Vapor Pressure

➢ Vapour pressure is defined as the pressure exerted by the vapour

in equilibrium with the liquid (vapour ⇌ liquid) at a given
temperature.

➢ Vapour pressure may also be regarded as a measure of escaping

tendency of the liquid molecules. The higher the escaping
tendency the higher is the vapour pressure.
 Solution of L→L: (Solution of liquid in liquid)

Ideal & non-ideal solution:

A solution which obeys Raoult’s law strictly is called an ideal solution. A solution which show
derivation from Raoults law is called non-ideal or real solution.

Raoult’s Law:
It states that the relative lowering of the vapor pressure of a dilute solution is equal to the mole
fraction of the solute present in dilute Solution:

P − Ps n P= vap. Pressure of the solvent

= Ps= vap. Pressure of the solution
P n+ N n= no. of moles of solute
N= no. of moles of solvent
Derivation of Raoult’s Law:
The vapour pressure of the pure solvent is caused by the number of molecules evaporating
from its surface. When a non-volatile solute is dissolved in solution, the presence of solute
molecules in the surface blocks a fraction of the surface where no evaporation can take
place. This causes lowering of the vapour Pressure.

The vapour pressure of the solution is therefore determined by-

▪ the number of molecules of the solvent present at any time in the surface which is
proportional to the mole fraction.
 N
Ps  Ps = vap. Pressure of solution
n+ N N= mole no. of solvent
n = mole no. of solute
N
Ps = k k is the proportional const.
n+ N
N
=1
In case of pure solvent, n= 0. So, mole fraction
O+N
Vap. pressure P= k. So,
N
Ps = P
n+ N
Ps N
or, =
P n+ N w
P − Ps n m
or, 1−
Ps
= 1−
N = =
P n+ N P n + N w +W
m M
P − Ps n
or, = = mole fraction of solute
P n+ N
P1: The vapour pressure of ether (mol mass = 74) is 442 mm Hg at 293 K. If 3g of a
compound A are dissolved in 50 g of ether at this temperature, the vapour pressure falls to
426 mm Hg. Calculate the molecular mass of A. Assume that the solution of A in ether is
very dilute.
P2: 18.2 g of urea is dissolved in 100 g of water at 50°C. The lowering of vapour
pressure produced is 5 mm Hg. Calculate the molecular mass of urea. The vapour
pressure of water at 50°C is 92 mm Hg.
Binary Liquid System:

Completely Miscible Liquids:

Two volatile liquid which are completely miscible with one another in all proportion.

P= total pressure
PA = Partial vapour pressure of A in vapour
PB = Partial vapour pressure of B in vapour
P= PA + PB
nA
PA = P
nA + nB
nB
PB = P
nA + nB
nA= moles of A in the vapour
nB= moles of B in the vapour
Ideal System: Raoult’s Law:

PA = PAo.XA……….(1) PA/PB= Partial Pressure (of A/B)

PB = PBo.XB……….(2) XA = mole fraction of A in the liquid phase
XB = mole fraction of B in the liquid phase
PO = Vapour pressure of the pure component (A or B)

Duhem-Margules Law:
For mixture of two liquid: There must be some connection between the relative amounts of the
two components (XA and XB) and their partial vapour pressures (PA and PB).

α= constant for both the components (A and B)

By putting α=0, the above equation takes form of Raoult’s law.
Deviation from Raoult’s Law:

If γAB = γAA: solution will show the same vapour pressure as predicted by the
Raoult’s law. It is said an ideal solution

If γAB > γAA: Negative deviation. Molecule A will escape less readily and the
vapour pressure will be less than that predicted by Raoult’s law.

