Scribd
Upload
21 views18 pages

Lecture - 26 - Phase Equilibrium

The document discusses phase equilibria and vapor pressure. It defines a phase as a region of uniform properties and describes dynamic equilibrium between vapor and liquid phases. Vapour pressure is defined as the pressure exerted by a vapor in equilibrium with its liquid. Raoult's law states that vapor pressure of a solution is equal to vapor pressure of the pure solvent times its mole fraction. Ideal mixtures obey Raoult's law while non-ideal mixtures can show positive or negative deviations.

Uploaded by

Kezia Jeffrey 11 Science
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
21 views18 pages

Lecture - 26 - Phase Equilibrium

The document discusses phase equilibria and vapor pressure. It defines a phase as a region of uniform properties and describes dynamic equilibrium between vapor and liquid phases. Vapour pressure is defined as the pressure exerted by a vapor in equilibrium with its liquid. Raoult's law states that vapor pressure of a solution is equal to vapor pressure of the pure solvent times its mole fraction. Ideal mixtures obey Raoult's law while non-ideal mixtures can show positive or negative deviations.

Uploaded by

Kezia Jeffrey 11 Science
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 18

Module G: Phase

Equilibria
Phase
• A phase is a region of space throughout which all
physical properties of a material are essentially
uniform.

• The term phase is sometimes used as a synonym for state of


matter.
Phase Equilibrium

• In all cases we will find that the rate of passage from one phase
to another depends on:

1. The surface area of contact between the two phases


2. The concentration of substance in the phase of origin.
Phase Equilibrium
• Evaporation only takes place on the surface of the liquid.

• In a closed container there is constant evaporation from the


surface.
• Particles continue to break away from the surface of the liquid
– but are trapped in the space above the liquid.

4
Phase Equilibrium
• As the gaseous particles bounce around, some of them will hit
the surface of the liquid again, and be trapped there.

• Hence, there is an equilibrium set up in which the number of


particles leaving the surface is equal to the number of
particles returning to the surface.

5
Vapour Pressure
• In this equilibrium, there will be a fixed number of the
gaseous particles in the space above the liquid.

• When these particles hit the walls of the container, they


exert a pressure.

• The pressure exerted by a vapour in dynamic equilibrium


with its liquid is called the vapour pressure.
• Liquids with high vapour pressures at room temperature are said to
be volatile, and those with very low vapour pressures are non-
volatile

6
Vapour Pressure and Boiling Point
• The boiling point of a liquid is the temperature at
which its vapour pressure is equal to the pressure
of the gas above it.

• The normal boiling point of a liquid is the


temperature at which its vapour pressure is equal
to one atmosphere (760 mm Hg/torr).

• The higher the vapour pressure of a liquid, the


lower will be its boiling point.
7
8
Vapour Pressure and Boiling Point
• Liquids with a high vapour pressure indicate that there is a
high concentration of molecules leaving the surface of the
liquid and entering the vapour phase.

• If the molecules are escaping easily from the surface, it must


mean that the intermolecular forces are relatively weak.

• So a small amount of heat is required to break them


completely and boil the liquid.

• Thus, the liquid has a low boiling point.


Review: Raoult’s Law
• The vapour pressure of a solution of a non-volatile solute is
equal to the vapour pressure of the pure solvent at that
temperature multiplied by its mole fraction.

• is the vapour pressure of the pure solvent at a particular


temperature.
• is the mole fraction of the solvent, i.e. the fraction of the total
number of moles of solvent present.

10
Raoult’s Law & Binary Mixtures
• Ideal mixtures
• An ideal mixture is one which obeys Raoult's Law.

• Intermolecular forces before and after mixing are approximately


the same.
• Examples of ideal mixtures
• There is actually no such thing as an ideal mixture! However,
some liquid mixtures get fairly close to being ideal.
• Hexane and heptane
• Benzene and methylbenzene
11
• propan-1-ol and propan-2-ol
Raoult’s Law & Binary Mixtures
• In a pure liquid, the more energetic molecules have enough
energy to overcome intermolecular attractions and escape
from the surface to form a vapour.

• If you have a second liquid, the same thing is true. At any


particular temperature a certain proportion of the molecules
will have enough energy to leave the surface.

12
Raoult’s Law & Binary Mixtures
• In an ideal mixture of these two liquids, the tendency of the
two different molecules to escape is unchanged.

• This is why mixtures like hexane and heptane get close to


ideal behaviour.
• They are similarly sized molecules and so have similarly sized van
der Waals attractions between them.

13
Raoult’s Law & Binary Mixtures
• Hence Raoult’s Law as applied to a mixture of two
volatile liquids is:

• The partial vapour pressure of a component in a


mixture is equal to the vapour pressure of the pure
component at that temperature multiplied by its mole
fraction in the mixture.

• Raoult's Law only works for ideal mixtures.

14
Raoult’s Law & Binary Mixtures
• In equation form, the total vapour pressure of the mixture is:

• Where and are the partial vapour pressures of the


components A and B.

• In equation form, the partial vapour pressures of the


components A and B reads:

15
Vapour Composition of a Binary
Mixture
• If you boil a liquid mixture, you would expect to find that
the more volatile substance escapes to form a vapour more
easily than the less volatile one.

• You can discover this composition by condensing the


vapour and analysing it.
Boiling Point Composition Diagrams
The diagram shows that the vapour over the surface of the
boiling liquid has a composition which is much richer in B -
the more volatile component.
Deviations from Raoult’s Law in Non-ideal
Mixtures
• In mixtures showing a
positive deviation from
Raoult's Law, the vapour
pressure of the mixture is
always higher than you
would expect from an ideal
mixture.

• You can also have mixtures


with vapour pressures
which are less than would
be expected by Raoult's
Law. These are negative
deviations. 18

You might also like