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Introduction to Chemical
Engineering Thermodynamics

Dr Tajammal Munir
Email: Muhammad.Munir@aum.edu.kw

Chapter 8: Phase Equilibria

III: Applications

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Learning outcomes

1. Define the following preliminary concepts (LO1)

• Formulating Raoult's law using chemical equilibrium and fugacity
concepts
• Bubble point and dew point calculations
• Understanding and application of phase diagrams
2. Apply above concepts to formulate & solve engineering
problems (LO2)

Engineering and Chemical Thermodynamics

Milo D. Koretzky
Wiley, 2nd Edition

Preliminary concepts (LO1)

Raoult's law?
• Definition: It states that the partial pressure of each component of
an ideal mixture of liquids is equal to the vapour pressure of the
pure component multiplied by its mole fraction in the mixture.

• Mathematically:

𝑝 = 𝑝∗ 𝑥 ya yb V

Where, 𝑝 is the partial pressure of the component i in the gaseous

xa xb
mixture (above the solution), 𝑝∗ is the vapor pressure of the pure L
a
component i, and 𝑥 is the mole fraction of the component i in the b
mixture (in the solution).

𝑝 = 𝑝∗ 𝑥

𝑃 =𝑝 + 𝑝
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Preliminary concepts (LO1)

Raoult's law?
• Definition: It states that the partial pressure of each component of
an ideal mixture of liquids is equal to the vapour pressure of the
pure component multiplied by its mole fraction in the mixture.

• Mathematically:

𝑝 = 𝑝∗ 𝑥 𝑝 = 𝑝∗ 𝑥 𝑃 =𝑝 + 𝑝 ya yb V

xa xb
L
a
• Graphically: b

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100 % b 100 % a

𝑝∗

150
Vapor pressure

100 𝑝∗

50

0
0 0.25 0.50 xa 0.75 1.0

1.0 0.75 0.50 xb 0.25 0

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Preliminary concepts (LO1)

Raoult's law?
• Definition: It states that the partial pressure of each component of
an ideal mixture of liquids is equal to the vapour pressure of the
pure component multiplied by its mole fraction in the mixture.

• Mathematically:

𝑝 = 𝑝∗ 𝑥 𝑝 = 𝑝∗ 𝑥 𝑃 =𝑝 + 𝑝 ya yb V

𝑝∗ = 𝑝 xa xb
L
a
b
𝑝 =𝑝 𝑥 𝑝 =𝑝 𝑥 For liquid phase

𝑝 =𝑃 𝑦 𝑝 =𝑃 𝑦 For vapor phase

𝑃 𝑦 =𝑝 𝑥 At equilibrium
𝜑 = 𝐹𝑢𝑔𝑎𝑐𝑖𝑡𝑦
𝜑 𝑃 𝑦 =𝛾 𝑝 𝑥 𝑓 =𝑓 𝛾 = 𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡
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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

𝑃= 𝑦𝑃= 𝑥 𝑃 +𝑥 𝑃 +𝑥 𝑃 +𝑥 𝑃

1= 𝑦 × 1 = 0.3 × 𝑃 + 0.3 × 𝑃 + 0.2 × 𝑃 + 0.2 × 𝑃

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

1= 𝑦 × 1 = 0.3 × 𝑃 + 0.3 × 𝑃 + 0.2 × 𝑃 + 0.2 × 𝑃

2477.07 2477.07
𝑙𝑛𝑃 = 9.2132 − → 𝑷𝒔𝒂𝒕
𝒏 𝑪𝟓 𝑯𝟏𝟐 = 𝑙𝑛 9.2132 −
𝑇 + −39.94 𝑇 + −39.94

2766.63 2766.63
𝑙𝑛𝑃 = 9.1325 − → 𝑷𝒔𝒂𝒕
𝑪𝟔 𝑯𝟏𝟐 = 𝑙𝑛 9.1325 −
𝑇 + −50.50 𝑇 + −50.50
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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

