CME2122: Separation Processes 1

Phase Equilibria & Separations

Dr Chun-Yang Yin, AMIChemE, MIEAust, FHEA

Senior Lecturer
Newcastle University International Singapore
 Introduction
Phase equilibrium relationships mass transfer between
phases contact-equilibrium processes).

Phase equilibrium thermodynamic state established

between two (or more) phases.

Multiple component system, at equilibrium, the

concentrations of all components in each phase no longer
change, and the distribution of components in the two phases
is completed and will be maintained.

The equilibrium state (and concentrations) may change with

temperature, pressure and composition.
http://www.polyu.edu.hk/edc/tdg/userfiles/file/490Q_ABCT/ICBPT_cht3Sep.pdf
 Equilibrium stage separations
Example: Distillation columns

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 Distillation

Distillation is a method of separating mixtures based on

differences in volatilities of components in a boiling liquid
mixture.

Distillation exploits the fact that different components have

different vapours pressures at a given temperature.

Or in its simplest form different chemicals have different

boiling points
 Rate controlled separations
Example: Gas Absorption, Stripping

Gomes, J. Sequestrao de CO2Uma Viso Integrada das Tecnologias Qumicas Disponveis. Habilitation,
Thesis, Universidade Tcnica de Lisboa, Lisboa, Portugal, 2010
 Phase rule
Gibbs phase rule:
F CP2
where
F is the degrees of freedom
C is the number of components
P is the number of phases
It is used to establish the number of independent ,intensive variables
such as T, P and concentration (as defined by degrees of freedom, F)
which must be fixed to completely define the system at phase
equilibrium related to design.
Phase diagrams can be used for this purpose
 Phase rule
Phase rule example:

CO2 air water

2 phases and 3 components

F = 3 2 + 2 = 3 (3 degrees of freedom)

This means if total P and T are fixed (eg. design spec requirement/limit),
only 1 variable is left that can be randomly set.
 Phase Diagram for a Pure Compound

Pure compound: C=1

Regions represent single phase - either
solid, liquid or vapour.
F=1 -1+2=2 i.e. need two
independent variables to specify the
system e.g. T and P in this case.
Lines conditions at which 2 phases co
-exist in equilibrium.
F=1 -2+2=1 i.e. need 1 variable to
specify system (2nd variable is
automatically fixed by the
equilibrium line).
At triple point, all 3 phases co exist.
F= 1 -3+2=0 (unique T, P at which
Licensed by creative commons - MIT
this occurs).
OpenCourseWare
Beyond the critical point, liquid and
vapour are indistinguishable.
 Distillation fundamentals
Distillation difference in composition between
the vapour and liquid phases when we boil the
mixture
In order to exploit this difference need to
understand the relationship between P and T and
vapour and liquid compositions of a given mixture
at equilibrium,
I.e. P, T, x ( liquid mole fraction), y Vapour mole
fraction.
We start from an explanation of vaporisation.

(Adapted from Russell, 2016)

 Mass fraction vs mol fraction
All solutions for distillation work with mol fractions.
Often you are given compositions as mass fractions.
You need to be able to convert between the two.

Question: A solution of ethanol in water contains 30% of ethanol by weight. Calculate

the mole fractions of ethanol and water in the solution. (Answers = 0.144, 0.856)

Molecular weight of ethanol, C2H5OH, is 46 and the molecular weight of water, H2O,
is 18.
Since, in 100 kg of the mixture there are 30 kg of ethanol and 70 kg of water,

mole fraction of ethanol = (30/46) / [(30/46 + (70/18)]

= 0.144
mole fraction of water = (70/18) / [(30/46 + (70/18)]
= 0.856
= (1 - 0.144)
(Adapted from Earle and Earle, 1983; Russell, 2016)
 Vaporisation
To understand distillation we first need to under stand vaporisation.
Molecules can move around randomly in a liquid but they are bound
together by loose forces of attraction that restrict their movement.
At the surface of the liquid some molecules can escape and enter the
vapour phase where they bombard the walls of the vessel.
The force of these molecules hitting the walls exerts pressure on vessel.
As the temperature rises the number of molecules leaving the liquid rises
and so does the pressure.
Eventually the numbers of molecules leaving the liquid matches the
number falling back and an equilibrium established.
The pressure exerted under these conditions is known variously as
Pure liquid vapour pressure
saturated vapour pressure
equilibrium vapour pressure
(Adapted from Russell, 2016)
 Antoine equation
The saturated vapour pressures of pure substance
calculated from the Antoine equation.

