LIQUID SOLUTION

Special Highlights
BRAIN TEASERS: GENERAL MISTAKE:

 TEACHER’S ADVICE:

LIQUID SOLUTIONS
1. SOLUTION
A homogeneous mixture of two or more pure substances whose composition may be altered within
certain limits is termed as solution.

Characteristics of Solution

(i) It is homogeneous in nature, yet retaining the properties of its constituents.

(ii) It is made of two parts i.e. a solute and a solvent.
Which component to take as solute and which component to take as solvent
depends on physical state of the components.

(iii) The component which has the same physical state in pure form as the solution is
called solvent and the other is called solute. Example, in case of solution of sugar and
water, sugar is the solute and water is solvent.
(iv) If both the components have same state as the solution, the one component which is
in excess is called solvent and the other is called solute. Example, alcohol in water,
benzene in toluene etc.
Types of Solution
[Link]. Solvent Solute Examples

1. Gas Gas Mixture of gases, air.

2. Gas Liquid Water vapour in air, mist.
3. Gas Solid Sublimation of a solid into a gas, smoke storms.
4. Liquid Gas CO2 gas dissolve in water (aerated drink), soda water.
5. Liquid Liquid Mixture of miscible liquids e.g. alcohol in water.
6. Liquid Solid Salt in water, sugar in water.
7. Solid Gas Adsorption of gases over metals, hydrogen over palladium.
8. Solid Liquid Mercury in zinc, mercury in gold i.e. all amalgams.
9. Solid Solid Homogeneous mixture of two or more metals
(i.e. alloys) e.g. copper In gold. zinc In copper.

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Which of the above types can never have a heterogenous mixture.

2. METHODS OF EXPRESSING THE CONCENTRATION OF A SOLUTION

There are many ways of expressing the concentration of a solution. These methods are as follows-

Students should memorize all the formulas and should be comfortable in

converting one concentration term to another.

Comment which of the following concentration terms are temperature dependent

and which are temperature independent.

(i) Mass percentage :

It may be defined as the number of parts by mass of solute per hundred parts by mass of solution.

For example. a 5% (by mass) solution of sugar in water means that 100 g of solution
contain 5 g of sugar.
Mass of any component
Mass Percentage =  100
total mass

(ii) Volume percentage :

It may be defined as the number of parts by volume of solute per hundred parts by volume of solution.

For example. a 25% (by volume) solution of ethyl alcohol means that 100 cm3. of
the solution contain 25 cm3 of ethyl alcohol and 75 cm3 of water.
Volume of component
Volume percentage =  100
total volume of solution
(iii) Mass fraction :
If WA is the mass of component A and WB the mass of component B in the solution, then the mass
fraction of component A and B is written as
WA
Mass fraction of A = W  W
A B

WB
Mass fraction of B = W  W
A B

(iv) Mole fraction

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 (i.e. solute and solvent) present in the solution.
Let us suppose that a solution contains the components A and B and suppose that a gram of A and
b gram of B are present in it. Let the molecular masses of A and B are MA and MB respectively.

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a
Then number of moles of A are given by nA = M
A

b
and number of moles of B are given by nB = M
B

Total number of moles of A and B = nA + nB

nA
Mole fraction of A, XA = n  n
A B

nB
Mole fraction of B, XB = n  n
A B

Sum of mole fractions of all components is always one.

nA nB
i.e. XA + XB = n  n + n  n = 1
A B A B

So if mole fraction of one component of a binary solution is known say XB. then the mole fraction
of XA = 1 – XB.

It may be noted that the mole fraction is always independent of the temperature.

(v) Mole percent

Mole percent is the number of moles of a component in 100 mole of the solute and solvent.
Mole percent = Mole fraction x 100
Example. for a solution containing 8 moles NH3 and 12 moles of H2O.
8 mole 2
Mole fraction of NH3, XNH = 12 moles  8 moles =
3 5

2
Mole percent of NH3 = × 100 = 40 mole %
5

(vi) Parts per million (ppm)

When a solute is present in trace amounts, its concentration is expressed in parts per million. It may
be defined as the number of parts by mass of solute per million parts by mass of the solution.

Mass of solute
Parts per million (ppm) = x 106
Mass of solution

(vii) Molarity (M)

Molarity of a solution is defined as the number of moles of the solute dissolved per litre of the solution.
It is represented by capital M. Mathematically.
Mass of the solution in gram per litre
Molarity (M) = Molecular mass of the solute
A solution having molarity “one” is called molar solution.
It may be remembered that both normality as well as molarity of a solution changes
with change in temperature.

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(viii) Molality (m) -
Molality of a solution may be defined as the number of moles of the solute dissolved in 1000 gm
(1 kg) of the solvent. It is represented by small ‘m’. Mathematically
Mass of the solute in gram per kg of solvent
Molality (m) =
Molecular mass of the solute

A solution containing one mole of solute per 1000 gm of solvent (1 kg) has molality equal to one and
is called molal solution. Molality is expressed in units of moles per kilogram (mol kg–1).

The molality of a solution does not change with temperature.

(ix) Normality :
Normality of a solution is defined as the number of gram equivalent of the solute dissolved per litre
of the solution. It is represented by N. Mathematically.

