Phase Equilibria

Learning Objectives

◉ To explain what equilibrium is and learn about phase

diagrams.
◉ To use the Gibbs phase rule to determine the number
of degrees of freedom for a separation process.
◉ To define relative volatility between two components
of a vapor-liquid mixture.
◉ To solve problems using vapor-liquid equilibrium
relations.
2
1. Phase Diagrams and Phase Rule

3
 Equilibrium

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

4
 Phase

◉ Defined as any homogeneous portion of a system

that has uniform physical and chemical
characteristics.
◉ For example, ice, water, and water vapor are three
separate phases, each is physically distinct and there
are definite boundaries between them.

5
 Types of Phase

◉ Gaseous phase – occurs only in one phase

◉ Liquid phase – often occurs in one phase
◉ Solid phase – crystalline phase, polymorphs

6
 Phase Diagram

◉ A graphical representation which

details the form(s) the material
takes under specific conditions.
◉ Phase diagrams illustrate the
variations between the states of
matter of elements or compounds
as they relate to pressure and
temperatures.

7
 Phase Diagram

◉ Triple Point – the point on a phase

diagram at which the three states
coexist
◉ Critical Point – the point on a phase
diagram at which the substance is
indistinguishable between liquid
and gaseous states

8
 Phase Diagram

◉ Fusion curve – the curve on a phase

diagram which represents the
transition between liquid and solid
states
◉ Vaporization curve – the curve on a
phase diagram which represents the
transition between gaseous and liquid
states
◉ Sublimation curve – the curve on a
phase diagram which represents the
transition between gaseous and solid
states
9
 Gibbs Phase Rule

◉ Predicts the number of phases that will

coexist within a system at equilibrium.
◉ It does not apply in non-equilibrium situations.
𝑭= 𝑪−𝑷+𝑵
Where,
F – number of degrees of freedom; number of
externally controllable variables (e.g. T, P, and
composition of a phase) which can be changed
independently without altering the number and
kinds of phases which coexist at equilibrium.
10
 Gibbs Phase Rule

𝑭=𝑪−𝑷+𝑵
Where,
C – number of components present
P – number of phases present
N – number of non-compositional variables

*𝑵 = 𝟏 𝑜𝑟 𝟐 for temperature (T) and pressure (P)

11
 Gibbs Phase Rule

Example:
How many phase-rule variables must be specified to fix the
thermodynamic state of an aqueous solution of ethanol in
equilibrium with its vapor?

𝑃=2 𝐹 = 2−2+2
𝐶=2 𝑭=𝟐
𝑁=2

12
 Gibbs Phase Rule

𝑭=𝑪−𝑷+𝑵
A
Where,
𝑃=1
𝐶=2
𝑁=1
𝐹 =2−1+1
𝑭=𝟐

13
 Gibbs Phase Rule

𝑭=𝑪−𝑷+𝑵
Where,
B 𝑃=2
𝐶=2
𝑁=1
𝐹 =2−2+1
𝑭=𝟏

14
 Gibbs Phase Rule

𝑭=𝑪−𝑷+𝑵
Where,
𝑃=3
C
𝐶=2
𝑁=1
𝐹 =2−3+1
𝑭=𝟎

15
 Phase Equilibria

◉ Many processes in chemical engineering do not only

involve a single phase but a combination of two
immiscible liquids, or a stream containing both gas
and liquid.
◉ There are three important criteria for different phases
to be in equilibrium with each other: temperature,
partial pressure, and Gibbs free energy (or chemical
potential)
16
2. V a p o r - Liquid Equilibrium Relations

17
 Va por - Liquid Equilibrium Relations

For equilibrium condition:

◉ Constant Operating Conditions
- There are no changes in temperature and
pressure.
◉ Constant Saturated Conditions
- The composition of the components does not
change anymore.

18
 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.

For a given system:

𝑋𝑖 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖 𝑖𝑛 𝑡ℎ𝑒 𝑙𝑖𝑞𝑢𝑖𝑑
𝑌𝑖 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑖 𝑖𝑛 𝑡ℎ𝑒 𝑣𝑎𝑝𝑜𝑟

19
 Equilibrium Constant, 𝐾𝑖

◉ The ratio of the mole fraction in the vapor to the mole

fraction in the liquid.