Antoine equation constants can be found in literatures.

Example:
www.eng.auburn.edu/~drmills/mans486/Diffusion%20Tube/A
ntoine_coefficient_table.PDF

Be careful of the units of the parameters!

 Vapour Pressures Correlation
Example: water

Derive the relationship (curve) between vapour pressure PVP (mm

Hg) with temperature T (K) using Antoines equation if the
constants for water are as follows: A=18.3036; B=3816.44; C= -
46.13. 1 bar = 750.062 mm Hg. Use the following temperature
range (379 573 K).

You can use the derived PVP vs. T chart to determine the phase(s)
that will exist under given operating conditions of P and T.

Compare your curve with the following database:

http://webbook.nist.gov/cgi/cbook.cgi?ID=C7732185&Mask=4&Type=ANTOINE&Plot=on
Daltons law of partial pressure

(Adapted from Russell, 2016)

Raoults law

(Adapted from Russell, 2016)

 Boiling Point diagram

Imagine mixture of A and B is heated in a

closed vessel while pressure remains
atmospheric.

Vapor-liquid equilibrium (VLE) relations

for binary mixture A and B boiling
point diagram

Upper line saturated vapour line (dew

point)

Lower line saturated liquid line

(bubble point)

2-phase region between the two lines

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http://www.chem1.com/
 Equilibrium (x-y) diagram

Licensed by Creative Commmons

(Mandagarn and Campanella, 2006)

45 line is used as benchmark to determine which is the richer component

See interactive simulation:

http://www.colorado.edu/learncheme/separations/PxyTxyDiagramsVLE.html
 Boiling point diagram x-y diagram
How do you create a x-y diagram from a boiling point diagram
for a similar system?

Where would you get equilibrium data from? Literature?

Discuss.
Equilibrium (x-y) diagram
Equilibrium (x-y) diagram
 Equilibrium (x-y) diagram
For Y (vapour Phase composition)
from Daltons law
PA y A PT
From Raoults Law
PA x A PA*
Substitution:
x A PA* y A PT
re-arranging:
PA*
yA xA
PT
 Example 1
The following table shows the vapor-pressure and equilibrium data for benzene-toluene
system (Christie, 1993). By using a graph paper, construct a equilibrium diagram for
benzene-toluene. Also, determine the vapor and liquid compositions in equilibrium at 95C
for benzene-toluene using vapor pressure at 101.32 kPa. (Answers = 0.411, 0.589, 0.632)
Relative volatility
 Relative volatility from vapour pressures
The relative volatility of the mixture can also be
calculated from the vapour pressures
 Non-ideal systems
Thus far simple cases of ideal systems.
Most real systems are non-ideal and assuming ideal behaviour can
only be used for initial design
Phase equilibria for these non-ideal systems will require a more
complex treatment it will either be measured or predicted using
Equations of state
Activity coefficient models eg UNIFAC
These will not be discussed further in this module though you
may encounter them in other modules. You should however be
able to recognise their behaviour.

(Adapted from Russell, 2016)

 Positive deviations from ideality

If total pressure of mixture is higher than that predicted by Raoults

law then the mixture is said to show positive deviations from
ideality.

If the deviation is large and the vapour pressures of each

component are similar bubble and dew points might meet.

If this happens, we will have a constant boiling mixture

(azeotrope) which limits the separation that can be achieved.
 Negative deviations from ideality
If the total pressure of a mixture is lower than that predicted by
Raoults law negative deviations from ideality

If the deviation is large and the vapour pressures of each

component are similar bubble and dew points might meet.

If this happens, we will have a constant boiling mixture (azeotrope)

which limits the separation that can be achieved.
 Azeotrope benzene (C6H6)/ethanol (C2H5OH) mixture

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See interactive simulation:
http://www.colorado.edu/learncheme/separations/VLEDiagramNonIdealMixture.html
 VLE - video
https://www.youtube.com/watch?v=XNLOo2RDhj0

Which component has higher vapour pressure / lower boiling

point?
 References
Earle, R. L. and Earle, M.D. (1983). Unit operations in food
processing. The New Zealand Institute of Food Science &
Technology
Russell, P. (2016). Lecture notes for CBE2034: Process
Operations and Particulates, Teesside University, UK.
Christie, J.G., 1993. Transport Processes and Unit Operations.
Prentice-Hall International, Inc, pp.393-397.
Dr. Nasir Al-Lagtah (some contribution of lecture notes)