Mass of solute in gram per litre

Normality N = Equivalent mass of the solute

A solution having normality equal to one is called “normal solution”. Such a solution contains one gram
equivalent of solute per litre of [Link] solution contains 0.5 gram equivalent of solute.
A decinormal solution contains 0.1 gram equivalent and a centinormal solution contains 0.01 gram
equivalent of solute per litre of solution.
Mass of the solution  1000
or Normality =
Equivalent mass of the solute  V
Where V is the volume in milliliter.

(x) Formality (F) :

It may be defined as the number of gram formula masses of the ionic solutes dissolved per litre of
the solution. Mathematically

Mass of the ionic in gram per litre

Formality (F) = Formula mass of the solute

Commonly, the term formality is used to express the concentration of the ionic solids which do not
exist as molecule but as network of ions.

Illustration
1. A storage battery contains a solution of H2SO4 30% by weight. Find out
(i) Molality (ii) Molarity (iii) Normality (iv) Mole fraction of H2SO4
3
(Given density of solution = 1.2 gm/cm )
Sol. 30% by weight  Wsolute = 30 gm, Wsolution = 100 gm, Wsolvent = 70 gm
100
Vsolution = mL
1.2
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30 70
nsolution = = 0.306 nsolvent = = 3.889
98 18
n solute  1000 0.306  1000
(i) Molality = w solvent = = 4.37 m
70
n solute  1000 0.306  1000
(ii) Molarity = Vsolution = 100 = 3.67 M
1 .2

w solute 1000 30 1000

(iii) Normality = = 100 = 7.34 N
E solute  Vsolution 49 
1 .2
Alternatively
Normality = n-factor × Molarity
= 2 × 3.67 = 7.34
x H 2SO 4 0.306
(iv) x H 2SO 4 = = = 0.07
n H 2SO 4  n H 2O 0.306  3.889

3. SOLUBILITY OF GASES
We are familiar that gases are completely miscible with each other. Gases also dissolve in liquids and
solids. For example, soda-water contains carbon dioxide dissolved in water under high pressure. Oxy-
gen is sufficientlysoluble in water to allow survival of aquatic life in lakes, rivers and [Link] example
of dissolution of a gas in a solid is the solubility of hydrogen gas in palladium.
The solubility of a gas in a liquid is determined by several factors. In addition to the nature of the gas and
the liquid, solubility of the gas depends on the temperature and pressure of the system. The solubility of
a gas in a liquid is governed by Henry’s Law which states that the solubility of a gas in a liquid is directly
proportional to the pressure of the gas.
Dalton, a contemporary of Henry, also concluded independently that the solubility of a gas in a liquid
solution is a function of the partial pressure of the gas. If we use the mole fraction of the gas in the solution
as a measure of its solubility, then:

Mole fraction of the gas in a solution is proportional to the partial pressure of the
gas. Or, partial pressure of the gas in solution = KH × mole fraction of the gas in
solution. Here KH is Henry’s law constant or p = KH x .

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If we draw a graph between partial pressure of the gas versus mole fraction of the gas in solution, then
we should get a plot of the type as shown in figure.

Figure : Experimental results for the solubility of HCl gas in cyclohexane

at 293 K. The slope of the line is the Henry's Law constant (KH)
Different gases have different KH values at the same temperature. This suggests that
KH is a function of the nature of the gas.
It is obvious that the higher the value of KH at a given pressure, the lower is the
solubility of the gas in the liquid. It has been observed that KH value for both N2 and
O2 increases with increase of temperature indicating that solubility of gases de-
creases with increase of temperature. It is due to this reason that aquatic species are
more comfortable in cold waters rather than warm waters.
Henry’s law finds several applications in industry and explains some biological phenomena. Notable
among these are:
• To increase the solubility of CO2 in soft drinks and soda water, the bottle is sealed under high pressure.
• To minimize the painful effects accompanying the decompression of deep sea divers, oxygen diluted with
less soluble helium gas is used as breathing gas.
• In lungs, where oxygen is present in air with high partial pressure, haemoglobin combines with oxygen to
form oxyhaemoglobin. In tissues where partial pressure of oxygen is low, oxyhaemoglobin releases
oxygen for utilization in cellular activities.

Limitations of Henry's Law : For Henry's law to be applicable

(i) Gas should not react with solvent.
(ii) Gas should not associate or dissociate in solution.
(iii) This law is not applicable for highly concentrated solutions.

Illustration
2. If N2 gas is bubbled through water at 293K, how many millimoles of N2 gas would dissolve in 1 litre of
water. Assume that N2 exerts a partial pressure of 0.987 bar. Given that Henry’s law constant for N2 at
293 K is 76.48 k bar.
Sol. The solubilityof gas is related to its mole fraction in the aqueous solution. The mole fraction of the gas in
the solution is calculated by applying Henry’s law. Thus,

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pN 0.987 bar
xN  2
  1.29  10 5
2 KH 76480 bar
As 1 litre water contains 55.5 mol of it, therefore, if n represents number of moles of N2 in solution,
n mol n
xN    1.29  10 5
2 n mol  55.5 mol 55.5
Thus, n = 1.29 × 10–5 × 55.5 mol = 7.16 × 10–4 mol
1000 m mol
= 7.16 × 10–4 mol × 1 mol = 0.716 m mol

