(a) (b)

Fig. 2.1

The effect of pressnre on solnbility of gas. The concentration of dissloved

gas is directly propertional to the pressure of gas npon the solution

and solution at temperature Tl and pressure Pl, and hence the rates of molecules entering into solution
and the dissolved gaseous molecules leaving the solution are equal. Now as shown in figure 2.1 (b) at
temperature Tl, the pressure increases from Pl to P2, the volume accomodated by gaseous solute on
the surface of solution decreases and hence the number of molecules of solute in unit volume increases.
So the number of gaseous molecules strtkmg the surface of solution increases and thus increases the
solubility and at the end equilibrium is established. Hence, the solubility of gaseous solute increases due
to the increase in the pressure of gaseous molecules in the solution.
Henry's law : The quantitative relation betwen solubility of gaseous solute in liquid solvent and
pressure was given by Henry in 1803. It can be expressed as "The solubility of a gaseous solute in a
liquid solvent at definite temperature is directly proportional to the pressure of the gas." On the basis
of this, Henry's law can be expressed as

Contemporarily Dalton independently concluded that

the solubility of a gaseous solute in liquid solution is a function
of the partial pressure of the gas. "If the mole fraction is
considered for the solubility of gaseous solute then the partial
pressure of a gaseous solute over the solution is directly
proportional to the mole-fraction of the gaseous molecules".
In the solution X is mole fraction of gaseous solute dissolved
in unit volume of solvent and its partial pressure is p, then
according to Henry's law it is expressed as
paX
0 0.010 0.020
p = KH ' X where, KH iS Henry's constant.

Fig' 2'2 If in the solution mole.-fraction of gas is X and its

Mole fraction of HCI in its
partial pressure is p and graph is plotted betwen them, the
solution in cyclohexane - - - 1 - -
graph IS a stright line as indicated m fig 2.2. The value of the
slope is equal to value of KH. The unit of KH is bar. The values of Henrys constant are different for
different gaseous solutes, at constant temperature. This indicates that KH is a function of the nature of
the gas. The values of KH also change with change in temperature for all the gaseous solutes which
___________________________________________________________________________
32 Chemistry 12
 Table 2.2 Values of Henary's Constant for Some Selected Gases in Water

The following results can be obtained from the KH values shown in table 2.2
1) The solubility of gaseous solute is lower with the higher values of
KH.
2) The KH values increase as temperature increase which means the decrease in solubility
of gaseous solute.
Limitations of Henry's law :
(i) This law is applicable to the gaseous solutes which show only ideal behaviour at high
temperature and low pressure.
ii) This law is applicable to solute which does not undergo association or dissociation when the
solute is dissolved in solvent.
iii) ) This law is applicable to gaseous solute which does not form any product by the chemical
reaction, when gaseous solute is dissolved in liquid solvent.
Uses of Henry's law : Henry's law is used in industrial field and to explain some biochemical
reactions :
(i) To increase the solubility of CO2 gas in cold-dri, soda-water, beer, champagne, the gases
are filled in bottle at high presures and then sealed.
ii) Due to higher partial pressure of oxygen gas entering into the lungs, it reacts with haemo-
globin and forms oxyhaemoglobin. The partical pressure of oxygen gas is low in tissue.
Hence, the oxygen is released from the oxohaemoglobin itself and is useful in the utilisation
of the function of cell.

Solutions 33
 Example 8 : Calculate the partial pressure of He gas over me solution, having 2.4 x 10-3
mole fraction of gas in its saturated solution at 273 K temperature. The value of Henry's constant
is 6.71 x 10-6 bar.

