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Phase Equilibrium in Chemical Thermodynamics

This document provides a tutorial on fundamentals of phase equilibrium, including concepts like using phase equilibrium to design separation processes involving vapor and liquid. It discusses Gibbs free energy and determining the direction of equilibrium. Several definitions of chemical potential are given based on thermodynamic functions used to define them. Fugacity is described and how it is used in equilibrium criteria. Partial molar properties are introduced. Several calculation problems are provided involving entropy changes in gas mixing, distillation column separation, vapor-liquid equilibrium, and boiling point elevation.

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Naveed Ahmad
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24 views3 pages

Phase Equilibrium in Chemical Thermodynamics

This document provides a tutorial on fundamentals of phase equilibrium, including concepts like using phase equilibrium to design separation processes involving vapor and liquid. It discusses Gibbs free energy and determining the direction of equilibrium. Several definitions of chemical potential are given based on thermodynamic functions used to define them. Fugacity is described and how it is used in equilibrium criteria. Partial molar properties are introduced. Several calculation problems are provided involving entropy changes in gas mixing, distillation column separation, vapor-liquid equilibrium, and boiling point elevation.

Uploaded by

Naveed Ahmad
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CAB 2023 CHEMICAL THERMODYNAMIC

Tutorial Five

Fundamentals of Phase Equilibrium – Part 1

Concepts

1. In your own word, describe how phase equilibrium concept could be used for designing separation process
involving vapour and liquid.

2. Consider a system approaching its equilibrium;

- What can you say about its Gibbs Free Energy value?
- How do you determine the direction of equilibrium using Gibbs Free Energy?

3. Give several definitions of chemical potential based on the thermodynamic functions used to define them.

4. Describe in your own words the fugacity concept and how do you used them in describing equilibrium criteria.

5. What is partial molar property and why such concept was introduced?

Calculations

1. How much entropy is produced when 2 kg  mol of nitrogen at 25oC, 1 bar are mixed with 3 kg  mol of
oxygen at 25oC, 1 bar to make a mixture at the same temperature and pressure [kcal/K]? Assume an ideal
mixture of ideal gases.
[Ans : Sp = 6.69 kcal/K]

2. The distillation column shows below separates n-hexane (A) from n-octane (B).

1
Qd

Feed Distillate

Boiler
Qb Bottom

The column is operated at a pressure such that the overhead product, hexane, is condensed with water at
15oC, and the bottom product, octane, is boiled at 75 oC. If the feed is 60 mol % A, 40mol % B, the distillate
and the bottoms products essentially pure A and B, respectively, how much entropy is produced per 100 kg 
mol of feed (kcal/K)? The heat needed by the boiler, Q b, is 2500 kcal/kg mol bottom products, and that
extracted in the condenser, Qd, is 2500 kcal/kg mol distillate. The remainder of the process is adiabatic.
Assume ideal solution and neglect temperature differences among the streams. Further assume the heat
transfer in the boiler and condenser occurs at the boiler and condenser respectively.
[Ans : Sp = 99.9 kcal/K]

3. An ideal vapor mixture is formed from three compounds at 1-bar total pressure: 40 % A, 30 % B, and 30 % C
(all mol %). At the mixture temperature the vapor pressures of the three are 1.20, 1.40, and 1.50 bar,
respectively. If the mixture is compressed isothermally, at what pressure does the first drop of liquid appear
(bar)? What is its composition? The liquid is an ideal solution.
[Ans : P = 1.3376 bar ; xa = 0.446 ; xb = 0.286 ; xc = 0.268]

2
4. An ideal solution is formed from 30 % A, 20 % B, 50% C (mol %) at 50 oC, 1 bar. To what pressure must the
system be reduced to form the first bubble of vapor (bar)? What is the composition of this bubble? The vapor
is an ideal gas mixture. The vapor pressure of the components at 50oC are:

PA0  0.9 bar


PB0  0.8 bar
PC0  0.7 bar

[Ans : P = 0.78 bar ; ya = 0.346 ; yb = 0.205 ; yc = 0.449]

5. Estimate the boiling point elevation caused by dissolving 1 mol of sucrose (MW = 342) in 1.000 kg water at
100oC (the measured value is 0.563oC).
[Ans : 0.504 oC]

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