University of Basra

College of Engineering
Chemical Engineering Department
Thermodynamics
The third stage
Dr. Mohammad N. Fares

Phase Equilibrium
 Phase Equilibrium
Definition of terms
•A phase is a quantity of matter characterized by both uniform physical
structure and uniform chemical composition. A phase can be solid, liquid,
vapor or gas.
•Processes such as distillation, absorption, and extraction bring phases of
different composition into contact and when the phases are not in equilibrium,
mass transfer between the phases alters their compositions
•Composition changes are the desired outcome, not only of chemical
reactions, but of a number of industrially important mass-transfer operations
•The extent of change and the rate of transfer depend on the departure of the
system from equilibrium
•For quantitative treatment of mass transfer the equilibrium T, P, and phase
compositions must be known
•The most commonly phases in industrial are vapor and liquid, although
liquid/liquid and liquid/solid systems are also found
 NATURE OF EQUILIBRIUM
Equilibrium is a word denoting a static condition, the absence of change.
In thermodynamics it means not only the absence of change but the absence of any
tendency toward change on the macroscopic properties of a system with time.
An isolated system consisting of liquid and vapor phases in intimate contact
eventually reaches a final state wherein no tendency exists for change to occur
within the system.
The temperature, pressure, and phase compositions reach final values which
thereafter remain fixed
 PHASE RULE.``

A Phase (π):It is a part of a system, uniform throughout in chemical composition and

physical properties, that is separated a uniform component part of the system that is
separated from the other homogeneous parts(e.g. solid, liquid, or gas)
gas by boundary
surface.
For example: If you have some ice floating in water, you have a solid phase present
and a liquid phase. If there is air above the mixture, then that is another phase.
The Degrees of Freedom ( F) is the number of independent intensive
variables (i.e. those that are independent of the quantity of material present) that
need to be specified in value to fully determine the state of the system. Typical
such variables might be temperature T, pressure P, or concentration Ci.

Phase rules gives the number of variables we need in order to determine the
intensive state of a system at equilibrium

F = C –π + 2

Where C is the number of components of the system

 For example: A system with one component

F = 1 –π + 2 =3- π
Case 1: One phase is present (a balloon full of carbon dioxide).

F =3- 1= 2
Two degrees of freedom: temperature and pressure are necessary to define the system and
each one of them can be varied independently.

Case 2: Two phases are present (liquid and vapor):

F =3- 2= 1
Temperature or pressure (one variable) is necessary to define the system.
Case 3: Three phases are present (solid, liquid and vapor ):

F =3- 3= 0
The system is invariant and is represented by a point in a plot of phase diagram
( T – P ), where the pressure and temperature are fixed by the equilibrium.
 Phase diagrams.
Graphical method to describe the effects of pressure and temperature on the phase of a
substance. A phase diagram shows exactly what phases are present at any given
temperature and pressure.
The phases will simply be the solid, liquid or vapor (gas) states of a pure substance. This
phase diagram is characterized by area, line and triple point.
Area: it represents a one phase (F = 2), where the two variables T and P are necessary
to define, like areas of solid, liquid, and vapor.

Line: it represents two phases (F = 1) in equilibrium. The system can be completely

define by T or P.

Triple point (T): it represents three phases (F = 0) in equilibrium. The system can
be completely define by T or P. It is only one point in the diagram.
If T or P change, the two phase will dissappear.

An aerosol is a suspension of tiny particles of liquid, solid, or both within a gas.

 Definition of Terms
1- Vapor: A substance that is below its critical temperature. which means that the
vapor can be condensed to a liquid by increasing the pressure on it without reducing
the temperature.

2-Gas : A substance that is above its critical temperature (but below the critical
pressure). For the same pressure, a vapor is more easily condensed while a gas is
normally non-condensable.

3- Boiling/bubble point Tbp: temperature at which the average liquid molecule has just
enough kinetic energy to escape from the surface of the liquid into the gas phase.

4-Dew point Tdp:temperature at which the average vapor molecule has just enough
kinetic energy to condense.

5-Saturated Temperature: Temperature at which the vapor and liquid will co-exist at a
given pressure. Commonly referred to as the boiling or condensation point.
6-Saturated liquid: a liquid at its boiling/bubble point (In thermodynamics a liquid
that is on the edge to start vaporizing is said to be saturated, i.e. a liquid that will start to
vaporize if more energy is added.)
7- Saturated vapor and Superheated vapor:
If a substance exists entirely as vapor at the saturation temperature, it is called a
saturated vapor. When the vapor is at a temperature greater than the saturation
temperature, it is said to exist as superheated vapor.

8-Vapor pressure: pressure at which the liquid and vapor phase are in equilibrium at a
given temperature

9-Subcooled liquid: The term subcooling also called undercooling refers to a liquid
existing at a temperature below its normal boiling point.