1= 𝑦 × 1 = 0.3 × 𝑃 + 0.3 × 𝑃 + 0.2 × 𝑃 + 0.2 × 𝑃

2697.55 2697.55
𝑙𝑛𝑃 = 9.2164 − → 𝑷𝒔𝒂𝒕
𝒏 𝑪𝟔 𝑯𝟏𝟒 = 𝑙𝑛 9.2164 −
𝑇 + −48.78 𝑇 + −48.78

2911.32 2911.32
𝑙𝑛𝑃 = 9.2535 − → 𝑷𝒔𝒂𝒕
𝒏 𝑪𝟕 𝑯𝟏𝟔 = 𝑙𝑛 9.2535 −
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𝑇 + −56.51 𝑇 + −56.51
L

Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

1= 𝑦 × 1 = 0.3 × 𝑃 + 0.3 × 𝑃 + 0.2 × 𝑃 + 0.2 × 𝑃

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

1= 𝑦 × 1 = 0.3 × 𝑃 + 0.3 × 𝑃 + 0.2 × 𝑃 + 0.2 × 𝑃

2477.07
𝑷𝒔𝒂𝒕
𝒏 𝑪𝟓 𝑯𝟏𝟐 = 𝑙𝑛 9.2132 − = 2.13 𝑏𝑎𝑟
333 + −39.94

2766.63
𝑷𝒔𝒂𝒕
𝑪𝟔 𝑯𝟏𝟐 = 𝑙𝑛 9.1325 − = 0.514 𝑏𝑎𝑟
333 + −50.50

2697.55
𝑷𝒔𝒂𝒕
𝒏 𝑪𝟔 𝑯𝟏𝟒 = 𝑙𝑛 9.2164 − = 0.757 𝑏𝑎𝑟
333 + −48.78

2911.32
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𝑷𝒔𝒂𝒕
𝒏 𝑪𝟕 𝑯𝟏𝟔 = 𝑙𝑛 9.2535 − = 0.28 𝑏𝑎𝑟
333 + −56.51 L

Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.1:

Solution:

1= 𝑦 × 1 = 0.3 × 𝑃 2.13 + 0.3 × 0.514 + 0.2 × 0.757 + 0.2 × 0.28

𝑦 +𝑦 +𝑦 +𝑦 = 0.3 × 2.13 + 0.3 × 0.514 + 0.2 × 0.757 + 0.2 × 0.28

𝑦 +𝑦 +𝑦 +𝑦 = 0.639 + 0.1542 + 0.1514 + 0.056

Significance

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:

𝑦𝑃 𝑦
𝑥 = →1=
𝑃 𝑃

𝑦 𝑦 𝑦 𝑦
1= + + +
𝑃 𝑃 𝑃 𝑃

0.3 0.3 0.2 0.2

1= + + +
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𝑃 𝑃 𝑃 𝑃
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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:

2477.07
𝑃 = 𝑙𝑛 9.2132 −
𝑇 + −39.94

2766.63
𝑃 = 𝑙𝑛 9.1325 −
𝑇 + −50.50

2697.55
𝑃 = 𝑙𝑛 9.2164 −
𝑇 + −48.78

2911.32
𝑃 = 𝑙𝑛 9.2535 −
𝑇 + −56.51
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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:
0.3 0.3 0.2 0.2
1= + + +
𝑃 𝑃 𝑃 𝑃

1
0.3 0.3
= +
2477.07 2766.63
𝑙𝑛 9.2132 − 𝑙𝑛 9.1325 −
𝑇 + −39.94 𝑇 + −50.50
0.2 0.2
+ +
2697.55 2911.32
𝑙𝑛 9.2164 − 𝑙𝑛 9.2535 −
𝑇 + −48.78 𝑇 + −56.51

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:
Put T = 349 K in equations below to get saturation pressure,