4. VAPOUR PRESSURE OF LIQUID

4.1 Vapour Pressure
If a sample of water in its liquid phase is placed in an empty container, some of it will vaporize to
form gaseous of water. This change is called evaporation. We can write an equation for evaporation
occurring spontaneously as if it were as chemical equation :
H2O(l)  H2O(g)
KP = PH 2 O
where
KP = equilibrium constant
PH 2 O = vapour pressure of H2O(g)
Thermostat Vapours
P

The pressure exerted by the vapour (molecules in the Liquid

vapour phase) over the surface of the liquid at the
Manometer
equilibrium at given temperature is called the vapour Physical equilibrium between
pressure of the liquid. liquid vapours

Is vapour pressure dependent on surface area and shape of the container?

Factors affecting vapour pressure

(a) Temperature : Vapour pressure  Temperature
The temperature at which the vapour pressure of the
liquid becomes equal to the atmospheric pressure is
called its boiling point.

Can you guess what will be the equation relating vapour pressure and
temperature.

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(b) Nature of liquid:

1
Vapour pressure of liquid 
The strength of intermolecular forces
acting between molecules
For example, CCl4 has higher vapour pressure because of the weak intermolecular forces acting between
its molecules than water which has stronger intermolecular forces acting between water molecules of
volatile liquid has lower boiling point than a non-volatile liquid.

4.2 Raoult’s Law (Vapour pressure for mixture of binary liquid) :

For a two component solution A (volatile) and B (volatile) the vapour pressure of solution is given
by

Vapour pressure of solution = Vapour pressure due to solvent + Vapour pressure

due to solute.
According to Raoult's Law partial pressure of a component is equal to its mole
fraction in solution multiplied with partial pressure in pure state

Thus PA = PºAXA
PºA= vapour pressure in pure state of A
XA = Mole fraction of A in solution
PA = Partial pressure of A in solution

Pto
P°A tal =P
A +P
B
P°B
Total vapour pressure of solution P = PºAXA + PºBXB

XA = 1 XA = 0
XB = 0 XB = 1
Illustration
3. At 25°C, the vapour pressure of methyl alcohol is 96.0 torr. What is the mole fraction of CH3OH in a
solution in which the (partial) vapor pressure of CH3OH is 23.0 torr at 25°C?
PCH OH 23
Sol. X CH 3OH = 0 3
PCH 3OH = 96 = 0.24

4.3 Determination of composition in vapour phase

Dalton’s Law v/s Raoult’s Law:
The composition of the vapour in equilibrium with the solution can be calculated applying Daltons’ law of
partial pressures. Let the mole fractions of vapours Aand B be YA and YB respectively. Let pA and pB be
the partial pressure of vapours Aand B respectively and total pressure P.

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A B A B A B A B A B A vapours (Dalton's law)

yA = mole fraction of A in vapour phase
yB = mole fraction of B in vapour phase

(YA + YB = 1)

A B A B A B A B A B A solution (Raoult's law)

XA = mole fraction of A in liquid phase
XB = mole fraction of B in liquid phase
Solution of (A & B)
(XA + XB = 1)

From Raoult's law P = PAoXA + PBo XB

PA= PAoXA and PB = PBo XB
From Dalton's law,
Partial pressure = Mole fraction × Total pressure
For A PA = yA × P = PAoXA
PAo X A
yA = .....(1)
P
Similarly

PBo X B
yB = .....(2)
P
Above formula is used for calculation of mole fraction of B in vapour phase
P  yA P  yB
on adding XA + XB = + =1
PAo PBo
1 y yB
 = Ao + o .....(3)
P PA PB
Above formula is used to calculate total vapour pressure when mole fractions are given in vapoure phase

P = PAoXA + PBo XB  This formula is used to calculate total pressure when mole
fraction are given in liquid phase
1 y y
 Ao  Bo This formula is used to calculate total pressure when mole
P PA PB
fraction are given in vapour phase

Can you Plot a graph of Pressure vs composition ( liquid and vapor phase)

Thus, in case of ideal solution the vapour phase is phase is richer with more volatile
component i.e., the one having relatively greater vapour pressure.

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Illustration
4. The vapour pressures of ethanol and methanol are 44.5 mm and 88.7 mm Hg respectively. An ideal
solution is formed at the same temperature bymixing 60 g of ethanol with 40 g of methanol. Calculate the
total vapour pressure of the solution and the mole fraction of methanol in the vapour.
60 40
Sol. No. of moles of C2H5OH = = 1.304, No. of moles of CH3OH = = 1.25
46 32
1.304
‘XA’of ethyl alcohol = = 0.5107
1.304  1.25
1.25
‘XB’ of methyl alcohol = = 0.4893
1.304  1.25
Partial pressure of ethyl alcohol = XA.PA0 = 0.5107 × 44.5 =22.73 mm Hg

Partial pressure of methyl alcohol = XB.PB0 = 0.4893 × 88.7= 43.40 mm Hg

Total vapour pressure of solution = 22.73 + 43.40 = 66.13 mm Hg
Partial pressure of CH 3OH
Mole fraction of methyl alcohol in the vapour =
Total vapour pressure
43.40
= = 0.6563
66.13

