =
Volume of solution in litre
, No. of moles of oxalic acid N 0-02
(0 01 mol L'1) -- --------------— -------------- (■•■ M = — = —-— = 0-1M)
No. of moles = O-Oi mol.
Step II Calculation
of no. of molecules of oxalic acid per 100 mL of solution.
1000 mL of oxalic acid solution contains moles = 0-01
001
100 mL of oxalic acid solution contains moles x 100 = 0 001 mol
100
Molecules of oxalic acid = 0-001 x NQ.0
= 10’3 x 6-022 x 1023 = 6-022 x 1020 molecules.
Q.4.The degree of dissociation of Ca(NOj)2 in dilute solution aqueous solution containing 7-0g of the solute per lOOg of
water at 100°C is 70 percent. If the vapour pressure of water at 100°C is 760mm, calculate the vapour pressure of the solution.
(I.l.T. 1991)
Solution : Step I Calculation

of the Van't Hoff factor (i)
Calcium nitrate dissociates in aqueous solution as :
Ca(N03)2 — ^ Ca2+(aq) + 2N03’ (aq) l-l
l-l
a - -------- 7 or 0-7 = — ----- 7 or l = 0-7 x 2 + 1 = 2-4
n-1 3-1
Solutions * 3.107
ilihiiitillliiiii
Step II. Calculation of vapour pressure of the solution
According 10 Raouit's Law
PA-PS . =f«B_ =«B
Ps ( .- Solution is dilute)
p;-ps i x W B x MA
(Solution)
Ps MB x W A
PA = 760mm, i = 2-4, WB = 7-0g, MB = 164 g mol'1 = (for calcium nitrate)
WA lOOg, MA = 18g mol"1
760 - Ps 2-4 x (7-0g)x (18gmorl)

760 (164gmor*)x (100g)
760 - Ps = 0-0184 or Ps = 760 - 0 0184 X 760

760
Ps = 760 - 13-98 -- 746-02 mm.
Q.5. A solution of urea in water boils at 100-18°C. Calculate the freezing point of the same solution. Molal constants
K, and K, are 1-86 and 0-512 K m'1 respectively.
Solution : ATy = K, x m and AT, = K, X m
AT> =
AT, K,
AT* = 100- 18°C - 100 0 - 0 18°C = 0-18K K, =
1-86 K m-‘, K, = 0-512 K nr1
AT, » -Ll x AT, = (1861C-y~‘|- x 0-18K = 0-654K = 0-654‘C 1 K, 0

(0-512K m_l)
Freezing point of solution = 0°C - 0-654°C = - 0-654°C.
Q.6. Addition of 0-643g of a compound to 50 mL of benzene (density = 0-879 g/mL) lowers the freezing point from 5-51
“C to 5-03°C. If K,for benzene is 5-12, calculate the molar mass of compound. (I.I.T. 1992)
Solution : Mass of benzene (WA) = V x d = (50 mL X 0-879 g/mL) = 43-95g = 0-04395 kg WB =
0-643g, AT, = 5-51 - 5-03 = 0-48°C = 0-48K Kf = 5-12K kg mol-*
K, x WB
Molar mass of compound (MB)_ A-jy x v/A
= (5-12 K kg mor^x (0-6436)1 = mol-t.
(0-48K) x (0-04395 kg)

Q.7. What mass of a non-volatile solute urea (NH2CONH2) need to be dissolved in l00g of water in order to
decrease the vapour pressure of water by 25% ? Also calculate the molality of the solution.
(I.I.T. 1993)
Solution : Step 1 Calculation of mass of urea

Q
Vapour pressure of water = PA
• 3.108 Solutions
Vapour pressure of solution (P A) = - l / 4PA) = 3/4 pA

