528 14 PHYSICAL CHEMISTRY

14
C H A P T E R
Solutions

C O N T E N T S

WAYS OF EXPRESSING
CONCENTRATION
MOLARITY
MOLALITY
NORMALITY
SOLUTIONS OF GASES IN GASES
HENRY’S LAW
SOLUTIONS OF LIQUIDS IN
LIQUIDS
SOLUBILITY OF COMPLETELY
MISCIBLE LIQUIDS
SOLUBILITY OF PARTIALLY
MISCIBLE LIQUIDS

PHENOL–WATER SYSTEM
TRIMETHYLAMINE–WATER
SYSTEM
NICOTINE–WATER SYSTEM
VAPOUR PRESSURES OF LIQUID-
LIQUID SOLUTIONS
AZEOTROPES
THEORY OF FRACTIONAL
DISTILLATION
STEAM DISTILLATION
SOLUTIONS OF SOLIDS IN LIQUIDS
SOLUBILITY–EQUILIBRIUM
CONCEPT
DETERMINATION OF SOLUBILITY
SOLUBILITY OF SOLIDS IN SOLIDS
A
solution is a homogeneous mixture of two or more
substances on molecular level. The constituent of the
mixture present in a smaller amount is called the Solute
and the one present in a larger amount is called the Solvent. For
example, when a smaller amount of sugar (solute) is mixed with
water (solvent), a homogeneous solution in water is obtained.
In this solution, sugar molecules are uniformly dispersed in
molecules of water. Similarly, a solution of salt (Na+ Cl–) in water
consists of ions of salt (Na+,Cl–) dispersed in water.
CONCENTRATION OF A SOLUTION
The concentration of a solution is defined as : the amount
of solute present in a given amount of solution.
Concentration is generally expressed as the quantity of
solute in a unit volume of solution.
Quantity of solute
Concentration =
Volume of solution
A solution containing a relatively low concentration of
solute is called Dilute solution. A solution of high concentration
is called Concentrated solution.

528
 SOLUTIONS 529

Solute
molecules

Solvent
molecules

Figure 14.1
Molecular model of a solution.
TYPES OF SOLUTIONS
The common solutions that we come across are those where the solute is a solid and the solvent
is a liquid. In fact, substance in any three states of matter (solid, liquid, gas) can act as solute or
solvent. Thus there are seven types of solutions whose examples are listed in Table 14.1.
TABLE 14.1. TYPES AND EXAMPLES OF SOLUTIONS
State of Solute State of Solvent Example

1. Gas Gas Air

2. Gas Liquid Oxygen in water, CO2 in water
(Carbonated drinks)
3. Gas Solid Adsorption of H2 by palladium
4. Liquid Liquid Alcohol in water
5. Liquid Solid Mercury in silver
6. Solid Liquid Sugar, Salt
7. Solid Solid Metal alloys : Carbon in iron
(Steel)

Of the seven types of solutions mentioned in Table 14.1, we will discuss only the important ones
in detail.
WAYS OF EXPRESSING CONCENTRATION
There are several ways of expressing concentration of a solution :
(a) Per cent by weight
(b) Mole fraction
(c) Molarity
(d) Molality
(e) Normality
Per cent by Weight
It is the weight of the solute as a per cent of the total weight of the solution. That is,
Wt.of solute
% by weight of solute = × 100
Wt.of solution
530 14 PHYSICAL CHEMISTRY

For example, if a solution of HCl contains 36 per cent HCl by weight, it has 36 g of HCl for 100
g of solution.
SOLVED PROBLEM. What is the per cent by weight of NaCl if 1.75 g of NaCl is dissolved in
5.85 g of water.
SOLUTION
Wt. of solute (NaCl) = 1.75 g
Wt. of solvent (H2O) = 5.85 g
∴ Wt. of solution = 1.75 + 5.85 = 7.60 g
Hence concentration of NaCl % by weight
1.75
= × 100
7.60
= 23.0
MOLE FRACTION
A simple solution is made of two substances : one is the solute and the other solvent. Mole
fraction, X, of solute is defined as the ratio of the number of moles of solute and the total number of
moles of solute and solvent. Thus,
Moles of solute
X solute =
Moles of solute + Moles of solvent
If n represents moles of solute and N number of moles of solvent,
n
X solute =
n+N
Notice that mole fraction of solvent would be
N
X solvent =
n+N
Mole fraction is unitless and
Xsolute + Xsolvent = 1