4.4 Vapor pressure when a non volatile solute is dissolved in solvent :

When a small amount of a non-volatile solute is added to the liquid (solvent). It is found that the
vapour pressure of the solution is less than that of the pure solvent. This is due to the fact that the
solute particles occupy a certain surface area and evaporation takes place from the surface only. The
particles of the solvent will have a less tendency to change into vapour i.e. the vapour pressure of
the solution will be less than that of the pure solvent and it is termed as lowering of vapour pressure.
For a solution of non-volatile solute with volatile solvent.
P = PA XA P = vapour pressure of solution
PA = PºA XA PA = vapour pressure of solvent
If mole fraction of solute is XB, then XA = mole fraction of solvent and PºA = vapour pressure of pure
solvent.
XA + XB = 1
PA = PºA (1–XB) = PºA – PºAXB
PAo  PA
XB =
PA0

 PAo  PA 
(PºA– PA) is the lowering of vapour pressure whereas  0  is called relative lowering
 PA 
of vapour pressure.

Vapour pressure of pure solvent – Vapour pressure of solution

Mole fraction of solute =
vapour pressure of solvent

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Illustration
5. The vapour pressure of pure liquid solventAis 0.80 atm. When a nonvolatile substance B is added to the
solvent its vapour pressure drops to 0.60 atm. What is the mole fraction of component B in the solution?
Ans. 0.25
PA0  Psol 0  80  0  60
Sol. XB = = = 0  25
0  80
0
PA

So Raoult’s law can also be defined as “For a solution containing non-volatile solute,
at a particular temperature. The relative lowering of vapour pressure is equal to
mole fraction of the solute”.

Vapour pressure of solutions having non volatile solute will always be less
than that of solvent, however vapour pressure of solutions with volatile
solute may be more or less than that of pure solvent.

4.5 Types of Solutions

(a) Ideal Solution : An ideal solution may be defined as the one which obeys Raoult’s law over all
concentration ranges at a given temperature. The total vapour pressure of an ideal solution containing
liquidsAand B is given bythe following equation.
P  PA  PB  PAo X A  PBo X B
In an ideal solution of two components A and B, all attractive forces between A and B molecules or
between A andA molecules or between B and B molecules (A–B,A–Aand B–B) must be identical so
that the escaping tendency of an A or B molecule is independent of whether it is surrounded by A
molecules, B, molecules or varying proportions ofAand B molecules. The escaping tendency of pure
liquid Ain solution remains the same. Similarly the escaping tendency of B remains the same. Liquids
form ideal solution only when theyhave nearly same molecular size and related constitution so that they
have similar molecular environment in the pure state as well as in [Link] ideal solution is rare
but manyliquids form nearlyideal solution. Liquid heptane and hexane form an ideal solution because the
interaction between a hexane molecule and another heptane molecule is the same as the interaction
between two heptane molecules other examples of ideal solutions are:

benzene + toluene, chlorobenzene + bromobenzene;

ethyl bromide + ethyl iodide; n-butyl chloride + n-butyl bromide
ethyl alcohol + methyl alcohol

Conditions for forming ideal solution:

Two liquids on mixing form an ideal solution onlywhen
1. both have similar structures and polarityso that they have similar molecular environment.
2. both have similar molecular sizes.
3. both have identical intermolecular forces.
(b) Non-ideal solutions : Solutions which do not obey Raoult’s law over all concentration ranges at
constant temperature are called non-ideal solutions.

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Distinction between ideal & non ideal solutions

[Link]. Ideal solution Non Ideal solution
1. They obey Raoult’s Law They do not obey Raoult’s Law

2. H mixing  0  no heat is H mixing  0  heat is absorbed

absorbed or released during or released during dissolution
dissolution

3. Vmixing  0  the total volume Vmixing  0  the total volume

of the solution is equal to the sum of the of the solution is not equal to the sum of the
volume of the pure liquids mixed to form volume of the pure liquids mixed to
the solution form the solution.
4. In ideal solution PA = PA0XA In non ideal solution PA  PA0XA

5. Components of ideal solution can be Components of non ideal solution can not be
separated in pure form by fractional separated in pure form by fractional
distillation distillation

Types of non-ideal solutions

(I) Non ideal solutions showing positive deviation
(II) Non ideal solutions showing negative deviation.

(I) Non ideal solutions showing positive deviation

Condition for forming non-ideal solution showing positive deviation from Raoult’s law.
Two liquidsAand B on mixing form this type of solution when
1. A—B attractive force should be weaker than A—A and B—B attractive forces.
2. ‘A’and ‘B’have different shape, size and charater.
3. ‘A’and ‘B’escape easily showing higher vapour pressure than the expected value.

Example :
acetone + ethanol acetone + CS2 water + methanol;
water + ethanol; CCl4 + toluene; CCl4 + CHCl3;
acetone + benzene; CCl4 + CH3OH; cyclohexane + ethanol

Graphical representation of vapour pressure of non-ideal solution showing positive deviation

V.P.= max.
B.P. = min.
P>
PA +
PB
Vapour pressure

P
A >
P o
B
X
B

XA= 0 Mole fraction XA= 1

XB= 1 XB= 0
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(II) Non ideal solutions showing negative deviation.