For the' solution,
PA*A - PA X *A
rtA + ns
(100 g) : (18 100
«A
mol; = —(WB g) _ Wg_ mol.
g mol-1) 18 (60 g mol ) 60
(100/18 mol)
3/4 P A = PA
(100 /18mol) +(W /60 mol)
3_ 100
4 18 10 18 x 60
100 x 60 + W x 18 0 6000 x 18 W
3^ 18 x 60 18
4 6000
or 6000 + 18W = 6000 X — = 8000.
6000 + I8W
2000
18W = 8000 - 6000 or W = 18 = 1 1 1 1 .
Mass of urea = l l l l g
Sup II Calculation of molarity of solution.
Mass of urea
Molarity of solution (M) = (llllg)
Molar mass (60 g moH) ill-1 m o l k-Ig
Mass of watering/1000 (kg) (100/1000 kg) 6 0 x 0 - 1
= 18-52 mol kg'1 = 18-52 m.
Q.8.Calculate the freezing point of a non-electrolyte aqueous solution having osmotic pressure of 2-0 atm
at 300 K (Ky = 1-86 K kg mol'1). (Roorkee 1993)
Solution : Step I Calculation of the molar concentration of the solution
n = CRT or C -
RT
(2'Oatm)
C= = 0-0812 mol L'1
(0-0821 litre atm K_1mot~^) x (300K)
Step 11. Calculation of freezing point of the solution
It is assumed that the molarity (concentration) of the solution is the same as molality.
m = 0-0812 mol kg'1
Now. ATy = Kf x m = (1-86 K kg mol'1) x (0 0812 mol kg'1) = 0151K.
Freezingpoint of solution (Ty) = T°y- ATy = 273K - 0 1 5 1K = 272-849 K.
Q.9. 8-0575 x 10'2 kg of Glauber's salt is dissolved in water to obtain 1 dmJ of a solution of density 1077-2 kg m'3. Calculate
the molarity, molality and mole fraction of Na2S04 in the solution. (/./. T. 1994)
Solution : Molecular mass of Glauber’s salt (Na2S04.10H2O)
= 2 x 23 + 32 + 4 x 16 + 10 x 18 = 322 a.m.u. = 322 gmol'1
Mass of Glauber’s salt = 8 0575 x 10"2 kg = 80-575 g
Solutions • 3.109
Mass _______(80’575 g)
Moles of Glauber’s salt = 0 • 25 mol
(322gmoTr)
Molar mass
Volume of the solution = 1 dm3 = 1L = 1000 mL
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
jn kg = Îsg /1000) = O'2508 ‘
m
Molality of solution <«) = Massof
ir 996-625g ..
Moles of water =----------------= 55 -37 mol
(18gmol *)
(0-25 mol) (0 25 mol)
Mole fraction of solute = 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 L‘l = 0-25M.
Q.10. The freezing point of a solution containing 0-2g of acetic acid in 20-0g of benzene is lowered by 0-45’C.
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 = 0-45°C = 0-45K, Kf = 5-12 K kg mol’1
(512 kg K mol-1) x (0-2g)x 1000

MB = 113-78 g mol I-I
(0-45K) x (20g)
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
0-473
«= = 0-946
(1/n-l) (1/2-1) 0-50
Degree of association (a) = 0-946 X 100 = 94-6%.
Q.ll. 0-85 g aqueous solution of NaN03 is approximately 90% dissociated at 27°C. 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-1n - i-I
a or 0-9 = or 1 1 = 0-9 + 1 = 1-9
1
• 3.110 Solutions
Calculation of osmotic pressure Initial

(0-85g)
no. of moles of NaN03 (nB) = 0 01 mol
(85 g mol !)
/ nBRT
Osmotic pressure (it) = (CRT - ———
19 x (0 01 mol) x (0 0821 Latin K~* mol-1) x 300 K ------ ToTlV)

-- =4-68 atm.
Q.12.A very small amount of non-volatile solute (that does not dissociate) is dissolved in 5<»-8 cm3 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
Mass of benzene (50 -5g)

No. of moles of benzene («A) = 0-65 mol
Molar mass of benzene (78-0gmol )
According to Raoult’s Law,
PA ~PS »B
( . Solution is dilute)
P°A "A
100 - 98-88
«B
100 0 -65 mol
1-12
«B x (0-65 mol) = 0-0073 mol
100
No. of moles of solute _ 0 - 0073 mol _ 0 145 m
Molality of solution (m) = = 0-145 mol kg 1
Mass of solvent in kg 0 0505 kg 0-0505 kg
Step II. Calculation ofmolal depression constant (Kj)
m = 0145m, ATy = 0-73° = 0-73K
AT
ATy = Ky x m or Ky = /
V- m
(0-73K)
Kr = 5-034 K m'1.
V =( 0 1 4 5 m )
Q.13.A solution of non-volatile solute in water freezes at -0-30°C. The vapour pressure of pure water at 298K is 23-51
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,
AT, K y x m or m —
K,
ATy = 0 - (- 0-30°C) = 0-30°C = 0-30K, Ky = 1-86 K m"
(0-30K)
= 0-16 m
(1-86K mol-1)
Solutions • s.m J
Step II. Calculation of mole fraction (x &) of the solute

0- 16m solution means that 0-16 mole of the solute is dissolved in 1 kg of the solvent (water)
nB 016
JfB 0 16 + 1000 (18
= 0-00287
"B + «A
Step III. Calculation of vapour pressure of solution APA

Mole fraction of solvent (xA) = I - JCB = 1 - 0-00287 = 0-99713 Vapour pressure of
solution = P°AxA = (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+
l-1 (-1
a - ---------- - or 0-23 = -- --- r or i = 1 23
n- 1 2-1
Step II. Calculation of molality of solution (m)
Mass of acetic acid (30g)

No. of moles of acetic acid (60g mol”1) = 0 05 mol
Normal molar mass (CH3COOH)
No .of moles of CH3COOH

Molality (m) Mass of water in kg
(0 05 mol) 0-05 x 1000

= 0-lm
500 x 0-997 500 x 0-997
kg
1000
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/m3.
(b) Match the following if the molecular weights of x, y and z are the same.
Solute Roiling point <°C) K*

X 100 0-68
y 27 0-53
z 253 0-98 (l.l.r. 2003)
Solution : (a) Density of water = 1000 kg/m3
1 Litre of water = i kg = 1000 g