𝒀𝒊
𝑲𝒊 =
𝑿𝒊

20
 Evaluation of 𝐾𝑖 for Ideal Systems

A. For ideal solutions (liquids)

◉ Raoult’s Law
𝑷𝒊 = 𝑷𝒊𝒐𝑿𝒊
Where,
𝑷𝒊 = 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑷𝒊𝒐 = 𝑣𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑿𝒊 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑖𝑛 𝑙𝑖𝑞𝑢𝑖𝑑
21
 Evaluation of 𝐾𝑖 for Ideal Systems

A. For ideal solutions (liquids)

◉ Antoine’s Equation

𝒍𝒐𝒈 𝑷𝒊𝒐 = 𝑨𝒊 − 𝑩𝒊
𝑪𝒊+𝑻
Where,
𝑷𝒊𝒐 = 𝑣𝑎𝑝𝑜𝑟 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 𝑖𝑛 𝑚𝑚𝐻𝑔
𝑨, 𝑩, 𝑪 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠
𝑻 = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑛 ℃ 22
 Evaluation of 𝐾𝑖 for Ideal Systems

B. For ideal gas mixtures

◉ Ideal Gas Equation
𝑷𝑽 = 𝒏𝑹𝑻
For component 𝒊 in the mixture: 𝑃𝑖𝑉 = 𝑛𝑖𝑅𝑇
𝑃𝑖 𝑛𝑖
Dividing the two equations: = = 𝑌𝑖
𝑃 𝑛
𝑃𝑖 𝑜 𝑋 𝑖
Combining with Raoult’s Law: 𝑌𝑖 =
𝑃
𝒀𝒊 𝑷𝒊 𝒐
Therefore, 𝑲 𝒊 = =
𝑿𝒊 𝑷
23
 Evaluation of 𝐾𝑖

From Experimental Data for Hydrocarbons

◉ De Priester Chart
◉ De Priester Equation (applicable only for operating
pressures of 50, 100, 150, 250 𝑝𝑠𝑖𝑎
𝟐
𝑻 𝑻 𝑻 𝟑
𝑲=𝒂+𝒃 +𝒄 +𝒅
𝟏𝟎𝟎 𝟏𝟎𝟎 𝟏𝟎𝟎
Where,
𝑻 = 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 𝑖𝑛 ℉
𝒂, 𝒃, 𝒄, 𝒅 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡𝑠 𝑑𝑒𝑝𝑒𝑛𝑑𝑒𝑛𝑡 𝑜𝑛 𝑃
24
 Evaluation of 𝐾𝑖

Example 1.1
Find 𝐾𝑖 for the following cases:
a.Benzene and Toluene at 1 𝑎𝑡𝑚 and 50℃ (ideal system)
b.n-octane and n-pentane at 80℃ and
1. at 1 𝑎𝑡𝑚 (as an ideal system)
2. at 100 𝑝𝑠𝑖𝑎

25
Evaluation of 𝐾𝑖

26
 Evaluation of 𝐾𝑖

Solution:
a.1 For benzene (1 𝑎𝑡𝑚 and 50℃)
𝑩𝒊
Using Antoine’s equation: 𝒍𝒐𝒈 𝑷𝒊𝒐 = 𝑨𝒊 −
𝑪𝒊+𝑻
Constants: 𝐴 = 6.87987
𝐵 = 1196.76
𝐶 = 219.161
𝑜 1196.76 𝑃𝐵 𝑜 271.3996 𝑚𝑚𝐻𝑔
log 𝑃𝐵 = 6.87987 − 𝐾𝑖 = =
219.161+50 𝑃 760 𝑚𝑚𝐻𝑔
𝑃𝐵𝑜 = 271.3996 𝑚𝑚𝐻𝑔 𝑲𝒊 = 𝟎. 𝟑𝟓𝟕𝟏
27
 Evaluation of 𝐾𝑖
PHB p. 2-53

28
 Evaluation of 𝐾𝑖

Solution:
a.1 For toluene (1 𝑎𝑡𝑚 and 50℃)
𝑪𝟐
Using: 𝒍𝒏 𝑷 = 𝑪𝟏 + + 𝑪𝟑 𝒍𝒏 𝑻 + 𝑪𝟒𝑻 𝑪𝟓 ; 𝑇 = 323.15 𝐾
𝑻
Constants: 𝐶1 = 76.945
𝐶2 = −6729.8
𝐶3 = −8.179
𝐶4 = 5.3017 × 10−6 𝑃𝑇 𝑜 12,256.3123 𝑃𝑎
𝐾𝑖 = =
𝐶5 = 2 𝑃 101,325 𝑃𝑎

