4.

Vapour Pressure of Pure Liquid and Solution

Vapour pressure: When aliquid is taken ina closed vessel, a part of the liquid evaporates and its vapours
occupy the available empty space. These vapours cannot escape as the vessel is closed. They would rather
have atendency to condense into liquid form. In fact an equilibrium isestablished between vapour phase
and liquid phase and the pressure that its vapour exert is termed as vapour pressure. Thus, vapour pressure
of a liquid may be defined as the pressure exerted by the vapours above the liquid surface in equilibrium
with the liquid phase at a given temperature.
The vapour pressure of a liquiddepends on the following factors:
Nature of the liquid: Liquids having weak intermolecular forces are volatile and therefore have greater
vapour pressure.
Temperature: Vapour pressure of aliquid increases with increase in temperature. This is because with
increase in temperature, the kinetic energy of the molecules increases and therefore large number of
molecules are available for escaping from the surface of the liquid.
(a) Vapour pressure of liquid-liquid solution:
Raoult's Law for solutions of volatile liquids: It states that for a solution of volatile liquids the partial
pressure of each component solution is directly proportional to its mole fraction. Mathematically,
PA C X PB XB
PA =PAX PB=PBXg
where p, and p are partial vapour pressures, x and xz are mole fractions, p, and p are the vapour
pressure of pure components A and B respectively.
Ifp is total vapour pressure then according to Dalton's law of partial pressure.
P=PA PB
=PÅ X t P!AB
=p(l-Xg) +PXB

Asp and pg are constants at a given temperature it is evident from the above equations that the total
vapour pressure varies linearly with the mole fraction xg (or x since XA = 1-X).
The composition of the vapour phase in equilibrium with the solution can be determined from the
partial pressure of the two components. If y, and yg are the mole fractions of components A and B
respectively in the vapour phase, then
PA = YA Protal'
PB =YB Ptotal
In general, Pi = Y;Potal
(b) Vapour pressure of solutions of solids in liquids
Raoult's law for a solution containing a non-volatile solute and volatile solvent: It states that the
relative lowering of vapour pressure is equal to mole fractions of solute which is non-volatile.
Mathematically, p=PA + PB
Or, p=PA(Since solute B is non-volatile)
p=PÀXA
p=PÅl-x) =På -Pixp
PÄ Xy =PÅ-p
 Or
pP
P
Or
Relative lowering of vapour pressure = Mole fraction of solute
5, ldeal and Non-Ideal Solutions
(a) ldeal solution: A solution is called an ideal solution if
it obeys Raoult's law over a wide range of concentration -Vapour
pressure (P
Total
=PAtPg)
(Fig. 1.1) at a specified temperature.
For an ideal solution,
p=PAtPr =PÅ XA tPAB
Liquids having similar nature and structure are likely to
form ideal solutions. Examples are:
Mixture of methanol and ethanol
Mixture of n-hexane and n-heptane
Mixture of benzene and toluene.
PA=PÅ XA
Reasons for formation of ideal solutions: A solution X =1 Mole fraction
of two miscible liquids A and B will be ideal if two XB= 0

essential conditions are fulfilled.

()If FA_A is the force of attraction between molecules Fig. 1.1: Vapour pressure diagram for
an ideal solution
of Aand FR-B iS that of molecules of B, then Aand
B will form an ideal solution only if,
FA-B =FA-A =Fp-B
(ii) The solution of A and B liquids will be ideal if A and B have similar structures and polarity.
Methanol and ethanol have the same functional group and almost same polarity and therefore,
form ideal solutions.
For an ideal solution
() Raoult's law is obeyed, i.e.. PA =PAx, and pp =P XB
(ii) Amiy H=0 and
Vapour pressure of solution
(iii) Amix V=0.
(b) Non-ideal solution: A solution which does not obey p=PAtPB
P
Raoult's law for all concentrations is called a non-ideal
solution. pressure
Vapour
p'A
Fora non-ideal solution pe

(i) Raoult's law is not obeyed,

i.e., Pa* P, X and pp P Xg
(ii) Amix H0and
(i) Amix V0.
A non-ideal solution can show either positive or negative
deviation from Raoult's law.
(A)Positive Deviation: The deviation will be called t =1
positive when the partial pressure of each component XB=0
Mole fraction xA=O
xg=1
and the resultant total pressure are greater than the
pressure expected on the basis of Raoult's law Fig. 1.2: Vapour pressure diagram showing
(Fig. 1.2). positive deviation
In such cases, the intermolecular forces between solvent-solute molecules (F, _p) are weaker than
those between solvent-solvent (FA-) and solute-solute (FR_) molecules. That is.
FA-B <FA -A and Fs-B
This shows that the molecules ot A or B Will escape more easily from the surface of the solution.
i.e., the vapour pressure of solution will be higher.
 Characteristics of a Solution Showing Positive Deviation
" PA>PÀ X SPB> P Xp
" Amiy H>0, i.e., + Ve,
" Amix V>0, i.e., + ve,
Some examples of the solution exhibiting positive deviations are:
(i) Ethyl alcohol and water
(ii) Acetone and carbon disulphide
(iii) Carbon tetrachloride and benzene
(iv) Acetone and benzene
(B) Negative Deviation: The deviation is called
Vapour
pressure p=PAtPB
negative deviation, if the partial pressure of each pA
component (A and B) and resultant total vapour
pressure are less than the pressure expected on the
basis of Raoult's law. (Fig. 1.3)
This type of deviation is shown by the solutions in
which PA
FA-B>FA-Á and FB-B
Due to this, there is decrease in the escaping
tendency of A or B molecules from the surface of
solution. Mole fraction xA =0
XA=1
Consequently, the vapour pressure of the solution xg=0 xB=1
will be lower.
Characteristics of a Solution Showing Negative Fig. 1.3: Vapour pressure diagram showing
negative deviation
Deviation

Ai H<0, i.e., ve, because weak A-A and B-B bonds are broken and strong A-B bond is
formed. Heat is consequently released.
Amix V<0, i.e., -ve,
Some examples of the solution showing negative deviations are
(i) HNO, and water
(ii) Chloroform and acetone
(ii) Acetic acid and pyridine
(iv) Hydrochloric acid and water
Table 1.2: Characteristics of Ideal and Non-ideal Solutions
S.No. Ideal Solutions Non-ideal Solutions
Positive Deviation Negative Deviation
(i) FA-A=FB -B= FA-B F -B<FA-4 and Fg-B FA-B> Fa-A and Fg-B
(ii) PA =PiNA: Pa=PoNe PA>PÅA : PB> PåB PA<PåA i Pa<Påka
(iii) Amiy H=0 Amiy H> 0, i.e., +ve Amix H<0, i.e., -ve
(iv) Amiy V= 0 Amix V>0, i.e., +ve Amix V<0, i.e., -ve

Azeotropes or Azeotropic mixture: Azeotropes are binary mixtures having the same compos1tion
liquid and vapour phase and boilat a constant temperature.
Types of Azeotropes:
either
(i) Minimum boiling azeotropes: These are the binary mixtures whose boiling point is less than
Raoult's
of the two components. The non-ideal solutions which show a large positive deviation from
law form minimum boiling azeotrope at a specific composition, e.g.., a mixture of 94.5% elnyt a
and 4.5% water by volume.
(i) Maximum boiling azeotropes: These are the binary mixtures whose boiling point is more than either
of the two components. The solutions that show large negative deviation from Raoults's law form
maximum boiling azeotrope at a specific composition, e.g., a mixture of 68% HNO, and 32% H,O by
mass.