• 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.
(b) Higher K, value of the solvent implies its higher polarity and thus, higher boiling point as well since the boiling
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 0-17°C and 0-13°C 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 ? (/■/■ T. 2004)
Solution : (a) Molecular mass of benzoic acid in acetone solvent
Kj, x WB x 1000
MR = AT, x WA
(1-7K kg moP1) x (l-22g) x 1000 . I22

(017K) x (100 g)
Molecular mass of benzoic acid in benzene solvent
K, x WB x 1000
MR AT,, x WA
(2-6 K kg moP1) x (122g)x 1000

= 244 g mol'
(0-13K) x (lOOg)
(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
\
✓H
o-c=o
1
C6H5
Solutions
Molal depression constant depends upon

1. Which of ihe following 0-1 M aqueous solution will (a) nature of the solute
have lowest freezing point ? (b) nature of the solvent
(a) Potassium sulphate (b) Sodium chloride (c) vapour pressure of solution
(c) Urea (d) Glucose.
(d) heat of solution. (Pb. C.E.T.
(M.L.N.R. 1990) 1991)
9. Mole fraction of glycerine CJHJ(OH>3 in solution
2. Molality is expressed in
(a) Grams/litre (b) Litres/moles containing 36gm of water and 46 gm of glycerine
is
(c) Moles/litre (d)
Moles/kg. (a) 0-46 (b) 0-40
(C.B.S.E. Med. 1990)
(c) 0-20 (d) 0-36 (C.P.MT.
3. The freezing point of equimolar aqueous solution be
1991)
will highest for 10. The molecular mass of sodium chloride as
determined by osmotic pressure method is :
C6HjNH3d (a) equal to 58-5
(a) (b) Ca(NO 3)2
(b) greater than 58-5
(C) La(N03)3 (d) C6Hi206.
(l.l.T. 1990) (c) less than 58-5
4. Osmotic pressure of a solution is 0-0821 atm at (d) none of the information is correct.
temperature of 300K. The concentration of solution in (Haryana C.E.T. sample Paper 1992)
moles/litre will be
11. The molarity of pure water is
(a) 0-33 (b) 0-066
(a) 55-6 (b) 50
(c) 0-3 x lO '2 (d) 3.(Roorkee 1990)
(c) 100 <d) 18. (K. C.E.T.
5. Which is not a colligative property ?
1993)
(a) ATy- fb) n 12. Which of the following liquid pairs will show
(c) AJb {d) K*. positive deviation from Raoult’s Law ?
(Pb. C.E.T. 1991) (a) Water-hydrochloric acid
6. The relative lowering in vapour pressure is (b) Water-nitric acid
proportional to the ratio between the number of
(a) solute molecules to solvent molecules (c) Acetone-chloroform
(b) solute molecules to the total number of (d) Ben2ene-methanol. (M.P.C.E.E. 1993)
molecules in solution 13. The law which states that the mass of a gas dissolved
(c) solvent molecules to the total number of in given mass of the solvent at any temperature is
molecules in solution directly proportional to the pressure of the gas
(d) solvent molecules to the total number of ions above the solution is:
in solution. (C.B.S.E. Med. 1991) (a) Joule’s law (b) Boyle’s law
7. 500g tooth paste sample has 0-2g fluoride ion
concentration. What is the concentration of fluoride (c) Henry’s law (d) Charle’s law.
in terms of ppm level ? 14. Increasing the temperature of an aqueous solution
will cause
fa) 250 fb) 200
(a) decrease in molarity
(c) 400 (d) 1000.
(A.l.I.M.S. 1991) (b) decrease in molality
(c) decrease in mole fraction (l.l.T. 1993)
(d) decrease in % (w/w).
• 3.114 Solutions
15. The vapour pressure of a solution of 5g of non- 23. An elevation in b.p. of a solution of lOg of solute
electrolyte in lOOg of water at a particular (molar mass = 100) in 100 g of water is AT*. The
temperature is 2985 Nm'2. The vapour pressure of ebullioscopic constant for water is :
pure water at this temperature is 3000 Nm"2. The (a) 10 (b) 10AT„
molecular mass of solute is :
(a) 180 (b) 90 (c) AT* (d) AV10.
(c) 270 (d) 200. (I.I.T. 1993) (C.B.S.E. Med. 1995)
16. The molal freezing point for water is 1-86° C/m. 24. A 0-2 molal aqueous solution of a weak acid (HX)
Therefore, tne freezing point o f O l m NaCI is 20 percent ionised. The freezing point of this
solution in water is expected to be : solution is (Given = 1-86°C kg mol"1 for water)
(a) - 1-86°C (b) -0 186°C (a) - 0-45°C (b) - 0-90°C
(c) - 0-372°C (d) + 0-372°C. (c) - 0-31°C (d) -0-53°C.
(M.L.N.R. 1994) (LI T. 1995)
17. Van’t Hoff factor for 0-1 M ideal solution is : 25. 0-1 M NaCI and 01M CH3COOH solutions are
(a) 0-1 (b) 1 kept in separate containers. If their osmotic
(c) 0 01 (d) None of these. pressures are P[ and P2 respectively then what will
be the correct statement ?
(M.L.N.R. 1994)
18. At 25°C, the highest osmotic pressure is expected (a) P, > P2 (b) P, = P2
