Vapor Pressure

(a) Initially, no molecules of the liquid in the vapor phase (zero

vapor pressure)
(b) On heating, a liquid phase is formed and vaporization begins.
At equilibrium, no. of molecules leaving the liquid is equal
to the no. of molecules returning to liquid phase. These equal
rate produce stable vapor pressure that does not change as
long as the temperature remains constant

 At any temperature some molecules in a liquid have enough

energy to escape and enter the vapor phase.
As the temperature rises, the fraction of molecules that have
enough energy to escape increases.

 The rate of evaporation is constant at any given temperature.

The rate of condensation increases when concentration of
molecules in vapor phase increases.
A state of dynamic equilibrium ( rate of forward process is
exactly balanced by rate of reverse process ) is reached when
rates of condensation = evaporation.
Therefore, the vapor pressure is the pressure exerted by its
vapor when the liquid and vapor states are in dynamic
equilibrium.

Vapor pressure of solution

The vapor pressure of a solvent above a solution is lower than
the vapor pressure of pure solvent.
-The solute particles replace some of the solvent molecules at the surface.
A concentrated solution will draw pure solvent vapor into it
due to tendency to mix.
Results in reduction in vapor pressure.

Vapor pressure lowering

The vapor pressure of the solution is directly proportional to
the amount of the solvent in the solution.
The difference between the vapor pressure of the pure solvent
and the vapor pressure of solvent in solution is called vapor
pressure lowering.

Raoults Law for non-volatile solute

The vapor pressure of the solvent above a solution containing
a non-volatile solute (a solute that does not have a vapor
pressure of its own) is directly proportional to the mole
fraction of solvent in the solution. This behavior is summed up
in Raoult's Law:
Psolvent = XsolventPosolvent
where:
Psolvent is the vapor pressure of the solvent above the solution,
Xsolvent is the mole fraction of the solvent in the solution
Posolvent is the vapor pressure of the pure solvent.

1) Calculate the vapor pressure of H20 in a solution prepared by

mixing 99.5g of C12H22O11 with 300ml of H2O.
99.5g C12H22O11

300 ml H2O

1 2211
342.30 122211

1.00
1

= 0.2907 mol C12H22O11

1 20
=
18.02 20

16.65 mol H2O

16.65 20
=
0.2907 122211:16.65 2

= 0.9828
PH2O = H2O . PH2O
= 0.9828 23.8 torr
= 23.4 torr #

Raoults Law + Daltons Partial Pressure Law for

volatile solute
A volatile solute (a solute that has a vapor pressure of its own)
will contribute to the vapor pressure above a solution in which
it is dissolved.
The total vapor pressure above a solution will be the sum of
the vapor pressure of solute and solvent.
Psolvent = XsolventPosolvent
Psolute = XsolutePosolute
Ptotal = Psolute + Psolvent

2) Calculate the component and total vapor pressure of a solution

prepared by mixing 3.95g of CS2 with 2.43g of C3H6O.
(Vapor pressure of CS2 = 515 torr, vapor pressure of C3H6O = 332 torr)

3.95g CS2

1 2
= 0.05187 mol
76.15 2

2.43g C3H6O
CS2 =

1 36
58.0 36

CS2

= 0.04184 mol C3H6O

0.05187 2
0.05187 2:0.04184 36

= 0.5535
PCS2 = CS2 . P CS2
= 0.5535 332 torr
= 285 torr

 C3H6O =

0.04184 36
0.05187 2:0.04184 36

= 0.4465
PC3H6O = C3H6O . PC3H6O
= 0.4465 332 torr
= 148 torr
Ptotal = 285 torr + 148 torr
= 443 torr #

Ideal solution
In ideal solution, the made solute-solvent interactions are
equal to the sum of the broken solute-solute and
solvent-solvent interactions
Ideal solutions are those that obey Raoults Law.
Real solutions show approximately ideal behavior when:
The solution concentration is low
The solute and solvent have similarly sized molecules
The solute and solvent have similar types of
intermolecular forces.

Nonideal solution
When solute-solvent interaction are stronger than the solutesolute & solvent-solvent interactions, the total pressure of the
solution will be less than predicted by Raoults Law
When the solute-solvent interaction are weaker than the
solute-solute & solvent-solvent interactions, the total vapor
pressure of the solution will be more than predicted by
Raoults Law