2.5 Solubility of SoHd Solute in SoHd Solvent

When solid solute is dissoved in solid solvent it gives solid

solution. The molecules are arranged in two ways :
(1) Substituted solid solution : As shown in fig 2.3, the
size of solid solute and solid solvent are almost me same, then me
solute atoms are arranged in solvent atoms and the solute atoms are
substituted in arrangement of atoms forming sohd solution. Such type
of solution is known as interstitial solid solution, e.g. brass, bronze,
steel, monel metal etc.
___________________________________________________________________________
34 Chemistry 12
 2.7 Vapour pressuresolid
(2) Interstitial of solution
solution : As shown in figure 2.4
when the sizes of sohd solute and sohd solvent have vast difference
A solid solute on dissolving in liquid solvent forms a solution. We have studied, such solutions.
then the small atoms are arranged in the interstitial holes formed
Now, let us study the vapour pressure of binary solutions which are obtained by dissolving solid solute
between big atoms. Such type of solutions are called interstitial sohd
in liquid solvent and liquid solute dissolved in liquid solvent. Solid solutes do not have remarkable
solution. e.g. Tungsten carbide (WC).
vapour
pressureSolubility
but liquid of solid
solute andsolute
liquid in liquidhave
solvent solvent
vapour: presures.
At constant
temperature and presure when the maximum amount of solid solute
is dissolved in given liquid solvent
Due tothen
thisthe
at concentration of solute is
certain temperature O atoms of atoms of
called its solubility. Now, no more solute can be dissolved in solution, solvent O solute
so
Thesuch a solution
factors which is called
affect mesaturated solution.are
vapour pressure Ingiven
a saturated
below.solution
the equilibrium is established
(i) The nature of between
liquid : sohd
The solute
weakerandthe
solution.
intermolecular forces between the molecules of
liquid, the
Solidgreater
solute +is Liquid
the vapour
solventpressure. This is because more and more molecules of liquid are
Liquid solution
converted into
It is notvapour phasethat
necessary andallhence the vapour
the solid solutespressure is more.
will dissolve in all the liquid solvents. For example
(ii) like
ionic solids Temperature
NaCl or KCI : Higher the temperature
are solube of liquid,
in polar solvent like watermorebutisnotthe vapour
soluble pressure, because
in non-polar solvent
the kinetic
like benzeneenergy of thetetrachloride,
or carbon molecules increases
becausedue to increase
generally ionicin solid
temperature
solutes,and hence in
dissolve more andliquid
polar more
molecules
solvents. leaving the surface of liquid and obtain the vapour phase and its vapour pressure increses.
Similarly non-ionic compounds like napthalene will dissolve in non-polar solvents like benzene, but does
2.8 Raoult's Law (For Non-volatile Solute)
not dissolve
When insolid
polarsolute
solvent likeinwater.
dissolve liquid Thus the solubility of solute depends on the nature of solute and
solvent. Moreover
solvent and the issolubility
liquid solution formed its depends
vapour upon another two important factors like temperature and
pressure.
pressure can be understood by simple
experiment givenofbelow.
Effect As shown: in
temperature figuresolid solute is dissolved in liquid solvent and solution is obtained
When
2.5, take
then two equal containers
the equilibrium A and B as
is estabhshed andgiven below :
fill pure solvent and solution of non-
Solute
volatile solute (Sohd)
in same + Solvent
solvent (Liquid) Solution (Liquid)
in the containers
If such
respectively. reaction
InitiaHy in bothin equilibirium
containers, keep is endothermic then according to Le-Chatelier's principle, on
increasing the temperature,
the level of both the and
the liquids (solvent forward
so- reaction will occur and hence the solubility win increase, and
if such reaction is exothermic, then onof increasing the temperature according to Le-Chatelier's principle,
lution) same, it will be found mat the level
the reverse
solvent reaction
is more will
reduced occur
than andofhence
the level the solubility
Q Solvent 0 Solute will decrease.
solution,Effect of pressure
because in
: Sohd solute substances when container A
dissolved in hquid solvents having
give hquid
solvent, its surface has totally solvent molecules Ca) VaPour Pressure of Cb) VaPour Pressure
solutions. Here, the substances are related with reactions may be in sohd or hquid state which possess
A t c ____ ^A vt /1^ 1 pure solvent of solution
the
ansnon-compressible
Hence more vapourproperty, so wrote
Is lormes. the effect
m ~ of pressure is very less or negligible.
container B having solution, Properties
2.6 Solution"Colligative me surface has Fig' 2'5 VaPour Pressure of soluuon
both solute and solvent molecules. So in
containersWhen
B thesolute
fractionsubstances are dissolved
of surface covered in molecules
by solvent pure solvent, the solutions
gets reduced aretheobtained.
as a result number Some
properties
of molecules of solvent
escapingchange
from viz.
the the vapour
surface is pressure
reduced ofanda solution prepared
hence vapour from aissolvent
pressure reducedis in
lesscontainer
than
that of pure solvent, while the boiling point increases and freezing point decreases.
B. Thus, me vapour pressure of a solution prepared from a solvent is always less man that of pure The osmotic presure
also changes.
solvent. The change
The lowering in these
of vapour properties
pressure dependwas
of solution onstudied
numberbyofRaoult
molecules
and aoflawsolute but not on
was proposed in nature
of solute.
1887, whichSuch properties
is called are law.
Raoult's called colligative
According properties
to Raoult's lawof solution. For example by taking Im aqueous
solution of glucose, NaCl and BaCl2 and if the colhgative properties are studied, it is observed that all
the solutons have
PJroof equal molal
of Raoult's law :concentration, yet the
For binary solution, number
Raoult's lawof particles present
is generaHy experessareas. not equal. In glucose
solution the concentration of number of particles of solute are 1 m, in NaCl solution the concentration
of number of particles are 2 m and in BaCl2 solution the concentration of number of particles is 3 m
The binary solution in which non-volatile solute is dissolved in the
Hence, their colligative properties are in proportion of 1:2:3 respectively. So these colhgative properties
solution, the vapour is only due to solvent. If the vapour pressure of solvent is denoted by pl and its
do not depend upon the concentration of solution but depend on the concentration of the number of
mole-fraction by XI men mathematical form is______________________________________________________________
particles of solute present in the solution.
36 Chemistry 12
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Solutions 35