by OT M solution of : (c) P| < P2 (d) P| = P2 = 0 atm.
(a) CaCI2 (b) KC1 (C.P.M.T. 1996)
(c) Glucose (d) Urea. 26. Azeotropic mixture of HC1 and H20 has
(C.B.S.E. Med. 1994) (a) 48% HCI (b) 82-2% HC!
19. Which of the following salts will have the same
value of Van't Hoff factor (f) as that of (c) 36% HCI (d) 20-2% HCI.
K4[Fe(CN)(,| (A.F.M.C. 1997)
(,a) AI2(S04)3 (b) NaCI 27. Which is not affected by temperature ?
(c) A1(N03)3 {d) Na2S04. (a) Normality (b) Molality
(C.B.S.E. Med. 1994)
20. 12g of urea is dissolved in 1 litre of water and (c) Molarity (d) Formality.
68-4g of sucrose is also dissolved in 1 litre of (A.I.l.M.S. 1997)
water. The lowering in the vapour pressure of first 28. If all the following four compounds were sold at
case is the same price, which would be the cheapest for
(a) equal to second (b) greater than second preparing antifreeze solution for a car radiator ?
(c) less than second (d) double the second. (a) CH3OH (b) C2H5OH
(E.A.M.C.E.T. 1995) (c) C2H4(OH)2 (d) C3H5(OH)3
21. Isotonic solutions have same (A.M.U. 1997)
(a) Molar concentration 29. The vapour pressure of a solvent decreases by 10
(b) Molality mm mercury when a non-volatile solute is added
(c) Normality to the solvent. The mole fraction of the solute in
the solution is 0-2. What should be the mole
(d) None of these. (A.F.M.C. 1995) fraction of the solvent if the decrease in vapour
22. When mango is placed in aqueous solution of pressure is to be 20mm of mercury ?
hydrochloric acid, it
fo) 0-8 (b) 0-6
(a) Shriks (b) Swells
(c) Bursts (d) Nothing happens. (c) 0-4 (d) 0-4.
(C.B.S.E. Med. 1998)
(C.P.M.T. 1995)
Solutions * 3.115
30. A A solution of cane sugar (molar mass = 342) is 38. For determination of the molar mass of colloids,
isotonic with 1 % solution of a substance X. The polymers and proteins which coiligative property is
molar mass of X is used ?
(a> 171-2 (b) 68 4 (a) Diffusion pressure (b) Atmospheric pressure ft)
fc) 34-2 fd) 136-2. Osmotic pressure (d) Turgor pressure.
(C.B.S.E. Med. 1998) (C.B.S.E. Med. 2OOO)
31. A sugar syrup of weight 214-2 g contains 34-2g of 39. To 500 cm3 of water, 3 0 X 10‘3 kg of acetic acid is
sugar. The molal concentration of solution is : added If 23% of acetic acid is dissociated what will be
fa) 0-55 (b) 5-5 depression in freezing point ? K[ for water is 1-86 K
kg mol'1 and density of water is 0-997 g cm'3.
(c) 55 (d) 01. (U.T. 1998)
fn) 0 186K (b) 0-228K
32. Which has highest boiling point at 1 atm pressure ? fc) 0-372K (d) 0-556K. (U.T. 2000)
(a) 0-1 M NaCl (b) 0-1 M Sucrose 40. The volume of water to be added to 100 cm3 of 0-5N
fc) 0-1 M BaCh (d) 0-1 M Glucose. H2SO4 to get decinormal solution is :
fa) 100 cm3 (b) 450 cm3
(M.P.P.M.T. 1998)
33. An aqueous solution freezes at -0186°C (Ky = 1-86, (c) 500 cm3 (d) 400 cm3.
K;, = 0-512). What is the elevation in boiling point'? (K.C.E.T. 2001)
(a) 0-186 (b) 0-512 41. Depression in freezing point is directly proportional to
(c) 0-86 <d) 0-0512. fa) mole fraction of the solution
f.M.P.P.M.T. 1998) (b) molarity of the solution
fc) molality of the solution
fd) molality of the solvent.
34. The osmotic pressure of 1M solution at 27°C is
(Tamil Nadu C.E.T. 2001)
(a) 2-46 atm (b) 24-6 atm 42. Which of the following aqueous solutions will have
(c) 1-21 atm (d) 12-1 atm. least (feezing point ?
(C.P.M.T. 1999)
35. The Van’t Hoff factor for 0-1M Ba(N03)2 solution is
2-74. The degree of dissociation is :
(a) 9 1 3 % (b) 87%
(c) 100% (d) 74%. (U.T. 1999) (a) 0-1 m urea f<>) 0-1 tn sucrose
36. Which of the following does not show positive
fc) 0-lm acetic acid (d) 0-1 m CaCl2-
deviation from Raoult’s Law ?
(e) 0-1 m NaCl (Kerala E.E.E. 2001)
fa) Benzene-chloroform
(b) Benzene-acetone 43. An aqueous solution of 6-3g oxalic acid dihydrate is
1 made upto 250mL. The volume of 0-1 N NaOH
required to completely neutralise 10 mL of this
(c) Benzene-ethanol
solution is :
f (d) Benzene-carbon tetrachloride. r- (M.P.P.M.T. 2000) fa) 40 mL (b) 20 ml.
i fc) 10 mL fd) 4 mL. (l.I.T. 2001)
37. Depression in freezing point for 1M urea, 1M glucose 44. 250 ml. of Na2C03 solution contains 2-65 grams of the
and 1M NaCl are in the ratio. carbonate. If 10 mL of the solution is diluted to one
(a) 1 : 2 : 3 (b) 3:2:2 litre, what is the concentration of the resultant
(c) 1:1:2 (d) None of these. solution ? (Molar mass of Na2C03 = 106).
fa) 0-1 M (b) 0-001 M
(Haryana C.E.E.T. 2000)
fc) 0-01 M (d) 10"4 M.
(E. A.M. C.E.T. 2001)