𝑃𝑇𝑜 = 12,256.3123 𝑃𝑎 𝑲𝒊 = 𝟎. 𝟏𝟐𝟏𝟎

29
 Evaluation of 𝐾𝑖
PHB p. 2-53

30
 Evaluation of 𝐾𝑖

Solution:
b.1 For n-octane (1 𝑎𝑡𝑚 and 80℃)
𝑪𝟐
Using: 𝒍𝒏 𝑷 = 𝑪𝟏 + + 𝑪𝟑 𝒍𝒏 𝑻 + 𝑪𝟒𝑻 𝑪𝟓 ; 𝑇 = 353.15 𝐾
𝑻
Constants: 𝐶1 = 96.084
𝐶2 = −7900.2
𝐶3 = −11.003
𝐶4 = 7.1802 × 10−6 𝑃𝑇 𝑜 23,280.9691 𝑃𝑎
𝐾𝑖 = =
𝐶5 = 2 𝑃 101,325 𝑃𝑎

𝑃𝑇𝑜 = 23,280.9691 𝑃𝑎 𝑲𝒊 = 𝟎. 𝟐𝟐𝟗𝟖

31
 Evaluation of 𝐾𝑖

Solution:
b.2 For n-octane (100 𝑝𝑠𝑖𝑎 and 80℃ ≈ 176℉)
𝟐
𝑻 𝑻 𝑻 𝟑
Using De Priester equation: 𝑲 = 𝒂 + 𝒃 +𝒄 +𝒅
𝟏𝟎𝟎 𝟏𝟎𝟎 𝟏𝟎𝟎
Constants: 𝑎 = −0.0198
𝑏 = 0.0704
𝑐 = −0.0614
𝑑 = 0.0256
2 3
176 176 176
𝐾 = −0.0198 + 0.0704 − 0.0614 + 0.0256 = 𝟎. 𝟎𝟓𝟑𝟓
100 100 100
32
 Evaluation of 𝐾𝑖

Practice Problem:
Solve for 𝐾𝑖 of n-pentane at 80℃ and
1. at 1 𝑎𝑡𝑚 (as an ideal system)
2. at 100 𝑝𝑠𝑖𝑎
De Priester constants: 𝑎 = −0.0025
𝑏 = 0.1099
𝑐 = 0.0660
𝑑 = 0.0323
33
 Va p o r - Liquid Equilibrium

Example 1.2
What are the equilibrium distribution coefficients, K, at
120℃ and 1500 𝑘𝑃𝑎 for the following compounds?
a.ethylene
b.n-pentane
c.n-heptane

34
Low-temperature range 35 High-temperature range
Evaluation of 𝐾𝑖

36
 Va p o r - Liquid Equilibrium

Answer:
a.ethylene - 𝑲 = 𝟖. 𝟓
b.n-pentane - 𝑲 = 𝟎. 𝟔𝟒
c.n-heptane - 𝑲 = 𝟎. 𝟏𝟕
37
 Va p o r - Liquid Equilibrium

According to Raoult’s Law:

𝑷𝑨
𝑿𝑨 =
𝑷𝑨𝒐
According to Dalton’s Law:
𝑷𝑨
𝒀𝑨 =
𝑷𝑻
Therefore,
𝑷𝑨𝒐
𝒀𝑨 = 𝑿
𝑷𝑻 𝑨
38
 Va p o r - Liquid Equilibrium

Example 1.3
A liquid phase contains 30% mole 𝐶6𝐻6 and 70% mole
𝐶7𝐻8 at 40℃.
a. Calculate the composition of the vapor phase in
equilibrium of the liquid.
b. Calculate the total pressure of the liquid phase.

39
 Va p o r - Liquid Equilibrium

Solution:
For benzene at 40℃
𝑩𝒊
Using Antoine’s equation: 𝒍𝒐𝒈 𝑷𝒊𝒐 = 𝑨𝒊 −
𝑪𝒊+𝑻
Constants: 𝐴 = 6.87987
𝐵 = 1196.76
𝐶 = 219.161
1196.76 𝑃𝐴 = 0.30(182.9292 𝑚𝑚𝐻𝑔)
log 𝑃𝐴 𝑜 = 6.87987 −
219.161+40
𝑃𝐴 = 54.8488 𝑚𝑚𝐻𝑔
𝑃𝐴 𝑜 = 182.8292 𝑚𝑚𝐻𝑔
𝑃𝐴 = 7312.5719 𝑃𝑎
40
 Va p o r - Liquid Equilibrium

For toluene at 40℃

𝑪𝟐
Using: 𝒍𝒏 𝑷 = 𝑪𝟏 + + 𝑪𝟑 𝒍𝒏 𝑻 + 𝑪𝟒𝑻 𝑪𝟓 ; 𝑇 = 313.15 𝐾
𝑻
Constants: 𝐶1 = 76.945
𝐶2 = −6729.8
𝐶3 = −8.179
𝐶4 = 5.3017 × 10−6
𝐶5 = 2
𝑃𝐵 = 0.70(7880.3387 𝑃𝑎)
𝑃𝐵𝑜 = 7880.3387 𝑃𝑎
𝑃𝐵 = 5516.2371 𝑃𝑎
41
 Va p o r - Liquid Equilibrium

b. 𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵 = 7312.5719 𝑃𝑎 + 5516.2371 𝑃𝑎
𝑷𝑻 = 𝟏𝟐, 𝟖𝟐𝟖. 𝟖𝟎𝟗 𝑷𝒂

𝑃𝐴 7312.5719 𝑃𝑎
a. 𝑌𝐴 = =
𝑃𝑇 12,828.809 𝑃𝑎
𝒀𝑨 = 𝟎. 𝟓𝟕
𝑌𝐵 = 1 − 𝑌𝐴 = 1 − 0.57
𝒀𝑩 = 𝟎. 𝟒𝟑

42
 Va p o r - Liquid Equilibrium

Example 1.4
The vapor pressure of n-heptane and toluene at 373 𝐾
are 106 𝑘𝑃𝑎 and 73.7 𝑘𝑃𝑎 , respectively. What are the
mole fraction of n-heptane in the vapor and in the liquid
phase at 373 𝐾 if the total pressure is 101.3 𝑘𝑃𝑎?

43
 Va p o r - Liquid Equilibrium

Given: 𝑃𝐴𝑜 = 106 𝑘𝑃𝑎

𝑃𝐵𝑜 = 73.7 𝑘𝑃𝑎
𝑃𝑇 = 101.3 𝑘𝑃𝑎
Solution: 𝑃𝐴 = 𝑃𝐴𝑜𝑋𝐴
𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵 𝑃𝐴 = 106 𝑘𝑃𝑎 (0.8545)
𝑃𝑇 = 𝑃𝐴𝑜𝑋𝐴 + 𝑃𝐵𝑜𝑋𝐵 𝑃𝐴 = 90.577 𝑘𝑃𝑎
𝑃𝑇 = 𝑃𝐴𝑜𝑋𝐴 + 𝑃𝐵𝑜(1 − 𝑋𝐴)
𝑃𝐴 90.577 𝑘𝑃𝑎
101.3 = 106 𝑋𝐴 + 73.7 (1 − 𝑋𝐴) 𝑌𝐴 = =
𝑃𝑇 101.3 𝑘𝑃𝑎
𝑿𝑨 = 𝟎. 𝟖𝟓𝟒𝟓 ; 𝑿𝑩 = 𝟎. 𝟏𝟒𝟓𝟓 𝒀𝑨 = 𝟎. 𝟖𝟗𝟒𝟏 ; 𝒀𝑩 = 𝟎. 𝟏𝟎𝟓𝟗
44
 Va p o r - Liquid Equilibrium

According to Henry’s Law:

𝑷𝑨 = 𝑯𝑿𝑨
Where,
𝑯 = 𝐻𝑒𝑛𝑟𝑦′𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

45
Henry’s Law

PHB p. 2-90

46
 Va p o r - Liquid Equilibrium

Example 1.5
Calculate the composition of the liquid and gas phase for
a mixture of air and liquid water at 68℉ and 760 𝑚𝑚𝐻𝑔.

Given: 𝑇 = 68℉ ≈ 20℃

𝑃𝑇 = 760 𝑚𝑚𝐻𝑔
𝐴 − 𝑎𝑖𝑟
𝐵 − 𝑙𝑖𝑞𝑢𝑖𝑑 𝑤𝑎𝑡𝑒𝑟
47
Evaluation of 𝐾𝑖

48
 Va p o r - Liquid Equilibrium

Solution:
For water at 20℃
𝑩𝒊
Using Antoine’s equation: 𝒍𝒐𝒈 𝑷𝒊𝒐 = 𝑨𝒊 −
𝑪𝒊+𝑻
Constants: 𝐴 = 8.07131
𝐵 = 1730.63
𝐶 = 233.426
1730.63
log 𝑃𝐵 𝑜 = 8.07131 −
233.426+20 *𝑃𝐴 = 𝑃𝐴 𝑜 and 𝑃𝐵 = 𝑃𝐵 𝑜
𝑃𝐵𝑜 = 17.4733 𝑚𝑚𝐻𝑔 = 𝑃𝐵 (assuming pure components)
49
 Henry’s Law

𝑃𝑇 = 𝑃𝐴 + 𝑃𝐵 𝑋𝐵 = 1 − 𝑋𝐴
𝑃𝐴 = 𝑃𝑇 − 𝑃𝐵 𝑿𝑩 = 𝟎. 𝟗𝟗𝟗𝟗𝟖𝟓
𝑃𝐴 = 760 − 17.4733
𝑃𝐴 742.5267 𝑚𝑚𝐻𝑔
𝑃𝐴 = 742.5267 𝑚𝑚𝐻𝑔 𝑌𝐴 = =
𝑃𝑇 760 𝑚𝑚𝐻𝑔
𝑃𝐴 = 𝐻𝑋𝐴 𝒀𝑨 = 𝟎. 𝟗𝟕𝟕 ; 𝒀𝑩 = 𝟎. 𝟎𝟐𝟑
𝐻 = 6.64 × 104 𝑎𝑡𝑚
742.5267

𝑿𝑨 = 760
= 𝟏. 𝟒𝟕𝟏𝟒 × 𝟏𝟎−𝟓
6.64×104
50
 Va por - Liquid Equilibrium

◉ Volatility – tendency of the substance to vaporize

𝑜
𝑃𝐴 𝑜 𝑃𝐴
From 𝑌𝐴 = 𝑋𝐴 and 𝐾𝐴 =
𝑃𝑇 𝑃𝑇
Therefore, 𝒀𝑨 = 𝑲𝑨𝑿𝑨 and 𝒀𝑩 = 𝑲𝑩𝑿𝑩
◉ Relative Volatility – a measure of comparing the vapor
pressures of the components in a liquid mixture.
𝑲𝑨 (𝒀𝑨/𝑿𝑨)
𝜶𝑨𝑩 = = = 𝒀𝑨𝑿𝑩
𝑲𝑩 (𝒀𝑩/𝑿𝑩) 𝒀𝑩𝑿𝑨
◉ For binary system,
𝒐
𝒀𝑨(𝟏−𝑿𝑨) 𝑷𝑨
𝜶𝑨𝑩 = =
𝑷𝑩𝒐
𝑿𝑨(𝟏−𝒀𝑨)
51
 Va p o r - Liquid Equilibrium

Example 1.6
What is the relative volatility of n-heptane and n-octane
at 20 𝑝𝑠𝑖𝑎 and 80℉?

Given: 𝑇 = 80℉ ≈ 299.82 𝐾

P = 20 𝑝𝑠𝑖𝑎
𝐴 − 𝑛 − ℎ𝑒𝑝𝑡𝑎𝑛𝑒
𝐵 − 𝑛 − 𝑜𝑐𝑡𝑎𝑛𝑒
52
53
 Va p o r - Liquid Equilibrium

Answer:
For n-heptane - 𝑲 ≈ 𝟎. 𝟎𝟔
For n-octane - 𝑲 = 𝟎. 𝟎𝟐
𝐾 0.06
Therefore, 𝜶 𝑨𝑩 = 𝐾 𝐴 = 0.02 = 𝟑
𝐵

54
 Evaluation of 𝐾𝑖

Another Solution:
For n-heptane at 80℉
𝑪𝟐
Using: 𝒍𝒏 𝑷 = 𝑪𝟏 + + 𝑪𝟑 𝒍𝒏 𝑻 + 𝑪𝟒𝑻 𝑪𝟓 ; 𝑇 = 299.82 𝐾
𝑻
Constants: 𝐶1 = 87.829
𝐶2 = −6996.4
𝐶3 = −9.8802
𝐶4 = 7.2099 × 10−6
𝐶5 = 2
𝑷𝑨𝒐 = 𝟔, 𝟓𝟖𝟗. 𝟐𝟔 𝑷𝒂
55
 Evaluation of 𝐾𝑖

Solution:
For n-octane at 80℉
𝑪𝟐
Using: 𝒍𝒏 𝑷 = 𝑪𝟏 + + 𝑪𝟑 𝒍𝒏 𝑻 + 𝑪𝟒𝑻 𝑪𝟓 ; 𝑇 = 299.82 𝐾
𝑻
Constants: 𝐶1 = 96.084
𝐶2 = −7900.2
𝐶3 = −11.003
𝐶4 = 7.1802 × 10−6 𝑃𝐴 𝑜 6,589.26 𝑃𝑎
𝛼𝐴𝐵 = 𝑃𝐵𝑜
=
𝐶5 = 2 2,053.946 𝑃𝑎

𝑷𝑩𝒐 = 𝟐, 𝟎𝟓𝟑. 𝟗𝟒𝟔 𝑷𝒂 𝜶𝑨𝑩 = 𝟑. 𝟐𝟎𝟖𝟏

56
Thanks!
ANY QUESTIONS?

57