temperature. The solubility of gases increase with increase of pressure.

For solution of gases in a solvent, consider a system as shown in

Fig. 1.1 (a). The lower part is solution and the upper part is gaseous
system at pressure p and temperature T. Assume this system to be in
a state of dynamic equilibrium, i.e., under these conditions rate of
gaseous particles entering and leaving the solution phase is the same.
Now increase the pressure over the solution phase by compressing the
gas to a smaller volume [Fig. 1.1 (b)]. This will increase the number of
gaseous particles per unit volume over the solution and also the rate
at which the gaseous particles are striking the surface of solution to
enter it. The solubility of the gas will increase until a new equilibrium
is reached resulting in an increase in the pressure of a gas above the
solution and thus its solubility increases.
Henry was the first to give a
quantitative relation between
pressure and solubility of a gas in
a solvent which is known as
Henry’s law. The law states that
at a constant temperature, the
solubility of a gas in a liquid is
directly proportional to the
partial pressure of the gas
present above the surface of
liquid or solution. Dalton, a
contemporary of Henry, also
Fig. 1.1: Effect of pressure on the solubility of a gas. The concluded independently that the
concentration of dissolved gas is proportional to the solubility of a gas in a liquid
pressure on the gas above the solution.
solution is a function of partial
pressure of the gas. If we use the mole fraction of a gas in
the solution as a measure of its solubility, then it can be
said that the mole fraction of gas in the solution is
proportional to the partial pressure of the gas over
the solution. The most commonly used form of Henry’s
law states that “the partial pressure of the gas in
vapour phase (p) is proportional to the mole fraction
of the gas (x) in the solution” and is expressed as:
p = KH x (1.11)
Here KH is the Henry’s law constant. 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 Fig. 1.2.
Different gases have different KH values at the same
temperature (Table 1.2). This suggests that KH is a
function of the nature of the gas.
Fig. 1.2: Experimental results for
It is obvious from equation (1.11) that higher the
the solubility of HCl gas in value of KH at a given pressure, the lower is the solubility
cyclohexane at 293 K. The of the gas in the liquid. It can be seen from Table 1.2
slope of the line is the that KH values for both N2 and O2 increase with increase
Henry’s Law constant, KH. of temperature indicating that the solubility of gases

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 Table 1.2: Values of Henry's Law Constant for Some Selected Gases in Water

Gas Temperature/K KH /kbar Gas Temperature/K KH /kbar

He 293 144.97 Argon 298 40.3

H2 293 69.16 CO2 298 1.67
N2 293 76.48
Formaldehyde 298 1.83×10-5
N2 303 88.84
O2 293 34.86 Methane 298 0.413
O2 303 46.82 Vinyl chloride 298 0.611

increases with decrease of temperature. It is due to this reason that

aquatic species are more comfortable in cold waters rather than in
warm waters.

Example 1.4 If N2 gas is bubbled through water at 293 K, 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 kbar.

Solution The solubility of gas is related to the mole fraction in aqueous solution.
The mole fraction of the gas in the solution is calculated by applying
Henry’s law. Thus:
p (nitrogen) 0.987bar
x (Nitrogen) = = = 1.29 × 10–5
KH 76,480 bar
As 1 litre of water contains 55.5 mol of it, therefore if n represents
number of moles of N2 in solution,
n mol n
x (Nitrogen) = = = 1.29 × 10–5
n mol + 55.5 mol 55.5
(n in denominator is neglected as it is < < 55.5)
Thus n = 1.29 × 10–5 × 55.5 mol = 7.16 × 10–4 mol
7.16×104 mol × 1000 mmol
= = 0.716 mmol
1 mol

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.
· Scuba divers must cope with high concentrations of dissolved gases
while breathing air at high pressure underwater. Increased pressure
increases the solubility of atmospheric gases in blood. When the
divers come towards surface, the pressure gradually decreases. This
releases the dissolved gases and leads to the formation of bubbles
of nitrogen in the blood. This blocks capillaries and creates a medical
condition known as bends, which are painful and dangerous to life.

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 To avoid bends, as well as, the toxic effects of high concentrations
of nitrogen in the blood, the tanks used by scuba divers are filled
with air diluted with helium (11.7% helium, 56.2% nitrogen and
32.1% oxygen).
· At high altitudes the partial pressure of oxygen is less than that at
the ground level. This leads to low concentrations of oxygen in the
blood and tissues of people living at high altitudes or climbers. Low
blood oxygen causes climbers to become weak and unable to think
clearly, symptoms of a condition known as anoxia.
Effect of Temperature
Solubility of gases in liquids decreases with rise in temperature. When
dissolved, the gas molecules are present in liquid phase and the process
of dissolution can be considered similar to condensation and heat
is evolved in this process. We have learnt in the last Section that
dissolution process involves dynamic equilibrium and thus must
follow Le Chatelier’s Principle. As dissolution is an exothermic
process, the solubility should decrease with increase of
temperature.

