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INTRODUCTION TO CHEMICAL ENGINEERING

VAPOUR/LIQUID EQUILIBRIUM

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EQUILIBRIUM/VAPOUR PRESSURE

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 PHASE DIAGRAMS
• The properties of compounds can
conveniently be displayed via phase
diagrams.

• Phase diagrams enable one to view

the properties of two or more phases
as functions of temperature,
pressure, specific volume,
concentration, and other variables.

• Phase diagrams will be discussed in4

terms of water.
Experiment to demonstrate phase diagram

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Fig 8.1 Apparatus used to explore the p, V, and T properties of water.
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Figure 8.2 Results of an experiment in heating a fixed amount of a
pure compound in a closed vessel (a constant volume) as shown on a 7
phase diagram of p versus T at constant V.
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Phase Diagram in 3D
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Representing the quality of a wet steam on a diagram

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• Difference between the terms gas and
vapour.

• A gas that exists below its critical

temperature is usually called a vapour
because it can condense.

• Gas or non-condensable gas describes

a gas above the critical point.

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Fig. 1: Various common processes as represented on a p*-T 13

diagram
Quiz

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• If the vapour and liquid of a pure
component are in equilibrium, then
the equilibrium pressure is called the
vapour pressure. This is usually
denoted by p*.
• At a given temperature, there is only
one pressure a which the liquid and
vapour phases of a pure substance
may exist in equilibrium.
• Either phase alone may exist, of
course, over a wide range of
conditions. 15
EQUILIBRIUM

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 Definition of terminologies
– Boiling
– Bubble point
– Condensation
– Dew point
– Evaporation
– Freezing (solidifying)
– Melting (fusion)
– Melting curve
– Normal boiling point
– Normal melting point
– Saturated liquid/saturated vapour
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– subcooled liquid
– sublimation
– Sublimation curve
– sublimation pressure
– Supercritical pressure
– Superheated vapour
– Two-phase region
– Vaporization

• At the top of mount Kenya, how does boiling

take place ?
• A pure conpound can change at constant
volume from a liquid to a vapour, or the
reverse, via a constant temperature process as
well as a constant pressure process.
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Gibbs phase rule for nonreactive systems. If chemical
reactions occur in the system, at equilibrium each
independent reaction contributes another independent
constraint; thus, if there are r reactions the DF are further
reduced by r.

The Gibbs Phase Rule is useful for understanding how

many intensive variables must be specified to fully fix, for
example, the composition of phases and streams in a
process. Applications of it are encountered in chemical
engineering separation operations including distillation,
absorption/stripping, liquid-liquid extraction, and
crystallization (Aside: what phases are contacted in
each of these processes?).
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 Example
How many degrees of freedom exist for each of the
following scenarios? What intensive variables could be
specified to completely determine the intensive state of
the system?

(i). Pure liquid water.

(ii) A mixture of liquid, solid, and water vapor of the same

species (c = 1).

(iii) A vapor-liquid mixture of acetone and methyl ethyl

ketone.
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• The change that occurs at H is the
increase or decrease in the fraction
of vapour or liquid, respectively, at
the fixed temperature. The pressure
does not change until all of the
vapour, or liquid, has completed the
phase transition.

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