If γAB < γAA: Positive deviation. Molecule A will escape more readily and the
vapour pressure will be higher than that predicted by Raoult’s law.
If a mixture of two liquids behaves ideally, then according to Raoult’s Law, the plot of
the partial pressure of each component against its respective mole fraction in the liquid
phase should be straight line passing through the origin:

Only limited number of cases are known that obey Raoult’s Law over the whole range of
concentration:

(i) Ethylene dibromide / Proptlene dibromide at 85oC

(ii) Benzene/ Ethylene dichloride at 50oC
(iii) n-hexane/n-heptene at 30oC
(iv) Ethyl bromide/ ethyl iodide at 30oC
(v) n-butyl chloride/n-butylbromide at 50oC
Deviation from Raoult’s Law:
If the two components of the liquid mixture differ in:
(a) Internal pressure: (T δP/dT)V: measure of the alternative force between the
molecules
(b) Polarity
(c) Length of hydrocarbon chain or analogous grouping or
(d) One or other of the components is associated in the liquid state

Then the system does not behave ideally.

Positive derivations from Raoult’s Law:

▪ The four factors (a-d) mentioned above results in positive deviation.

▪ The measured vapour pressures are greater than those to be expected from
equation (1) and (2) and are in harmony with equation (3) and (4) with α
having a positive value.
The dotted curves approaches the ideal one as the system approaches to pure A or pure B. i.e, A
tends to obey Raoult’s Law when the conc. of B becomes very small. If the positive derivations
from ideality is very large the total vap. Pressure curves show a maximum.

System with positive derivations are very common, in fact, most homogenous liquid
mixtures fall into this category.

System with small +ve deviation:

CCl4/heptane at 50oC

Larger deviation:
Ethyl ether/ acetone at 20o and 30o C
Heptane/ethyl alcohol at 50oC
Negative deviation from Raoult’s Law:
If A and B attract one another strongly and if there is partial compound formation between A
and B in the liquid phase, the vapour pressure of each constituent may be less than that required
by Raoult’s Law and α in equation (3) and (4) is negative.

Negative deviation is not very common.

Examples:
Pyridine/Formic, acetic or propinic acid
i.e. a basic and an acidic component

Chloroform/ketone, ether, ester, amine

HCl, HNO3, Perchloric acid/H2O
Composition of liquid and vapour:
From the vapour Pressure curves, the composition of the vapour in equilibrium with any
particular liquid at a given temperature can be found making the assumption that
xA α PA
x B α PB
Again, more important general conclusion can be reached from Konowaloff’s rule:

“The vapour is relatively richer in the component whose addition to the liquid
mixture results in an increase in total vapour Pressure”
Konowaloff’s made the first systematic measurements of the total vapour pressures of
homogenous liquid systems, showing that mixtures could be divided into three types:

(i) Vapour pressure decreased regularly with composition/ b.p. rises steadily with
change of composition from more volatile to less volatile component
(ii) Vap. pressure showed a maximum/ b.p. minimum
(iii)Vap. pressure showed a minimum/ b.p. maximum

If distillation is carried out, then composition of the vapour (i.e. distillate) can be
determined from vapour pressure curves.
a) b.p. increases regularly:
# A → has lower b.p.
B → has higher b.p.
according to the law:
upper curve → vapour
lower curve → liquid
Here, vapour always contains more A
# when a liquid of composition l
boils at t, the vapour of composition
V will be evolved. The vap. is richer
in A, the remaining liquid become
relatively richer in B and its b.p.
consequently rises.
#line joining l-V is called tie line:
The line joining two points l and V
Giving the composition of systems
In eqm is called a tie line.
#Examples:
CS2/benzene
acetone/tolune
acetone/ether
chloroform/CCl4
Chlorobenzene/bromobenzene
b) Minimum b.p.:
Two curves meet at the minimum M, So that here
liquid and vapour in eqm have the same composition.
The liquid represented by M will therefore boil at a
constant temperature and distil over completely
without change of composition, such systems, which
distil unchanged is called azeotropic mixture.
Azeotropic mixture behaves in distillation as if it
were a single substance, although the variation of its
composition with pressure shows it to be a mixture.

#Positive derivation from Raoult’s law.