• 3.116 Solutions
45. Colligative properties of the solutions are those (ii) Pure solute --- > Separated solute molecules
properties which depend on the AH2.
(a) shapes of the particles (Hi) Separated solvent and solute molecules ; AH
Solution on formed will be ideal if
(b) nature of the solvent
(c) nature of the particles only — AHj *+* AH2 + AH3
(d) number of the particles only (b) AHsol^_ AH, + AH; - AH3
(t) AHso( ^ ■ -ÂH3 - AH, -AH2
(e) volume of the solution. (Kerala P.M.T.
(d) AHso, AH3 - AH| - AHj
2002) (C.B.S.E. Med. 2003)
46. Colligative properties are used for the 52. What is the effect of the addition of sugar on the
determination of boiling and freezing points of water ?
(a) molar mass (a) Both boiling and freezing points increase
(b) Both boiling and freezing points decrease
(b) equivalent mass (c) Boiling point decreases and freezing point
(c) arrangement of molecules increases.
(d) melting and boiling points (d) Boiling point increases and freezing point
decreases.
(e) both (a) and (b j. (Kerala C.E.T. 2002) (e) Boiling point increases and freezing point is
47. 2-5 litre of 1M NaOH solution is mixed with a not affected. (Kerala C.E.T. 2003)
3- 0 litres of 0-5 M NaOH solution. The 53. The volume of water to be added to N/2 HC1 to
molarity of the resulting solution is : prepare 500 cm3 of N/10 solution is :
(a) 0-80 M (b) 1 -0 M (a) 45 cm3 (b) 400 cm3
(c) 450 cm 3 (d) 100 cm3
(c) 0-73 M (d) 0-50 M.
(Kamatka C.E.T. 2003)
(C.B.S.E. Med. 2002) 54. During depression in freezing point in a solution, the
48. What is the Van’t Hoff factor when benzene following are in equilibrium.
vapour pressure falls from 165mm to 162 mm (a) liquid solvent and solid solvent
on addition of 6g of CH3COOH to 3 moles of (b) liquid solvent and solid solute
benzene ? (c) liquid solute and solid solute. (l.l.T. 2003)
(a) 0-56 (b) 0-325 55. Mixture of X = 0-02 mol of [Co(NH3)jS04]Br and
(c) 2 (d) 0-07 0-02 mol of [Co(NH3)5Br]S04 was prepared in 2 litre
of solution.
(U.P.S.E.A.T. 2002) 1 litre of mixture X + excess of AgNC>3 ----- ► Y
49. If liquids A and B form an ideal solution, 1 litre of mixture X + excess of BaCl2 -------- ► Z
(a) the free energy of mixing is zero. No. of moles of Y and Z are :
(b) the free energy as well as the entropy of (a) 0 01,0-01 (b) 0-02,0 01
mixing are each zero. (c) 0-01,0-02 (d) 0-02,0-02
(c) the enthalpy of mixing is zero. (l.l.T. 2003)
(d) the entropy of mixing is zero. 56. Which of the following statements is true ?
(A.I.E.E.E. 2003) (a) The relative lowering in vapour pressure of a
50. In a 0-2 molal aqueous solution of a weak acid solution is equal to the mole fraction of the
HX, the degree of ionisation is 0-3. Taking Kf solute.
for water as 1-85, the freezing point of the (b) Passage of solute molecules towards solution
solution will be nearest to side through semipermeable membrane is
osmosis.
(a) - 0-260°C (b) +0-180<’C
(c) Boiling point of solution is always lower than
(C) - 0-480°C (d) -0-360°C that of the solvent.
(A.I.E.E.E. 2003) (d) Boiling point a liquid is the temeprature at
51. Formation of solution from two components can which its vapour pressure becomes equal to 200
be considered as : mm. (Orissa J.E.E. 2003)
(i) Pure solvent---- > Separated solvent
molecules
; AH,
• 3.117
Solutions
57. The average osmotic pressure of benzoic acid is 7-8 (c) Raoult's Law (d) Le-chatelicr principle.
bar at 37°C. What is the concentration of aqueous (A.F.M.C. 2004)
KCt solution that could be used in blood stream ? 60. Which of the following colligative properties can
(a) 0-16 mol L1 (b) 0-32 mol L_l provide molar mass of proteins polymers or colloids)
l
with greater precision ?
(c) 0-60 mol L~ (d) 0-45 mol L"1.
(a) Relative lowering in vapour pressure
(A.I.I.M.S2004)
58. After adding a solute, the freezing point of a solution (b) Elevation of boiling point
decreases to - 0186. Which is the correct value of (c) Depression in freezing point
TAi> if kf - 1-86 and kt, = 0-512 ? (d) Osmotic pressure
(a) 0-521 (b) 0 0521 (e) Rast’s method. (Kerala P.M.T. 2004)
(c) 1-86 (c) 00186. 61. A 0 004 M solution of Na2S04 is isotonic with a 0 01
(Orissa J.E.E. 2004) M solution of glucose at the same temperature. The
59. Relative lowering in vapour pressure of solution apparent degree of dissociation of Na2S04
containing non-volatile solute is directly proportional is :
to mole fraction of solute. Above statement is : (a) 25% (b) 50%
(a) Henry Law (b) Dulong and Petit Law (c) 75% (d) 85%.
(l.l.T. Screening 2004)
jA^nsivers
10
1. (a) '2. (d) 3. (d) 4. (c) 5. (d) 6. (b) 7. (c) 8. (b) 9. (O . <0
11. (a) 12. (d) 13. (c) 14. (a) 15. (a) 16 (c) 17. (b) 18. (a) 19. (a) 20 (a)
.26 27. (b) 29. (b) .30 (b)
21. (a) 22. (b) 23. (c) 24. (a) 25. (a) (d) 28. (a)
.36 39. (b) .
40 id)
31. (a) 32. (c) 33. <d) 34. (b) 35. (b) (a) 37. (c) 38. (c)
45. (d) .46 (a) 47. (C) 48. (a) .50
41. (O 42. (d) 43. (a) 44. (b) 49. (c) (c)
55. (a) .56 (a) 59. (<) .60 (d)
51. <a) 52. (d) 53. (b) 54. (a) 57. (b) 58. (b)
. .
61. (c)
Hints & Explanations