Intext Questions
1.6 H2S, a toxic gas with rotten egg like smell, is used for the qualitative analysis. If
the solubility of H2S in water at STP is 0.195 m, calculate Henry’s law constant.
1.7 Henry’s law constant for CO2 in water is 1.67×108 Pa at 298 K. Calculate
the quantity of CO2 in 500 mL of soda water when packed under 2.5 atm
CO2 pressure at 298 K.

1 . 4 Vapour Liquid solutions are formed when solvent is a liquid. The solute can be
Pressure of a gas, a liquid or a solid. Solutions of gases in liquids have already
been discussed in Section 1.3.2. In this Section, we shall discuss the
Liquid solutions of liquids and solids in a liquid. Such solutions may contain
Solutions one or more volatile components. Generally, the liquid solvent is volatile.
The solute may or may not be volatile. We shall discuss the properties
of only binary solutions, that is, the solutions containing two
components, namely, the solutions of (i) liquids in liquids and (ii) solids
in liquids.
1.4.1 Vapour Let us consider a binary solution of two volatile liquids and denote the
Pressure of two components as 1 and 2. When taken in a closed vessel, both the
Liquid- components would evaporate and eventually an equilibrium would be
Liquid established between vapour phase and the liquid phase. Let the total
Solutions vapour pressure at this stage be ptotal and p1 and p2 be the partial
vapour pressures of the two components 1 and 2 respectively. These
partial pressures are related to the mole fractions x1 and x2 of the two
components 1 and 2 respectively.
The French chemist, Francois Marte Raoult (1886) gave the
quantitative relationship between them. The relationship is known as
the Raoult’s law which states that for a solution of volatile liquids,

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 the partial vapour pressure of each component of the solution
is directly proportional to its mole fraction present in solution.
Thus, for component 1
p1 µ x1
and p1 = p10 x1 (1.12)
0
where p is the vapour pressure of pure component 1 at the same
1
temperature.
Similarly, for component 2
p2 = p20 x2 (1.13)
0
where p2 represents the vapour pressure of the pure component 2.
According to Dalton’s law of partial pressures, the total pressure
( p total ) over the solution phase in the container will be the sum of the
partial pressures of the components of the solution and is given as:
ptotal = p1 + p2 (1.14)
Substituting the values of p1 and p2, we get
ptotal = x1 p10 + x2 p20
= (1 – x2) p10 + x2 p20 (1.15)
= p10 + (p20 – p10) x2 (1.16)
Following conclusions can be drawn from equation (1.16).
(i) Total vapour pressure over the solution can be related to the mole
fraction of any one component.
(ii) Total vapour pressure over the solution varies linearly with the
mole fraction of component 2.
(iii) Depending on the vapour pressures
of the pure components 1 and 2,
total vapour pressure over the
solution decreases or increases with
the increase of the mole fraction of
component 1.
A plot of p1 or p2 versus the mole
fractions x1 and x2 for a solution gives a
linear plot as shown in Fig. 1.3. These
lines (I and II) pass through the points for
which x 1 and x 2 are equal to unity.
Similarly the plot (line III) of ptotal versus
x2 is also linear (Fig. 1.3). The minimum
0
value of ptotal is p1 and the maximum value
Fig. 1.3: The plot of vapour pressure and mole 0
is p2 , assuming that component 1 is less
fraction of an ideal solution at constant 0 0
volatile than component 2, i.e., p1 < p2 .
temperature. The dashed lines I and II
represent the partial pressure of the The composition of vapour phase in
components. (It can be seen from the plot equilibrium with the solution is determined
that p1 and p2 are directly proportional to x1 by the partial pressures of the components.
and x2, respectively). The total vapour If y1 and y2 are the mole fractions of the
pressure is given by line marked III in the
figure.
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 components 1 and 2 respectively in the vapour phase then, using Dalton’s
law of partial pressures:
p1 = y1 ptotal (1.17)
p2 = y2 ptotal (1.18)
In general
pi = yi ptotal (1.19)