Condition for forming non-ideal solution showing negative deviation from Raoult’s law.

Two liquidsAand B on mixing form this type of solution when

1. A—B attractive force should be greater thanA—Aand B—B attractive forces.
2. ‘A’and ‘B’have different shape, size and character
3. Escaping tendency of both components ‘A’and ‘B’is lowered showing lower vapour pressure
than expected ideally.
Example:
acetone + aniline; CH3OH + CH3COOH;
chloroform + diethyl ether, acetic acid + pyridine;
chloroform + benzene H2O + HNO3;
water + HCl
Cl
CH3
acetone + chloroform; Cl C H OC
CH3
Cl
Graphical representation of vapour of non-ideal solution showing negative deviation

V.P.= min.
Vapour pressure

B.P. = max.

+P B
P < PA
o XA
P
<PA
A >P
PA
B o
X
B

XA = 0 Mole fraction XA = 1
XB = 1 XB = 0

Distinction between non ideal solutions showing positive deviation & negative deviation

[Link]. Showing positive deviation Showing negative deviation

1. Hmix > 0. Hmix < 0.

(endothermic dissolution i.e. heat is absorbed.) (Exothermic dissolution i.e. heat is evolved.)

2. Vmix > 0. Vmix < 0.

(Volume is increased after dissolution) (Volume is decreased during dissolution)
3. pA > pA0 XA; pB > pBoXB , pA < pA0 XA; pB < pBoXB ,
 pA + pB > poAXA + pBoXB  pA + pB < poAXA + pBoXB

(vi) Azeotropes
The non-ideal solution showing large deviations from Raoult’s law can not be purified
by distillation. A solution at certain composition which continues to boil at constant
temperature without change in the composition of the solution.

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This mixture is called Azeotrope or Constant boiling [Link] are of two types:
(a) Azeotropes with Maximum vapour pressure and Minimum Boiling point : When liquid in a solution
do nothave great chemical affinityfor each other (+vedeviation from ideality)theirhigher escape tendencies
increase the vapour pressure much more than expected on the basis of Raoult’s law. In many cases, the
deviations are so extreme as to lead to a maximum in the curve. The point of maximum vapour pressure
means that the boiling point at this composition will be minimum and constant.
(b) Azeotropes with Minimum vapour pressure and Maximum Boiling Point :
When liquids in solution show –ve deviation from ideality, their escape tendencies and hence the vapour
pressure decreases than expected on the basis of Raoult’s law. In many cases, the maximum in the
temperature composition curve is obtained. The point of minimum vapour pressure in the curve means
that the boiling point of this composition will be maximum and constant.

5. COLLIGATIVE PROPERTIES

The properties of dilute solutions containing nonvolatile solute, which depends upon
relative number of solute and solvent particles but do not depend upon their nature
are called colligative properties.
Some of the colligative properties are
(i) Relative lowering of vapour pressure (ii) Elevation in boiling point
(iii) Depression in freezing point; and’ (iv) Osmotic pressure.
Factors thatAffect the Colligative Property : The number of solute particles in solution. To be more
accurate, the colligative property depends upon the fraction of solute and solvent particles in solution.
(1) Nature of the solvent
(2) Independent of the nature of the solute
(3) Extent of association and dissociation of solute particles in solution.
5.1 Relative Lowering of Vapour Pressure
As shown earlier the mathematical expression for relative lowering of vapour pressure is as follows
P
PA0
= XB = mole fraction of solute
P = PºA – PA = lowering of vapour pressure
PA = vapour pressure of pure solvent
Molecular mass of non-volatile substance can be determined from relative lowering of vapour pressure
PA0  P WB / M B
= W /M W /M
PA0 A A B B

For dilute solution WB/MB < WA/MA and hence WB/MB may be neglected in the denominator. So

PA  PA WB / M B WB MA WB / M A  PAo
 o


= = x or MB =
PA
WA / M A WA MB WA  PA  PA 

Illustration
6. One mole of a non-volatile solute is dissolved in two moles of water. The vapour pressure of the solution
relative to that of water is
(1) 2/3 (2) 1/3 (3) 1/2 (4) 3/2

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
Psolvent  P–solution
P° Psoln 1 1 Psolution
P 1 2
Sol. 
  (mole fraction of solute in solution) Or 
soln
 1– 
P°
Psolvent 1 2 3 Psolvent
P° 3 3

5.2 Elevation in Boiling Point

The boiling points elevates when a non-volatile solute is added to a volatile solvent. Which occurs
due to lowering of vapour pressure.
The boiling point of a liquid may be defined as the temperature at which its vapour pressure
becomes equal to atmospheric pressure.
Phase Diagram of water
The lines represent simultaneous values of pressure and temperature at which two phases may be
present at [Link] the temperatures and pressures that lie on the line OA, liquid water and its
vapor are at equilibrium. Along the line OB, ice and its vapor are at equilibrium, while the sets of
temperature and pressure at which both ice and liquid water are in equilibrium lie along OC. Only at the
pressure and temperature corresponding to the triple point (0.01ºC, 4.588 torr) are ice, water and
water vapor simultaneouslypresent at equilibrium. The areas between the curves represent temperatures
and pressures at which only one phase can exist.
C A