8. (b) is the correct answer.
1 .(•) K2S04 will form maximum ions in solution
(3)
Is the correct answer. Mole fraction - --------- glycerine ----
2 -(d) 9.(0 ^glycerine + Atwater
3. (d) Except glucose all other will form ions in
solution. 46
4 -(c) jt = CRT 92 0-5
46 36 0-5 + 2-0
rt 0-0821 92 18
RT 0 0821x 300
= 0-2.
= 0.33x 10~2 mol L-1 10. (O Since NaCI dissociates in solution, the
5 -(d) K6 (Molal elevation constant) is not a colligative molecular mass is expected to decrease.
properly.
Molarity (M) = —^77 = 55-55 mol. (l8gmol-1 J
6 .(b) is the correct answer. 11 .(a)
= 55-6
7.(0
ppm = J°'29J x 10s =400. (500g)
Solutions
12, (d) Addition of benzene will reduce H-bonding Freezing point of solution
£:v in CH3OH molecules resulting in increase = 0°C - 45rC = - 45"C.
in the vapour pressure. 25. (a) Since NaCI is a stronger electrolyte than
13, (it) Conceptual problem. CH3COOH, it will dissociate to greater
14, (a) Molarity decreases upon increasing the extent. Therefore P, > P2
temperature as volume increases.
26. (d) is the correct answer.
, , pA - Ps .. W B MA 27. (b) Molality is not affected.
5 ()
- PA ' MB WA 1
28. (a) AT/cc
3000 - 2985 = (59) (189)
3000 WB (100g) AT/will be maximum in case of CH3OH
because its molar mass is the least.
MB =180 (by calculation)
16. (c) ATf = iKfm = 2 x 1 -86cC/m x 0-1 m
= 0372CC _Ap *B
29. (b) _
F.P = 0 - 0-372°C = - 0-372°C Ap'
(b) For ideal solution, Ap' 20
i = 1. *s ^* B* ~ = 0 - 2 X — =q.4
17. (a) CaCI^ will give maximum no. of ions (3) in
solution. Mole fraction of solvent.
18. (a) Both will give same no of ions in aqueous = 1 - 0 4 = 0 6.
solution.
19. _ W B x R x T 71
30. (b) =
MB X V
R, T and V are constants for isotonic
K4[Fe(CN)6] 4K++ [Fe(CN)6]«- solutions
AI2(S04)3 --------^ 2AI3* + 3S042’
20.
(a) Both have same lowering in V.P as they have
same no. of moles. 1 = _5_
MB 342
12g
Urea =
60^ = 02 342
or MB = = 68.4
68-4g 31. (a) Weight of water (W A)
Sucrose 342 g = 0-2.
= 214-2- 34-2 = 180g
21. (a) Isotonic solutions have same molar .. . ... W B 1000
concentration Molality = —x ------ -----
22. (b) It swells due to osmosis Mg WA
(34-2g) 1000
10 1000
23. (c) AJb=Kbx x -------- = K*.
100 100 (342 g mol1) (1809)
24 (a) HX ionises in solution
100
HX ^H+ + X“ = 0-55m,
180
i-1 /-I 32. (c) 0-1 M BaClg because it will form maximum
a = -—ror 02 = —\
n- 1 ions (3) in solution
33. (d) For the same solution.
/ = 1 -2
ATfr _ AT/
ATr = ix K/x m
= 1 2 x (1 -86°C mol'1) x (0-2 m) Ke -'K,
= 0-45°C
Solutions • 3.119
waiakiMj
AT, = 500 cm3
Volume of water to be added = 500 - 100 =
or AT6 ~ -j- x Kb 400 cm3
x 0-512. 41. (c) Conceptual problem
1-86(0-186° C)
42. (d) 0-1 m CaCI2 because it will give maximum
= 0 0512°C. ions in solution.
34. (b) it = CRT 43. (a) Equivalent mass of oxalic acid
= (1 mol L-1) x (0-0821 L atm = = 63
K"1 mor1) x 300 K
= 24 6 atm. Normality of oxalic acid
35. (b) Ba(N03)2 -» 3a2t + 2 N03_ j-1 6-3
100 0-4N
2-74-1 63
0
a = n- 1 3- 1 25
1-74 0
= 0-87.
(oxalic acid) (NaOH)
Degree of dissociation = 0-87 x 100 N,V, =NZV2
= 87 %. V2 =x V2
0-4 x 10 =0-1 = 40 mL
01
36. (a) Benzene - chloroform shows negative 44. (b) Molarity of solution
0-4 x(M)
10
deviation from Raoult’s Law because
attractive forces will increase. _ 2 65 1000
37. (c) 1 M urea and 1 M glucose have same AT, = 0-1 M
106 250
value but the value is double for NaCI (Concentrated) (Diluted)
solution. The ratio is 1:1:2. M-iVi = M2V2
38. (c) Conceptual problem 0-1 X 10 = M2 x 1000
39. (b) CH3COOH dissociates in water as :
0-1x 10
CH3COOH --- --- ^CH3COQ- + H+
M? = = 0-001 M
1000
/ -1 i-1 45. (d) Conceptual problem
a or 0-23 =
n-1 2-1 46. (a) Conceptual problem
/ = 1 + 0-23 = 1 -23 47. (c) M,V, + M2V2 = M3(V1 + V2)
WR 1000 M^V^ + MZV2
Molality (m) = —x —— M3 = ---- -----------
MB W A
(V, + v2)
(3g) 1000 1 X 2-5 + 0-5 x 3
M3 =
(60g) (500x 0-997) 2- 5+3
4- 0
(3g)x 1000
5 - 5= 0.73M
(60g) x (498-5g) =0'1
AT, = /'x K,x m 48. (a) Observed molar mass of CH3COOH :
= 1-23x 1-86x0-1 =0-228 K. P