#Examples:
ethyl alcohol/water
ethyl acetate/alcohol
ethyl alcohol/benzene
# Separation into two pure components is thus
methyl alcohol/choloroform impossible.
# The distillation tends towards the
acetone/CCl4 mixture of minimum b.p.
c) Maximum b.p.:
#M is the azeotropic mixture

#negative deviation from Raoult’s Law

#examples:
Water/hydrogen chloride
pyridine/formic acid
pyridine/acetic acid
pyridine/propinic acid
(i.e. mixtures of an acid and base)
chloroform/ketone
chloroform/ether
chloroform/ester
chloroform/amine
Azeotropic mixture: A mixture which distils without change in composition is
known as an azeotropic mixture.
Azeotrope: Greek work means “boiling without changing”
Liquid-Vapour Phase:
Completely miscible liquid pairs

a2a2/a4 gives one distillation, thus t-c diagram shows a number of distillation by
which A and B can be separated. Distillation for separating two liquids in fraction
may be termed as fractional distillation(see reverse page)
Fractionating column:

Instead of so many individual steps of vaporisation and condensation, a device is

utilized in which only one distillation is carried out with the effect of many
distillations. Such a device is known as a fractionating column which is a very
important modern appliance in many industries.

Mixture of the compounds A+B is heated in a round

bottom flask. Compound A has lower b.p than B. The
vapour will be richer in A. Vapour will reach in plate 1,
some vap will condense on the plate and rest vapour
will pass upward through a whole and reach in plate 2.
This vap is much richer in A. This process shall
continue till the vap phase become pure A. Pure A will
escape by side–tube and can be condensed and
collected in a Container M.
Partially Miscible Liquids:

It is not necessary that one liquid should be H2O: e.g. Phenol/water, amiline/hexane,
CS2/CH3OH (at ordinary temp)
 Liquid-Liquid Phase Diagram(Partially miscible liquids):
(i) Phenol-Water system (ii) Ethyl amine-Water System:

A= unsat. Solution of phenol in H2O

B= unsat. Solution of H2O in phenol
L1= solution is saturated with phenol and layer L2 will form
L2=solution is saturated with H2O and second layer L1 will form
S= If cooled, then at L2 second layer L1 will form
If the homogenous liquid having critical composition C is cooled down form Tc, critical
opalescence will be observed: bluish haze due to scattering of light brought about by local
variation of density within the liquid.
Tuc: Upper critical temperature or upper consulate temperature is the upper limit
of temperature at which phase separation occurs. Above Tuc, the two components
are fully miscible. This temperature exists because the greater thermal motion
leads to greater miscibility of the two component.

Tlc: Lower critical temperature/lower consulate temperature- below which they

mix in all proportions and above which they form two phases. In the case, at low
temperature the two components are more miscible because they form a weak
complex, at higher temperatures the complexes break up and two components are
less miscible.

Phenol-water system:
#At 65 oC and upwards, the two components are completely miscible
in all proportion. This temp is called critical solution temp or
consulate temp(CST)
(iii) Nicotine-Water System:
Some system have both upper and
lower critical temperatures. This is
because after the weak complexes
have been disrupted, leaving to
partial miscibility, the thermal
motion at higher temperatures
homogenizes the mixture again, just
as in the case of ordinary partially
miscible liquids. The most famous
example is nicotine-water, which are
partially miscible between 61 oC and
210 oC.
Immiscible liquid pair:

Pair of liquids (A and B) which are

insoluble in each other.
So, total presure:

Ptot = PAo + Pbo

So, total vap. Pressure is higher than any of
the individual component (A or B). Thus,
the mixture will boil at a lower temp. than
any of the two component (see the fig.):

The mixture boils at a lower temp. than any

of the pure liquid. This property of the
mixture has been used to separate/purify
many organic liquids which are immiscible
with H2O. The method is known as “steam
distillation”.
Apparatus for Steam Distillation: