ChE 421

Sir Bossing
Phase Equilibria

 Equilibrium is “state of balance”. The rate of transfer of matter or heat from

one phase to the other is equal to the rate of transfer in the reverse direction
at equilibrium.
 The driving forces causing material or heat transfer are balanced at
equilibrium.
 Stability of configuration w/ lowest free energy (internal energy of a system and
also randomness or disorder of the atoms or molecules (entropy))
 Any change in temperature, pressure and composition cause an increase in free
energy and away from equilibrium thus forcing a move to another state.
 Also called as equilibrium or constitutional diagrams

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Phase Equilibria

 Phase – homogeneous portion of a system that has uniform physical and

chemical characteristics.
Types of phase:
Gaseous phase –occurs only in one phase (normally, gases always mix)
Liquid phase – often occurs in one phase. Two immiscible liquids are considered
as 2 phase. Ex. Salt water
Solid phase
Crystalline phase: ZnO and SiO2
Polymorphs: wurtzite and sphalerite ZnS are different phases

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Phase Diagram

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Phase Diagram

 • Triple point – the point on a phase diagram at which the three states of
matter: gas, liquid, and solid coexist
 • Critical point – the point on a phase diagram at which the substance is
indistinguishable between liquid and gaseous states
 • Fusion(melting) (or freezing) curve – the curve on a phase diagram
which represents the transition between liquid and solid states

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Equilibrium

 A state of condition of balance or constancy

 A condition wherein the maximum possible composition is reached given the
set of conditions
 Also termed as “saturated conditions”

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Applications of the Equilibrium Concept to
Vapor-Liquid Equilibrium Criteria

 For Equilibrium condition:

 Constant Operating Conditions
 There are no changes in temperature and pressure

 Constant Saturated Conditions

 The composition of the components does not anymore change

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Equilibrium Constant, Ki

 The ratio of the mole fraction in the vapor to the mole fraction in the liquid.
Yi
Ki =
Xi
 Ideal Stage
 It refers to the contact stage or a medium which means that the resulting products
are in saturated condition or the maximum composition.

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Evaluation of Ki
Ideal systems
For ideal solutions (liquids):
The Raoult’s law applies: Pi = Pi°Xi
Where: Pi = partial pressure
Pi° = vapor pressure
Xi = mole fraction in liquid
Recall that vapor pressure Pi is usually evaluated through the use of Antoine’s
equation:
Log Pi° = Ai – Bi/ (Ci + T)
where: Pi° = vapor pressure in Torrs

A,B,C = constants (Appendix E)

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T = temperature in °C
Evaluation of Ki
For Ideal Gas Mixture:
The Ideal Gas Law applies: PV = nRT

For the mixture: PV = niRT equation 1

For component i in the mixture: cV = niRT equation 2

Dividing equation 2 by 1
Pi ni
= = Yi equation A
P n

Combining Raoult’s Law with equation A

Pi °Xi
Yi =
Pi
Therefore,
𝐘𝐘𝐢𝐢 𝐏𝐏𝐢𝐢 °
𝐊𝐊 𝐢𝐢 = =
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𝐗𝐗 𝐢𝐢 𝐏𝐏
Evaluation of Ki
2. From Experimental Data for Hydrocarbons
a. De Priester Chart
b. De Priester Equation – Appendix D

Note: Applicable only for operating pressures of 50, 100, 150, 250 psia

De Priester Equation:
K = a + b (T/100) + c (T/100)2 + d (T/100)3

Where: K = equilibrium constant

T = temperature in °F
a, b,C. c,
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Jr.= constants dependent on P
Exercises:

Find Ki for the following cases:

a. Benzene and Toluene
- at 1 atm and 50 °C (ideal system)

b. n-octane and n-pentane at 80 °C and

b.1 at 1 atm (as an ideal system and using the chart)
b.2 at 100 psia

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Gas Equilibrium
PA PA PA °
XA = YA = YA = XA
PA ° PT PT

Vapor Pressure Data (Table 2-7 Handbook) or Appendix C-1

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Sample Problem:

1. A liquid phase contains 30% mole C6H6 and 70% mole C7H8 at 40 °C
a. Calculate the composition of the vapor phase in equilibrium of the liquid
b. Calculate the total pressure of the liquid phase

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Sample Problem:

2. The vapour pressure of n-heptane and toluene at 373 K are 106 and 73.7 kPa.
What are the mole fraction of n-heptane in the vapour and in the liquid phase at
373 K if the total pressure is 101.3 kPa?

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Henry’s Law

Henry’s Law
PA=HXA
H- Henry’s constant (Appendix B)

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Sample Problem:

Calculate the composition of the liquid and gas phase for a mixture of air and
liquid H2O at 68 °F and 760 mmHg

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Volatility
PA ° YA YB
YA = XA KA = ; KB =
PT XA XB

YA = K A XA
Relative Volatility
YA
KA �X Y X
𝛂𝛂𝐀𝐀𝐀𝐀 = = YB A
= YA X B
KB �X B A
B

For Binary System

YA (1−XA )
𝛂𝛂𝐀𝐀𝐀𝐀 =
XA (1−YA )

Assuming it follows Raoult’s Law

PA °
𝛂𝛂𝐀𝐀𝐀𝐀 =
PB °
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Sample Problem:

What is the relative volatility of n-heptane and n-octane at 20 psia and 80 °F?

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Boiling Point Concentration Diagram

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Boiling-point diagram for system benzene (A)-
toluene (B) at a total pressure of 101.32 kPa.

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Boiling-Point Diagrams and xy Plots

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Sample Problem. Use of Raoult’s Law for
Boiling-Point Diagram
 Calculate the vapor and liquid compositions in equilibrium at 95ºC (368.2K)
for benzene-toluene using the vapor pressure from the table 11.1-1 at 101.32
kPa.

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Rodolfo C. Sotto Jr.
A common method of plotting the equilibrium data is shown in figure
below where yA is plotted versus xA for the benzene-toluene system. The
45º line is given to show that yA is richer in component A than is xA.

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Vapor-Liquid Equilibrium Relations

An azeotrope is a mixture of two or more liquids in such a ratio that its

composition cannot be changed by simple distillation.

This occurs because, when an azeotrope is boiled, the resulting vapor has the
same ratio of constituents as the original mixture.
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Single-Stage Equilibrium Contact for
Vapor-Liquid System

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Sample Problem. Equilibrium Contact of
Vapor-Liquid Mixture
 A vapor at the dew point and 101.32 kPa containing a mole fraction of 0.40
benzene (A) and 0.60 toluene (B) and 100 kg mol total is contacted with 110
kg mol of a liquid at the boiling point containing a mole fraction of 0.30
benzene and 0.70 toluene. The two streams are contacted in a single stage,
and the outlet streams leave in equilibrium with each other. Assume constant
molal overflow. Calculate the amounts and compositions of the exit streams.

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Solution

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Rodolfo C. Sotto Jr.
Sample Problem:

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