Liquid
Boiling
Pressure (torr)

760 water
point
Solid
water
Water
4.588 O vapor
Triple
B point

0.01ºC 100ºC
Temperature
Phase Diagram of Water
So when a non-volatile solute is added to a volatile solvent results lowering of vapour pressure and
consequent elevation of boiling point
B D
where
Tb = Tb – T°b Atmospheric E
F
Vapour pressure

Tb = elevation in B.P. Pressure

v en
t
l
P = lowering of V.P. So
on
A luti
XB = mole fraction of solute So
C T
K = elevation constant b

T°b = boiling point of solvent

Tb = boiling point of solution T T
Temperature O

Elevation in boiling point

It is found that elevation of boiling point is directly proportional to the number of moles of the solute
in given amount of the solvent(m).
Tb  m
Tb  Kbm

Where 'm' is the molality of solution.

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Where Kb is ebullioscopic or boiling point elevation constant. When molality of the solution is equal
to one. Then
Tb = Kb
Hence molal elevation constant of the solvent may be defined as the elevation in its boiling point when
one mole of non-volatile solute is dissolved per kg (1000 gm) of solvent. The unit of Kb are K kg
mol–1.
WB 1000
Because molality of solution m = M . W
B A

1000  K b  WB
So Tb = Kb WB . 1000 MB = Tb  WA
MB WA
Where WA = mass of solvent, WB = mass of solute,
MA = Molar mass of solvent, MB = Molar mass of solute.

Determination of Kb of solvent :

RTb2
Kb  .......(3)
1000L v

where R is molar gas constant, Tb is the boiling point of the solvent on Kelvin scale and Lv the latent heat
of vaporization of solvent in calories per gram.
2  (373) 2
For water Kb   0.515 K-kg/mol
1000  540

If energy is taken in joule then use R = 8.314 JK–1 mole–1

Energy is taken in calorie then use R = 2 cal K–1 mole–1
Illustration
7. An aqueous solution of glucose boils at 100.01°C. The molal elevation constant for water is
0.5 K mol–1 Kg. The number of molecules of glucose in the solution containing 100 g of water is
(A) 6.023  1023 (B) 6.023  1022 (C) 12.046  1020 (D) 12.046  1023
Ans. (C)

ΔTb 0.01
Sol. Tb = Kb.m Or m=  = .02 mole Kg–1 of water
Kb 0.5

So, the number of moles of glucose in 100 g of water

0.02 100
= = 0.002 moles of glucose = 0.002  6.023  1023 = 2  6.023  1020
1000

5.3 Depression in Freezing Point

The freezing point of a pure liquid is fixed. If a non-volatile solute is dissolved in a liquid the freezing
point of the solution is lowered. The freezing point is that temperature at which the solvent has the
same vapour pressure in two phases liquid solution and solid solvent. Since the solvent vapour pressure
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 LIQUID SOLUTION

in solution is depressed. Its vapour pressure will become equal to that of the solid solvent at a lower
temperature
Tf = T°f – Tf
It is found that depression in freezing point is directly proportional to the number of moles of the solute
in given amount of the solvent(m).
Liquid solvent

Vapour pressure
Hence Tf  m Solid
solvent
Tf = Kf m
T
Where m = molality of the solution. f

Kf = molal depression constant T T° f f

When molarity (m) of the solution is one. then Temperature

 Tf = Kf
Hence molal depression constant or molal cryoscopic constant may be defined as “the depression in
freezing point when one mole of non-volatile solute is dissolved per kilogram (1000 gm) of solvent”
and molar depression constant is defined as “the depression in freezing point when one mole of non-
volatile solute is dissolved per litre (1000 ml) of solvent.”
The molecular mass of the non-volatile solute may be calculated by the use of following mathematical
equation
K f  WB 1000
MB = WA  Tf

Where WA = mass of solvent, WB = mass of solute,

MA = Molar mass of solvent, MB = Molar mass of solute.

Determination of Kf of solvent
Kf is characteristic of a particular solvent and can be calculated from the thermodynamical relationship.

RTf2
Kf  ......(3)
1000Lf

where Tf is the freezing point of solvent in absolute scale and Lf the latent heat of fusion in calories per
gram of the solvent. For water,
0.002  (273) 2
Kf   1.86 K-kg/mole
80

If energy is taken in joule then use R = 8.314 JK–1 mole–1

Energy is taken in calorie then use R = 2 cal K–1 mole–1

Kb , Kf for various Solvents

Solvent B.P. Kb F.P. Kf

Acetic acid 118.1°C 2.93 17°C 3.9
Benzene 80.2°C 2.53 5.4°C 5.13
Water 100°C 0.53 0ºC 1.86

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Antifreeze solutions -
Water is used in radiators of vehicles as cooling liquid. If the vehicle is to be used
at high altitudes where temperature is sub-zero. water would freeze in radiators.
To avoid this problem. a solution of ethylene glycol in water is used in radiators
which will lower the freezing point lower than zero.
Illustration
8. What is the percent by mass of iodine needed to reduce the freezing point of benzene to 3.5°C? The
freezing point and cryoscopic constant of pure benzene are 5.5°C and 5.12 K/m respectively.
Sol. Tf = Tf0 – Tf = Kf . m
5.5°C – 3.5°C = 5.12 × m
2
m  0.39mmolal
5.12
 Mass of iodine needed for 1000g of benzene = m × molecular mass of iodine I2
= 0.39 mol/kg × 254 g/mol = 99.06 g/kg
 1000g + 99.06g solution contains 99.06g I2
99.06g  100
100g solution contains  9.01%
1099.06g