°A ~ Ps _ ^
40. (d) = N2V2 PA "A
(0-5 N) x (100 cm3) s (0-1N) x V2
61
X
(0-5N)x (100cm3) 165 MB 3
V, = (0-1N)
Solutions
165 x 6 S042“ + BaCI2 —* BaS04 (2)

M0 3x3
= 110
(0-01 mol) (0-01 mo!)
56. (a) Conceptual problem.
Normal molar mass
Observed molar mass 57. (b) it= CRT or C =
60 Q _ _________ (7-7 atm) ________

= = 0 55 (close to 0-56)
49. (c ) Conceptual problem. ~ 7o-0821Latm IC'morV 31 OK = 0-31
50. (c) HX H+ + X- ; n = 2 mol L-1.
58. (b) We know that AT6 = K& x m
- nn /-I and ATf = Kf x m
° - Tîror 0 3 *
i - 1-3
ATf s i xK / x m ATf = ~ or AT6 = K
= 1-3 x 1 85 x 0 2 = 0-481 .. c ATfj b
AT ■V
f
Kf
Freezing pt. of solution = (0 - 0-481 )“C = -
ATf, 0-186 x 0
0-481°C
521 = 0-0521 K.
51. (a ) For an idea! solution, 59. (c) is the correct answer.
1-86
AH so i = AH ^ + A H 2 - t - AH 3
52. (d ) Conceptual problem. 60. (d) is the correct answer.
53. (b ) V x 0-5 N = 500 cm3 x 0-1 N 61. (c) Since the solutions are isotonic, they have
w (500cm3) X (0-1N) „„„ 3 the same osmotic pressure also.
v
*—ioifi)—l-,00cm
^ NajS04 - ^glucose
Volume of water added = 500 - 100 =
400 cm3 /x 0-004 RT =
54. (a ) Conceptual problem. 0-01 RT 0 - 0 1
/ 0-004 2-5
55. (a ) Concentration of tons in 1 litre of the Na2S04 ~
solution after mixing will be reduced to half 2Na+ + S042"
i.e. 0-01 mol. v H
Br + AgN03 ------- > AgBr(Y) i - 1=2-5-1 1-5
a
(001 mol) (0-01 mol) 2
n-1 3-1
0-75 or 75%.
Solutions • 3.121
ASSERTION-REASON Type QUESTIONS