SOLVED PROBLEM. Calculate the mole fraction of HCl in a solution of hydrochloric acid in water,
containing 36 per cent HCl by weight
SOLUTION
The solution contains 36 g of HCl and 64 g of H2O
⎛ 1mol HCl ⎞
Number of Moles of HCl = (36 g HCl) ⎜ ⎟
⎝ 36.5g HCl ⎠
= 0.99
⎛ 1mol H 2 O ⎞
Number of Moles of H2O = (64 g H2O) ⎜ 18g H O ⎟
⎝ 2 ⎠
= 3.55
moles of HCl
X HCl =
moles of HCl + moles of H 2 O
0.99
= = 0.218
3.55 + 0.99

MOLARITY
In current practice, concentration is most often expressed as molarity. Molarity (symbol M) is
defined as the number of moles of solute per litre of solution. If n is the number of moles of solute
 SOLUTIONS 531

and V litres the volume of solution,

Moles of solute
Molarity =
Volumein litres
n
or M = ...(1)
V (in litres)
For one mole of solute dissolved in one litre of solution M = 1 i.e., molarity is one. Such a
solution is called 1M (read “1 molar”). A solution containing two moles of solute in one litre is 2M
(“two molar”); and so on. As evident from expression (1), unit of molarity is mol litre–1.

Moles of solute
Molarity =
Volumein litres
Calculation of Molarity
Molarity of a solution can be calculated with the help of the expression (1) if moles of solute (n)
and volume V (in litres) are known. When the amount of solute is given in grams and its molecular
weight is MW, it can be converted to moles :
1mol
n= xg× mol
MW g
Substituting in expression (1)
1mol 1
M = xg× × ...(2)
MW g V
From expression (1) can also be found the amount of solute in grams if molarity is given.

SOLVED PROBLEM 1. What is the molarity of a solution prepared by dissolving 75.5 g of pure
KOH in 540 ml of solution.
SOLUTION
Molecular mass of KOH = 39.1 + 16.0 + 1.0
= 56.1
Calculation of moles of KOH:
1mol
75.5g KOH × = 1.35 mol
56.1g
Calculation of volume in litres :
1litre
540 ml × = 0.540 litres
1000 ml
532 14 PHYSICAL CHEMISTRY

Calculation of Molarity :
n
M =
V
1.35mol
= = 2.50 M
0.540litre
Thus the solution is 2.50 M.

SOLVED PROBLEM 2. What weight of HCl is present in 155 ml of a 0.540 M solution ?

SOLUTION
M = 0.540
155
V in litres = = 0.155litre
1000
n = M×V
= 0. 540 mol/litre × 0.155 litre
= 0.0837 mol of HCl
36.5g
0.0837 mol of HCl × = 3.06 g HCl
mol HCl
Thus 3.06 g of HCl is present in 155 ml of the given solution.

MOLALITY
Molality of a solution (symbol m) is defined as the number of moles of solute per kilogram of
solvent :
Moles of solute
Molality (m) = Mass of solvent in kilograms

A solution obtained by dissolving one mole of the solute in 1000 g of solvent is called one molal
or 1m solution.
Notice the difference between molality and molarity. Molality is defined in terms of mass of
solvent while molarity is defined in terms of volume of solution.

SOLVED PROBLEM. What is the molality of a solution prepared by dissolving 5.0 g of toluene
(C7H8) in 225 g of benzene (C6H6) ?
SOLUTION
Calculation of number of moles of solute :
Molecular mass of toluene = 12 × 7 + 1 × 8 = 92
5
No. of moles 5 g of toluene = = 0.0543
92
225 g
Mass of solvent in kg = = 0.225 kg
1000
No.of moles of solute 0.0543
Molality = =
Mass of solvent in kg 0.225
= 0.24 m
 SOLUTIONS 533