10-Azeotrope: a constant-boiling mixture, i.e., a mixture that behaves like a single

component.
 Dew point and Bubble point Calculations with Raoult's Law

Raoult’s Law for ideal phase behavior relates the composition of liquid and vapor
phases at equilibrium through the component vapor pressure, Pisat.

or

Where
xi is a liquid phase mole fraction,
yi is a vapor phase mole fraction,
Pisat is the vapor pressure of pure species i.

The product yi P is known as the partial pressure of species i.

Notes

•If experimental data are not available, estimation of VLE can still be done.
•The simplest method assumes ideal vapor and ideal liquid phases.
•It is not very accurate for some mixtures, but is a good first approximation.

•The Raoult’s law, simple model for VLE, provides a realistic description of actual
behavior for a relatively small class of systems.
•Nevertheless, it is useful for displaying VLE calculations in their simplest form, and it
also serves as a standard of comparison for more complex systems.
•A limitation of Raoult’s law is that it can be applied only to species of known vapor
pressure, and this requires the species to be “subcritical” i.e., to be at a temperature
below its critical temperature.
•Raoult's Law can be applied to each component that distributes between the two
phases in the system.
•For example, if we have a binary mixture of A and B, then we can write Raoult's Law
for both components.
•If we do that and then add the two equations together, we obtain a convenient
relationship between the liquid mole fractions and the total pressure:

Engineering interest centers on dew point and bubble point calculations; there
are four classes:
 1-For bubble point calculations

For a binary system:

2-For dew point calculations

The calculations revolve around the use of two key equations:

1-Raoult’s law for ideal phase behavior: ….(1)

2-Antoine’s Equation ….(2)

 1- BUBL P Calculation (T, xi known).

Calculate P1sat and P2sat from Antoine’s Eq. (2).

•For the vapour-phase composition ( bubble ) we can write:

….(3)

•Substitute y1 and y2 in Eq. (3) by using Raoult’s law:

….(4)

Re-arrange and solve Eq.(4) for P

- Now you can obtain y1 from Eq.(1)

- Finally, y2 = 1 - y1
 2- DEW P Calculation (T, y1 known).

•Calculate P1sat and P2sat from Antoine’s Equation

•For the liquid-phase composition (dew) we can write:

….(5)

Substitute x1 and x2 in Eq. (6) by using Raoult’s law:

….(6)

Re-arrange and solve Eq. (6) for P

- Now you can obtain x1 from Eq.

- Finally, x2 = 1 - x1
 3-BUBL T Calculation (P, x1 known).

•Since T is an unknown, the saturation pressures for the mixture components cannot
be calculated directly. Therefore, calculation of T, y1 requires an iterative approach,
as follows:

•Re-arrange Antoine’s equation so that the saturation temperatures of the components at

pressure P can be calculated:

….(7)

•Select a temperature T’ so that T1sat < T’ < T2sat

•Calculate P1sat(T’) and P2sat(T’)

•Solve Eq. (4) for pressure P’
•If ǀ P- P’ ǀ < ε , then P’ = P ; If not, try another T’-value
•Calculate y1 from Raoult’s law
 4- DEW T Calculation (P, y1 known).

•Same as before, calculation of T , x1 requires an iterative approach:

•Re-arrange Antoine’s equation so that the saturation temperatures of the components at

pressure P can be calculated from Eqn. (7)

….(7)

•Select a temperature T’ so that T1sat < T’ < T2sat

•Calculate P1sat(T’) and P2sat(T’) from Antoine’s Eq.

•Solve Eq. (6) for pressure P’

•If ǀ P- P’ ǀ < ε , then P’ = P ; If not, try another T’-value

•Calculate x1 from Raoult’s law.

 Example 1

With the numerical values for mole fractions and pressure, equation (E-2) becomes
Example 2
Example 3
Example 4
Example 5
 Flash distillation.
Flash distillation is a single stage separation technique.

A liquid mixture feed is pumped through a heater to raise the temperature and enthalpy of
the mixture.
It then flows through a valve and the pressure is reduced, causing the liquid to partially
vaporize.
Once the mixture enters a big enough volume the liquid and vapor separate.
 VLE FROM K-VALUE CORRELATIONS

K -value measure the tendency of species to favor the vapor phase.

Ki > 1 Species I exhibit a higher concentration in the vapor phase.

Ki < 1 Species I exhibit a higher concentration in the liquid phase.

Allowing elimination of one set of mole fractions x or y, two types of calculations

result:

Bubble point calculation: and then

Find the set of K-values that satisfies equation above

Dew point calculation: and then

Find the set of K-values that satisfies equation above

Figures 1 and 2 show monographs for the k-values of light hydrocarbons as function of T and P