For I.I.T./A.M.M.S. Examinations
The questions given below consist of Assertion (A) and Reason (R). Use the following
key to select the correct answer.
(a) I f both assertion and reason are correct and reason is correct explanation for assertion.
(b) If both assertion and reason are correct bat reason is not correct explanation for
assertion,
(c) If assertion is correct but reason is incorrect.
(d) If assertion is incorrect but reason is correct.
(e) If assertion and reason both are inccorrect.
Molality is preferred to molarity for expressing the concentration of the solution.
1. Assertion Molality can be determined more easily than molarity.
Reason Van’t Hoff factor for benzoic acid is less than 1 in benzene.
2. Assertion Benzoic acid associates in benzene.
Reason Isotonic solutions donot show any osmosis when placed side by side.
3. Assertion Isotonic solutions have same solute concentration.
Reason
Ethyl alcohol and water form maximum boiling azeotrope.
4. Assertion Attractive forces in solution tend to increase.
Reason
In an ideal solution, AH mixing is zero.
5. Assertion A ............ B interactions are the same as A ................ A and B ............... B interactions.
Reason
Addition of ethyl alcohol lowers the freezing point of water.
6. Assertion Impurities always lower the freezing point of a solvent.
Reason Out of various colligative properties, only osmotic pressure is used to determine
7. Assertion the molecular masses of polymers.
Polymer solutions donot possess a constant boiling point or freezing point.
Greater the molal depression constant of the solvent used less is the freezing point
Reason of the solution.
Assertion
8. Depression in freezing point depends upon the nature of the solvent.
Molarity of the solution changes with temperature.
Reason
Molarity is a colligative property.
9. Assertion
01 M NaCl solution boils at higher temperature than 0-1 M BaCl2 solution.
Reason Elevation in boiling point depends upon the number of solute particles in the
10. Assertion
solution. 1
Reason
jQ-tis-wers
1. (C) 2. (a) 3, (c) 4. (e) S. (a) 6. (a) 7. (cf 8. fa) 9. (c) 10. (d)
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.
7. (c) Polymer solutions have very small elevation in ooiling point and depression in freezing point.
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.

Solutions Dinesh

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Solutions

T TABLE 3.1 Types of Solutions

Liquid Gas Humidity in air

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

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

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 (0-05 mol)

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

Gram formula mass of solute

Difference between Molarity and Molality

Molar mass of acid

N,V, + N2V2 = N3 (Vi + V2)

Mole Fraction (x)

Mole fraction of A (JCa) =

Mole fraction of B (xB) = "B

Sum of mole fractions (xA + xB) = nA 'B

^ Tools for Numerical Problems

Gram moles of solute Molality (m) Mass of solvent ip Kg

Gram equivalents of solute

GJ Problems on Mass Percent/Volume Percent/ppm

(6x 10~3g) .. 1f)6 " (lOSOgT =

££ Problems on Molarity/Molalrty/Mole Fraction

Mass of NaOH / Molar mass of NaOH

According to available data :

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

Mass of H2S04/L of solution = ---------- ---— x (1000 mL) = 930 g

Ba(OH)2 Ba2* (aq) + 20H' (aq)

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

Molality of CH3OH solution = 1*13 molal

Volume of solution . Mass of solution = (1036-16 g) = 1042.4 cnr

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

= 1-8 (mol kg"1) = 1-8 m

No of gram equivalents of HjSO*

Mass of oxalic acid

Volume of resulting solution = 600 mL = = 0-6 L

_ (15-0g) / (36-5 g equiv-1) (0 6

100 mL of sample contains H2SO4 = 70 g

(1-4924 Vg)/(98 gmor1)

Step II. Calculation of molality of solution

Step III. Calculation of mole fraction of NaOH

Mass of Na2S203 (474 g) iriA

Molality of Na+ ions = No of mqlesof Na+ ions = (6 mol) = 7.73 m

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

/n„ , ,, . (1000 - 1127)

Mass of water (95-0g)

(b) Calculation of molality of solution.

(c) Calculation of mole fraction of solute.

Mole fraction of solute (xB) = «B (0-0316 mol)

♦ 3.3. TYPES OF SOLUTIONS

Gas Water Ethanol Benzene

Nitrogen 0015 0-130 0-104

Factors Influencing the solubility of a Gas

Gas + Liquid ^ ^ Dissolved gas ; AH = -ve

= KH x Mole fraction of the gas in the solution

_____ Partial pressure of the gas ____

T TABLE 3.3. KH values of different gases in water

He 293 10-9 x 107

N2 303 6-68 x 107

From the data collected, it is quite obvious that

*N,2 = 1-29 x 10"5 ; "H2O = 2—( = 55-55 mol

Solution. According to Henry’s Law,

_ Partial pressure of the gas

PA = APA and PB = BP°B (According to Raoult’s Law)

_ Mass of ethanol _ (46g)

Mass of methanol 64 g

Mole fraction of ethyl acetate (xg) = — __ (0 284 mol) _