NORMALITY
Normality of a solution (symbol N) is defined as number of equivalents of solute per litre of the
solution :
Equivalents of solute
Normality ( N ) =
Volume of solution in litres
Thus, if 40 g of NaOH (eq. wt. = 40) be dissolved in one litre of solution, normality of the solution
is one and the solution is called 1N (one-normal). A solution containing 4.0 g of NaOH is 1/10 N or
0.1 N or decinormal.
SOLVED PROBLEM. 5 g of NaCl is dissolved in 1000 g of water. If the density of the resulting
solution is 0.997 g per ml, calculate the molality, molarity, normality and mole fraction of the solute,
assuming volume of the solution is equal to that of solvent.
SOLUTION
Mass of NaCl
Number of moles of NaCl =
Molecular mass NaCl
5
= = 0.0854
58.5
By definition,
No. of moles of solute × 1000
Molality =
Mass of solvent in grams
0.0854
= × 1000 = 0.0854 m
1000
Mass of solution in grams
Volume of the solution =
Density in gm per ml
1000 + 5
= = 1008 ml
0.997
= 1.008 litre
Number of moles of solute
Now Molarity =
Volume of solution in litres
0.0854
= = 0.0847 M
1.008
Number of gram equivalents of solute
and Normality =
volume of solution in litres
0.0854
= [∵ Mol mass of NaCl = Eq. wt. of NaCl]
1.008
= 0.0847 N

To Calculate Mole Fraction of the Solute

1000
No. of moles of water in 1000 ml = = 55.5
18
[∵ 1 ml of Water = 1 g of water]
Total number of moles = No. of moles of solute + No. of moles of solvent
= 0.0854 + 55.5
= 55.5854
534 14 PHYSICAL CHEMISTRY

No. of moles of NaCl

Mole fraction of NaCl =
Total moles
0.0854
=
55.5854
= 1.536 × 10–3
SOLUTIONS OF GASES IN GASES
When a gas is mixed with another gas a completely homogeneous solution results provided of
course they do not react chemically. It is obvious that such gaseous solutions will have the following
characteristic properties :
(1) Complete miscibility. According to the Kinetic Theory, a gas consists of tiny molecules
moving about in vacant space and thus when one gas is dissolved in another gas they form a
homogeneous solution quite readily. In such a gaseous mixture, the components can be present to
an unlimited extent.
(2) Dalton’s law of Partial pressures. Since in a gaseous mixture the constituent molecules exist
separately, it is obvious that the properties of the mixture will be the sum of properties of the
components. Thus Dalton (1842) was the first to show that the total pressure exerted by a gaseous
mixture is the sum of the individual or partial pressures of the component gases. If p1, p2, p3... be the
partial pressures of the constituents, the total pressure P of the mixture is given the expression
P = p1 + p2 + p3 + ...
Like other gas laws, Dalton’s law holds strictly only when the partial pressures are not too high.
This law can be experimentally tested by comparing the total pressure of a gaseous mixture with the
sum of the individual pressure of each gas before mixing.
SOLVED PROBLEM. At constant temperature, 250 ml of nitrogen under 720 mm pressure and 380
ml oxygen under 650 mm pressure were put into a one-litre flask. What will be the final pressure of
the mixture ?
SOLUTION
Since PV = P'V' at constant temperature (Boyle’s Law)
PN2 × 1000 = 720 × 250 or PN2 = 180 mm Hg
PO2 × 1000 = 380 × 650 or PO2 = 247 mm Hg
Total pressure P = PN + PO (Dalton’s Law)
2 2

= 180 + 247 = 427 mm Hg

HENRY’S LAW
The solubility of a gas in a solvent depends on the pressure and the temperature. When a gas is
enclosed over its saturated solution, the following equilibrium exists.
gas U gas in solution
If pressure is increased on the system, the equilibrium will move in the direction which will
reduce the pressure (Le Chatelier Principle). The pressure can be reduced by more gas dissolving in
solvent. Thus solubility or concentration of a gas in a given solvent is increased with increase of
pressure. A kinetic molecular explanation of the effect of pressure on gas-solution system is illustrated
in Fig. 14.2.
The relationship between pressure and solubility of a gas in a particular solvent was investigated
by William Henry (1803). He gave a generalisation which is known as Henry’s Law. It may be stated
as : for a gas in contact with a solvent at constant temperature, concentration of the gas that
dissolves in the solvent is directly proportional to the pressure of the gas.
 SOLUTIONS 535

(a) (b) (c)

Figure 14.2
(a) Equilibrium exists between the gas molecules and those in solution;
(b) When pressure is applied, gas volume decreases and concentration in
gas phase increases; (c) More gas molecules pass into solution to reestablish
equilibrium whereby the pressure above the gas is decreased.

