Title
Thermodynamics II
Solution Thermodynamics: Applications
Department of Chemical Engineering
College of Engineering
Al-Imam Muhammad Ibn Saud
Islamic University
Prepared by
Dr. Ahmed Fayez Nassar
A. F. Nassar 1
Contents of the Lecture
• Introduction
• Liquid-Phase Properties from VLE Data
• Models for the Excess Gibbs Energy
• Property Changes of Mixing
• Heat Effects of Mixing Processes
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Introduction
All of the fundamental equations and necessary definitions of solution
thermodynamics are given in Chapter 11.
In Chapter 12, we examine what can be learned from experiment.
Considered first are measurements of vapor/liquid equilibrium (VLE) data,
from which different correlations are derived.
Second, we treat mixing experiments, which provide data for property
changes of mixing. In particular, practical applications of the enthalpy change
of mixing, called the heat of mixing, are presented in details.
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Introduction
Liquid VLE Data for Methyl
Ethyl Ketone (1) /
Toluene (2) at 50°C
Vapor
These VLE data can be used to calculate
the fugacity and the activity coefficients and
several other properties.
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Liquid-Phase Properties from VLE Data: Fugacity
Since the vapor and liquid phases are at equilibrium:
Note that we can calculate the
fugacity coefficients using
Lee/Kesler method (or Virial
Method), if the experiment
pressure is high (i.e. without
assuming the ideal gas).
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Liquid-Phase Properties from VLE Data: Fugacity
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Liquid-Phase Properties from VLE Data: Activity Coeff.
Activity coefficient is defined as:
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Liquid-Phase Properties from VLE Data: Activity Coeff.
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Liquid-Phase Properties from VLE Data: Excess Gibbs Energy
Excess Gibbs Energy can be calculated as:
We will also calculate:
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Liquid-Phase Properties from VLE Data: Excess Gibbs Energy
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Liquid-Phase Properties from VLE Data: Excess Gibbs Energy
l’Hopital
Rule
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Liquid-Phase Properties from VLE Data: Data Reduction
But we know that:
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Liquid-Phase Properties from VLE Data: Data Reduction
Margules equations (~ 1900)
For the Methyl Ethyl Ketone / Toluene
data studied before:
Note: this model might not represent the data well
enough because:
1. The experiments might contain some errors
2. Not suitable for all solutions
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Models for the Excess Gibbs Energy
Like Margules Equations:
Redlich/Kister (1952) suggested:
Note: Like Chapter 10
Then Note: this is not valid for MEK/Toluene mixture
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Models for the Excess Gibbs Energy
van Laar equations:
Starting from:
Notes:
1. All the above models are empirical (no theory behind them)
2. The models are only for binary systems
3. They are not universal (might fit some solutions, and might be not suitable for others)
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Models for the Excess Gibbs Energy: Local-Composition Models
The local composition models theory takes into account the effect of the volumes of
the molecules of the different species in the solution on the interaction between the
particles (intermolecular forces).
The parameters of these models are function of the specific volumes and temperature.
Wilson equation (1964)
Binary Interaction
Parameters
Specific volumes of
components at T
NRTL equation (Non-Random-Two-Liquids) (1968)
UNIQUAC equation (1975)
UNIFAC equation (depend on the groups inside the molecule) (1977)
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Property Changes of Mixing
For ideal solutions:
For real solutions:
Thus
The Property Changes of Mixing =
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Property Changes of Mixing
The Property Changes of Mixing =
For ideal solutions:
Thus
We can also deduce that
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Property Changes of Mixing
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Heat Effects of Mixing Processes: Heats of Solution
The Heat of Mixing =
For binary system:
Heat of mixing data are available for a very limited number of temperatures. Thus we
can calculate it for any other temperature as follows:
Heats of Solution is used for dissolving gases or solids in liquids. It is based on
dissolving 1 mol of solute.
It is defined as: moles solvent/mole solute
heat of solution
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per mole of solute 20
Heat Effects of Mixing Processes: Heats of Solution
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Heats of solution at 25 °C for LiCl and HCl in water 21
Heat Effects of Mixing Processes: Enthalpy/Conc. Diagrams
Enthalpy / Concentration Diagrams represents a relation between the enthalpy of the
mixture and its concentration at different temperatures.
For mixing of solution “a” with “b” to give “c”:
a, b and c on the same line
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Heat Effects of Mixing Processes: Enthalpy/Conc. Diagrams
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H x diagram for H2SO4 (1) in H2O (2) 23
Heat Effects of Mixing Processes: Enthalpy/Conc. Diagrams
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H x diagram for NaOH (1) in H2O (2) 24
Heat Effects of Mixing Processes: Enthalpy/Conc. Diagrams
Ex. 12.7
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H x diagram for NaOH (1) in H2O (2) 25
Heat Effects of Mixing Processes: Enthalpy/Conc. Diagrams
12.44
12.49
Q/m = -123
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H x diagram for H2SO4 (1) in H2O (2) 26