5.4 Osmotic Pressure

(a) Osmosis : Spontaneous flow of solvent molecules through a semipermeable membrane from a
pure solvent to the solution (or from a dilute solution to a concentrated solution) is termed as osmosis.
Osmotic Semi
pressure permiable
membrane
Piston

Pure liquid
Solution
Solvent

(b) Osmotic Pressure :

When a solution is separated from the pure solvent with the help of a semipermeable membrane. There
occurs the flow of solvent molecules from the pure solvent to the solution side. The flow of solvent
molecules from a region of higher concentration of solvent to the region of lower concentration of solvent
is termed as the phenomenon of osmosis. This also happens when two solution of different concentra-
tions are separated by a semipermeable membrane.

As a result of osmosis a pressure is developed which is termed as osmotic pressure. It is defined in

various methods.
(1) The excess hydrostatic pressure which builds up as a result of osmosis is called osmotic
pressure.
(2) The excess pressure that must be applied to the solution side to prevent the passage of solvent
into it through a semipermeable membrane.
(3) Osmotic pressure of a solution is equal to the negative pressure which must be applied to the
solvent in order to just stop the osmosis.
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(4) The osmotic pressure of a solution may be defined as the extra pressure which should be applied
to the solution to increase the ‘chemical potential of solvent in solution equal to the chemical
potential of the pure solvent at the same temperature.

(c) Theory of Dilute Solutions : The osmotic pressure of a dilute solution was the same as the solute
would have exerted if it were a gas at the same temperature as of the solution and occupied a volume
equal to that of the solution. This generalization is known as Van’t Hoff theory of dilute solutions.
The osmotic pressure is a colligative property. So the osmotic pressure is related to the number of
moles of the solute by the following relation
V= nRT
n n
= RT
T ( = C)
V V
 = CRT
Here C = concentration of solution in moles per litre;
R = solution constant;
T = temperature in Kelvin degree;
n = number of moles of solute; and
V = volume of solution.
This equation is called Van’t Hoff’s equation.

(d) Determination of molecular mass from. osmotic pressure : The molecular mass of a substance
i.e. solute can be calculated by applying the following formula
WRT
M = V

Accurate molecular mass will only be obtained under following conditions

(i) The solute must be non-volatile;
(ii) The solution must be dilute; and
(iii) The solute should not undergo dissociation or association in the solution.

Solution constant R - The solution constant R has the same significance and value as the gas constant.
i.e.
R = 0.0821 litre-atm K–1 mol–1
= 8.314 X 10–7 erg K–1mol–1
= 8.314 JK–1 mol–1
= 8.314 Nm K–1 mol–1

(e) Type of solutions :

(I) Isotonic solution : The two solutions having equal osmotic pressure are
termed as isotonic solution.
(II) Hypertonic solution : A solution having higher osmotic pressure than some’
other solution is said to be called hypertonic solution.

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(III) Hypotonic solution : A solution having a lower osmotic pressure relative

to some other solution is called hypotonic solution.

(f) Semipermeable membrane :

A membrane which allows the passage of solvent molecules but not that of solute. When a solution
is separated from the solvent by it is known as semipermeable membrane.
Some example of it are as follows
(a) Copper ferrocyanide Cu2[Fe(CN)6]; (b) Calcium phosphate membrane; and
(c) Phenol saturated with water.

(g) Reverse Osmosis :

If a pressure greater than the osmotic pressure is applied on the concentrated solution, the solvent starts
to flow from concentrated solution to dilute solution (or pure solvent). This is reverse osmosis. One of its
chief uses is desalination of sea water to get pure drinking water.
Illustration
9. The solute ‘A’is a ternary electrolyte and solute ‘B’is a non-electrolyte. If 0.1 M solution of solute ‘B’
produces an osmotic pressure of 2P, then 0.05 M solution ofAat the same temperature will produce an
osmotic pressure equal to
(A) P (B) 1.5 P (C) 2 P (D) 3 P
Ans. (D)
Sol. For ternary electrolyte, osmotic pressure = (0.05  3) (R) (T)
0.1
Osmotic pressure of B = 2P = (0.1) (R) (T) or P = RTT
2
P = 0.05 RT
Since temperature is the same, comparing the two equations, we obtain
the osmotic pressure of ternary electrolyte = 3P

10. The osmotic pressure of blood is 7.65 atm. at 310 [Link] aqueous solution of glucose which is isotonic
with blood has the percentage (wt./volume)
(A) 5.41 (B) 3.54 (C) 4.53 (D) 53.4
Ans. (A)
Sol. Since glucose and blood are isotonic, the osmotic pressures are the same. Therefore,
glucose = blood

w
Or 7.65  V =  0.0821 310 [w = amount of glucose present in V litres of solution]
180

w
Or 7.65  180 =  0.0821  310
V

w 7.65 180
Or = = 54.1 g L–1 or 5.41%
V 0.0821 310

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6. ABNORMAL MOLECULAR MASSES