Mathematically, Henry’s Law may be expressed as

C ∝P
or C =kP
where P = pressure of the gas; C = concentration of the gas in solution; and k = proportionality
constant known as Henry’s Law Constant. The value of k depends on the nature of the gas and
solvent, and the units of P and C used.
Limitations of Henry’s Law
It applies closely to gases with nearly ideal behaviour.
(1) at moderate temperature and pressure.
(2) if the solubility of the gas in the solvent is low.
(3) the gas does not react with the solvent to form a new species. Thus ammonia (or HCl)
which react with water do not obey Henry’s Law.
NH3 + H2O U NH4+ + OH–
(4) the gas does not associate or dissociate on dissolving in the solvent.
SOLVED PROBLEM 1. The solubility of pure oxygen in water at 20°C and 1.00 atmosphere
pressure is 1.38 × 10–3 mole/litre. Calculate the concentration of oxygen at 20°C and partial pressure
of 0.21 atmosphere.
SOLUTION
Calculation of k :
C =kP
C
or k =
P
536 14 PHYSICAL CHEMISTRY

Substituting values for pure oxygen,

1.38 × 10 –3 mole / litre mol / litre
k = = 1.38 × 10 –3
1.00 atm atm
Calculation of Concentration of O2 at given pressure
C =kP
mol / litre
Concentration of O2 = 1.38 × 10 –3 × 0.21atm
atm
= 2.9 × 10–4 mole/litre
SOLVED PROBLEM 2. At 20° C the solubility of nitrogen gas in water is 0.0150 g/litre when the
partial pressure of N2 is 580 torr. Find the solubility of N2 in H2O at 20°C when its partial pressure is
800 torr.
SOLUTION
We know that Henry’s law for a gas at two different concentration and pressures can be
written as
C1 C2
=k =k
P1 P2
Since k has the same value in two cases,
C1 C2
= ...(1)
P1 P2
In this example,
C1 = 0.0150 g/litre C2 = ?
P1 = 580 torr P2 = 800 torr
Substituting values in equation (1), we have
0.0150 g / litre C2
=
580 torr 800 torr
(800 torr) (0.0150 g / litre)
Thus C2 =
(580 torr)
= 0.0207 g/litre
Thus solubility of N2 in H2O at 20°C at pressure of 800 torr is 0.0207 g / litre.
Note. The above solution eliminates the calculation of k as was done in example 1.

SOLUTIONS OF LIQUIDS IN LIQUIDS

The solutions of liquids in liquids may be divided into three classes as follows :
Liquid-Liquid Systems

(1) Liquids that (2) Liquids that are (3) Liquids that are
are completely miscible partially miscible practically immiscible
e.g., alcohol and water e.g., ether and water e.g., benzene and water

We will now proceed to consider the more important properties of these three classes of solutions.
SOLUBILITY OF COMPLETELY MISCIBLE LIQUIDS
Liquids like alcohol and ether mix in all proportions and in this respect they could be
compared to gases. The properties of such solutions, however, are not strictly additive, and
 SOLUTIONS 537

therefore their study has not proved of much interest. Generally the volume decreases on mixing
but in some cases it increases. Sometimes heat is evolved when they are mixed while in others
it is absorbed. The separation of this type of solutions can be effected by fractional distillation.
SOLUBILITY OF PARTIALLY MISCIBLE LIQUIDS
A large number of liquids are known which dissolve in one another only to a limited extent e.g.,
ether and water. Ether dissolves about 1.2% water; and water also dissolves about 6.5% ether. Since
their mutual solubilities are limited, they are only partially miscible. When equal volumes of ether and
water are shaken together, two layers are formed, one of a saturated solution of ether in water and the
other of a saturated solution of water in ether. These two solutions are referred to as conjugate
solutions. The effect of temperature on the mutual solubility of these mixtures of conjugate solutions
is of special interest. We will study the effect of temperature on the composition of such mixtures
with reference to three typical systems :
(1) Phenol-Water system
(2) Triethylamine-Water system
(3) Nicotine-Water system
PHENOL–WATER SYSTEM
The curve in Fig. 14.3 (a) represents the miscibility of phenol and water. The left hand side of the
parabolic curve represents one of the two conjugate solutions which depicts the percentage of
phenol dissolved in water at various temperatures. The solubility of phenol increases with temperature.
The right hand side of the curve represents the other conjugate solution layer that gives the
percentage of water in phenol. The solubility of water in phenol also increase with increase of
temperature. The two solution curves meet at the maxima on the temperature-composition curve of
the system. This point here corresponds to temperature 66°C and composition of phenol as 33%.
Thus at a certain maximum temperature the two conjugate solutions merge, become identical and
only one layer results. The temperature at which the two conjugate solutions (or layers) merge into
one another to from one layer, is called the Critical Solution Temperature (CST) or Upper Consolate
Temperature. This is characteristic of a particular system and is influenced very much by the presence
of impurities. The determination of critical solution temperature may, therefore, be used for testing
the purity of phenol and other such substances.