2477.07
𝑷𝒔𝒂𝒕
𝒏 𝑪𝟓𝑯𝟏𝟐 = 𝑙𝑛 9.2132 − = 3.296 𝑏𝑎𝑟
349 + −39.94

2766.63
𝑷𝒔𝒂𝒕
𝑪𝟔𝑯𝟏𝟐 = 𝑙𝑛 9.1325 − = 0.870 𝑏𝑎𝑟
349 + −50.50

2697.55
𝑷𝒔𝒂𝒕
𝒏 𝑪𝟔𝑯𝟏𝟒 = 𝑙𝑛 9.2164 − = 1.256 𝑏𝑎𝑟
349 + −48.78

2911.32
𝑷𝒔𝒂𝒕
𝒏 𝑪𝟕𝑯𝟏𝟔 = 𝑙𝑛 9.2535 − = 0.494 𝑏𝑎𝑟
349 + −56.51
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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:
0.3 0.3 0.2 0.2
1= + + +
𝑷𝒔𝒂𝒕 𝑃 𝑃 𝑃 𝑃
𝒏 𝑪𝟓𝑯𝟏𝟐 = 3.296 𝑏𝑎𝑟

𝑷𝒔𝒂𝒕
𝑪𝟔𝑯𝟏𝟐 = 0.870 𝑏𝑎𝑟

𝑷𝒔𝒂𝒕
𝒏 𝑪𝟔𝑯𝟏𝟒 = 1.256 𝑏𝑎𝑟

𝑷𝒔𝒂𝒕
𝒏 𝑪𝟕𝑯𝟏𝟔 = 0.494 𝑏𝑎𝑟
0.3 0.3 0.2 0.2
𝑥 +𝑥 +𝑥 +𝑥 =1= + + +
𝑃 𝑃 𝑃 𝑃
0.3 0.3 0.2 0.2
𝑥 +𝑥 +𝑥 +𝑥 =1= + + +
3.296 0.870 1.256 0.494

𝑥 +𝑥 +𝑥 +𝑥 = 1 = 0.091 + 0.345 + 0.159 + 0.405

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.2:

Solution:
0.3 0.3 0.2 0.2
1= + + +
𝑃 𝑃 𝑃 𝑃

𝑥 +𝑥 +𝑥 +𝑥 = 1 = 0.091 + 0.345 + 0.159 + 0.405

Significance

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.3:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.3:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.3:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.3:

Solution:

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Applications of preliminary concepts (LO2)

Assessing bubble point and dew point calculation concepts

Example 8.3:

Solution:

𝑦 𝑃=𝑥 𝑃
𝑥 ,
𝑥 =
𝑃 𝑉 𝐿 𝑦 0.32 = 0.4 ∗ 0.56 → 𝑦 = 𝟎. 𝟕𝟎
+
𝑃 𝐹 𝐹

0.5
𝑥 = = 𝟎. 𝟒𝟎
0.56 1 2
+
0.32 3 3

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Applications of preliminary concepts (LO1)

Phase Diagrams?
• Definition: A phase diagram is a type of chart used to show conditions at
which thermodynamically distinct phases occur and coexist at equilibrium.

For Pxy, and Txy phase diagrams, please watch this video:
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https://www.youtube.com/watch?v=sN1kpR-cCuk C

Applications of preliminary concepts (LO1)

Phase Diagrams?
• Definition: A phase diagram is a type of chart used to show conditions at
which thermodynamically distinct phases occur and coexist at equilibrium.

• Constructing Txy phase diagram (example):

• Assume a binary mixture of a and b that follows Raoult’s law. Furthermore,

a is more volatile than b.

 xa = fraction of a in liquid, xb = fraction of b in liquid

 ya = fraction of a in vapour, yb = fraction of b in vapour
 𝐼𝑛 𝑙𝑖𝑞𝑢𝑖𝑑 𝑎𝑡 𝑎𝑛𝑦 𝑡𝑖𝑚𝑒 → 𝑥 + 𝑥 = 1, & 𝑖𝑛 𝑣𝑎𝑝𝑜𝑢𝑟 𝑎𝑡 𝑎𝑛𝑦 𝑡𝑖𝑚𝑒 → 𝑦 + 𝑦 = 1

Explaining phase diagrams (Click here)

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Summary

1. Define the following preliminary concepts (LO1)

• Formulating Raoult's law using chemical equilibrium and fugacity
concepts
• Bubble point and dew point calculations
• Understanding and application of phase diagrams

2. Apply above concepts to formulate & solve engineering

problems (LO2)

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