Vapour pressure of chloroform (CHCl3) and dichloromethane (CH2Cl2) Example 1.5

at 298 K are 200 mm Hg and 415 mm Hg respectively. (i) Calculate
the vapour pressure of the solution prepared by mixing 25.5 g of
CHCl3 and 40 g of CH2Cl2 at 298 K and, (ii) mole fractions of each
component in vapour phase.
Solution
(i) Molar mass of CH2Cl2 = 12 × 1 + 1 × 2 + 35.5 × 2 = 85 g mol–1
Molar mass of CHCl3 = 12 × 1 + 1 × 1 + 35.5 × 3 = 119.5 g mol-1
40 g
Moles of CH2Cl2 = 85 g mol 1 = 0.47 mol
25.5 g
Moles of CHCl3 = 119.5 g mol 1 = 0.213 mol

Total number of moles = 0.47 + 0.213 = 0.683 mol

0.47 mol
x CH2Cl2 = = 0.688
0.683 mol
x CHCl3 = 1.00 – 0.688 = 0.312
Using equation (2.16),
p total = p10 + (p20 – p10) x2 = 200 + (415 – 200) × 0.688
= 200 + 147.9 = 347.9 mm Hg

(ii) Using the relation (2.19), yi = pi/ptotal, we can calculate the mole
fraction of the components in gas phase (yi).
pCH2Cl2 = 0.688 × 415 mm Hg = 285.5 mm Hg
pCHCl3 = 0.312 × 200 mm Hg = 62.4 mm Hg
yCH2Cl2 = 285.5 mm Hg/347.9 mm Hg = 0.82
yCHCl3 = 62.4 mm Hg/347.9 mm Hg = 0.18

0
Note: Since, CH2Cl2 is a more volatile component than CHCl3, [ p CH2 Cl2 =
0
415 mm Hg and p CHCl3 = 200 mm Hg] and the vapour phase is also richer
in CH2Cl2 [ yCH2Cl2 = 0.82 and y CHCl3 = 0.18], it may thus be concluded
that at equilibrium, vapour phase will be always rich in the component
which is more volatile.

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1.4.2 Raoult’s According to Raoult’s law, the vapour pressure of a volatile component
Law as a in a given solution is given by pi = xi pi0. In the solution of a gas in a
special case liquid, one of the components is so volatile that it exists as a gas and
of Henry’s we have already seen that its solubility is given by Henry’s law which
Law states that
p = KH x.
If we compare the equations for Raoult’s law and Henry’s law, it
can be seen that the partial pressure of the volatile component or gas
is directly proportional to its mole fraction in solution. Only the
0
proportionality constant KH differs from p1 . Thus, Raoult’s law becomes
0
a special case of Henry’s law in which KH becomes equal to p1 .
1.4.3 Vapour Another important class of solutions consists of solids dissolved in
Pressure of liquid, for example, sodium chloride, glucose, urea and cane sugar in
Solutions of water and iodine and sulphur dissolved in carbon disulphide. Some
Solids in physical properties of these solutions are quite different from those of
Liquids pure solvents. For example, vapour pressure. Liquids at a given
temperature vapourise and under
equilibrium conditions the pressure exerted
by the vapours of the liquid over the liquid
phase is called vapour pressure [Fig. 1.4 (a)].
In a pure liquid the entire surface is
occupied by the molecules of the liquid. If a
non-volatile solute is added to a solvent to
give a solution [Fig. 1.4.(b)], the vapour
pressure of the solution is solely from the
solvent alone. This vapour pressure of the
solution at a given temperature is found to
be lower than the vapour pressure of the
pure solvent at the same temperature. In
Fig. 1.4: Decrease in the vapour pressure of the the solution, the surface has both solute and
solvent on account of the presence of solvent molecules; thereby the fraction of the
solute in the solvent (a) evaporation of the surface covered by the solvent molecules gets
molecules of the solvent from its surface reduced. Consequently, the number of
is denoted by , (b) in a solution, solute
solvent molecules escaping from the surface
particles have been denoted by and they
is correspondingly reduced, thus, the vapour
also occupy part of the surface area.
pressure is also reduced.
The decrease in the vapour pressure of solvent depends on the
quantity of non-volatile solute present in the solution, irrespective of
its nature. For example, decrease in the vapour pressure of water by
adding 1.0 mol of sucrose to one kg of water is nearly similar to that
produced by adding 1.0 mol of urea to the same quantity of water at
the same temperature.
Raoult’s law in its general form can be stated as, for any solution
the partial vapour pressure of each volatile component in the
solution is directly proportional to its mole fraction.
In a binary solution, let us denote the solvent by 1 and solute by
2. When the solute is non-volatile, only the solvent molecules are
present in vapour phase and contribute to vapour pressure. Let p1 be

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