1 Layers
65
60
50
M L N
50
2 Layers
Temperature oC
Temperature oC

2 Layers

18.5

1 Layer

A B C D
0 100 0 100
% By Weight of Phenol % By Weight of Triethylamine
(a) Phenol-Water system (b) Triethylamine-Water system

Figure 14.3
Temperature-composition curves.
538 14 PHYSICAL CHEMISTRY

At any temperature above the critical solution temperature, phenol and water are miscible in all
proportions. Outside the curve there is complete homogeneity of the system, i.e., one layer only
exists; and under the curve there may be complete miscibility but it depends upon the composition
of the mixture. It is clear from Fig. 14.3 (a) that at a temperature below 50°C a mixture of 90% phenol
and 10% water or 5% phenol and 95% water, will be completely miscible since the corresponding
points do not lie under the curve. Two layers will always separate out below the curve and the curve
gives compositions of the conjugate solutions constituting the two layers. At 50°C a mixture of equal
proportion of phenol and water (50% each) will form two layers whose compositions are given by A
and B. The line joining the points (M and N) corresponding to the compositions A and B is called the
tie line. This line helps in calculating the relative amounts of the two layers, which is here given by
the ratio MN/ML.
Some other liquid pairs behaving like phenol-water system are given below with their CST
values and the percentage of the first component being given in bracket.
(a) Methanol-Cyclohexane (49°C ; 29)
(b) Hexane-Aniline (59.6°C ; 52)
(c) Carbon disulphide-Methanol (49.5°C, 80)
TRIETHYLAMINE–WATER SYSTEM
The temperature-composition curve of mutual solubilities of triethylamine and water is given in
Fig. 14.3 (b). The left hand side of the curve indicates the solubility curve of triethylamine in water
and the right hand side of that of water in triethylamine. Unlike phenol-water system, the solubilities
decrease with the increase in temperature in this system. The two conjugate solutions mix up
completely at or below 18.5°C. This temperature is also called the critical solution temperature or the
lower consolate temperature. As in the above case, any point above the horizontal line corresponds
to heterogeneity of the system (two layers) while below it is complete homogeneity (one layer). Thus
an equi-component mixture (50–50) will be completely miscible at 10°C but at 50°C there will be
separating out two layers having compositions corresponding to the points C and D.
Common examples of this system with their lower critical solution temperatures and percentage
of the first component are given below.
(a) Diethylamine-Water (43°C ; 13)
(b) 1-Methylpiperidine-Water (48°C ; 5) 208
200
NICOTINE–WATER SYSTEM
The behaviour of this type of system is as if it were a
combination of the first two types. At ordinary temperature
nicotine and water are completely miscible but at a higher
150
temperature the mutual solubility decreases and as the
Temperature oC

temperature is raised further the two liquids again become

miscible. In other words, the mutual solubility increases 2 Layers
both on lowering as well as raising the temperature in certain
ranges. Thus we have a closed solubility curve and the 100
system has two critical-solution-temperatures, the upper
208°C and the lower 61°C. The effect of pressure on this
system is that the lower critical temperature is raised while 61
the upper critical temperature is lowered gradually until A B
finally they become one. At this point the liquids are 50
0 100
miscible at all the temperatures (Fig. 14.4). % By Weight of Nicotine
Glycerine – m-Toluidine ; and Water – β-Picoline are Figure 14.4
other examples of this type. Miscibility of nicotine and water.