Vapour pressure lowering, boiling point elevation, freezing point depression and osmotic pressure are
colligative properties which depend upon the fraction of solute and solvent particles in solution and not
upon the chemical nature of the solute. If solute molecules dissociates in solution, there are more particles
in solution and therefore, lowering of vapour pressure shows an increased effect.
NaCl (s) Na +(aq) + Cl(aq)
–

If the solute molecules associates in solution, there are less particles in solution, and therefore lowering of
vapour pressure shows a decreased effect.
nAB (AB)n
2C 6 H5COOH (C6 H 5COOH) 2

The molecular mass of a solute is inversely proportional to its molality :

If colligative molalityis 2 m, the calculated molecular mass is one-half of the actual molecular mass of the
solute. If colligative molality is 3 m, the calculated molecular mass is one third of the actual molecular
mass of the solute. The molecular mass of benzoic acid is 122 g/mol. But the molecular mass of benzoic
acid dissolved in benzene is found to be 244 g/mol byusing a colligative property. Benzoic acid associates
to form a dimer and therefore its colligative molality is one-half of the molality of benzoic acid. As
molecular mass of a solute is inversely proportional to molality, the molecular mass of benzoic acid
determined using a colligative property is double the actual molecular mass of benzoic acid. We can
summarize the results as:
(i) The extent of dissociation and colligative property :
A solute dissociates completelyor partiallyin solution makes available more particles than would otherwise
be present in solution and therefore, a colligative property shows an increased effect. For example,
molecular masses obtained of strong acids, bases and salts are much less than their normal [Link] an
example, one particle of potassium chloride on dissociation in water gives two particles, K+ and Cl– and
therefore, the molecular mass obtained bya colligative property is half of its normal molecular mass.
K  Cl(s)

 nH 2 O  
 K (aq 
)  Cl(aq )
1 mol 1mol 1 mol

(ii) The extent of association and colligative property:

A solute that associates in solution provides less particles that would otherwise be present in solution and
therefore, the colligative property shows the decreased effect. For example, benzoic acid in benzene is
found to have molecular masswhichisjusttwice its normal molecular mass.
It is found that compounds which are capable of forming hydrogen bonds, e.g., phenols, carboxylic aids,
alcohols: because of association show decreased effect of colligative property.
O H O
H5C6 C 6H5
O H O
A dimer of benzoic acid

7. VAN’T HOFF FACTOR

In 1886, Van’t Hoff, Jacobus Henricus (Dutch chemist, 1859,-1911) introduced a factor ‘i’known as
Van’t Hoff factor to express the extent to association or dissociation of a solute in solution. It can be
calculated as:
number of solute particles actually present in solution
i=
number of solute particles dissolved

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Observed colligative property observed molality normal molecular weight of solute

= = =
normal colligative property normal molality observed molecular weight of solute

The Van’t Hoff factor for a solute can be calculated by the following modified equations:
PA0  PA
(i) = i XB (ii) Tf = iKfm (iii) Tb = iKbm (iv)  = iCRT
PA0
where C is molarity of the solution.
Note: For non-electrolytes; i = 1
For electrolytes; i > 1 ( If solute particles undergo Dissociation in the solution)
i < 1 ( If solute particles undergoAssociation in the solution)
(iii) Application of Van’t Hoff Factor :

(a) Calculation of Degree of Dissociation of solute particles:

An nA
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1– n
Total number of moles present in solution = (1 – ) + n
Moles of solute actually present in solution
Van’t Hoff factor, i 
Moles of solute dissolved
(1  )  n i 1
=  1  (n  1) or  
1 n 1
(b) Calculation of Degree of Association of solute particles:
Let n moles of the solute, A, associate to form (A)n. If  is the degree of association.
nA An
No. of moles dissolved 1 mol 0
No. of moles after dissociation 1– /n
Total number of moles present in solution = (1 – ) + /n
  1  i 1 n
i  1   1    Hence    (i  1) 
  n  1 1 n
1
n

Illustration
11. Molal elevation constant Kb for water is 0.52 K/m. 0.1 molal solution of NaCl will boil at
(A) 100.52°C (B) 100.052°C (C) 101.04°C (D) 100.104°C
Ans. (D)
Sol. If vant Hoff factor is i, then
Tb = i Kb.m (for NaCl i = 2)
= 2  0.52 . 0.1 = 0.104.
And, so the boiling point of solution will be 100.104°C.

12. Asolution is prepared by dissolving 26.3g of CdSO4 in 1000g water. The depression in freezing point of
solution was found to be 0.284K. Calculate the Van’t Hoff factor. The cryoscopic constant of water is
1.86K kg solvent mol–1- solute.
Ans. 1.21
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Sol. Molecular mass CdSO4 = 112.4 +32 + 4 × 16 = 208.4 g/mol

Mass CdSO 4
Molality CdSO4 = Molecular mass CdSO  Mass solvent in kg
4

26.3g
= = 0.216m
 1000 
(208.4g / mol)   kg 
 1000 
Tf 0.284K
Tf = iKfm or i  K m  1.86K / m  0.126m = 1.21
f

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