Dr Major Mabuza

Chemical Thermodynamics 2A (CTDCHA2)

Learning Unit 5: Properties of Mixtures
Learning Unit 5: Properties of Mixtures 2
 Graduate Attributes

Development
Learning Unit 5: Properties of Mixtures 3
 Learning Outcomes

❑ Explain the quantitative behavior of vapor/liquid equilibrium from P-x-y, T-x-y, P-T and x-y diagrams for
binary systems.

❑ Interpret and apply P-x-y, T-x-y, P-T and x-y diagrams representing vapor/liquid equilibrium for binary
systems.

❑ Apply Henry’s law and Raoult’s law for gases dissolved in liquids.

❑ Apply the K-value correlation for bubble point and dew point calculations.

❑ Describe the fundamental property relationship for single- phase fluid systems.

❑ Explain the concept of chemical potential for phase equilibria.

❑ Explain the concept of fugacity and fugacity coefficient.

Learning Unit 5: Properties of Mixtures 4

 Learning Outcomes

❑ Determine fugacity/fugacity coefficient using generalized correlations and equations of state for gases and
liquids.

❑ Define activity and activity coefficient.

❑ Understand conventions for tabulating heat of solution and use them to compare heat effects of mixing.

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13.1. SIMPLE MODELS FOR VAPOR/LIQUID EQUILIBRIUM
 Raoult’s Law

❑ The figure below shows a vessel in which a vapor mixture and a liquid solution coexist in vapor/liquid
equilibrium.

❑ If the vapor phase is assumed to be in its ideal-gas state and the liquid phase is assumed to be an ideal
solution, we get the simple form of Raoult’s law:

❑ Two major assumptions required for Raoult’s law are:

✓ The vapor phase is an ideal gas.
✓ The liquid phase is an ideal solution.

❑ The first assumption implies that Raoult’s law can apply only for low
to moderate pressures.

❑ The second implies that it can have approximate validity only when
the species that comprise the system are chemically similar.
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 Raoult’s Law

❑ Raoult’s law is useful for displaying VLE calculations in their simplest form, and it also serves as a
standard of comparison for more complex systems.

❑ A limitation of Raoult’s law is that it can be applied only to species of known vapor pressure, and this
requires the species to be “subcritical,” i.e., to be at temperature below its critical temperature.

❑ Raoult’s law is valid for any species present at a mole fraction approaching unity, provided only the vapor
phase is an ideal. Hence, in this case, chemical similarity is not a requirement.

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 Dewpoint and Bubblepoint Calculations with Raoult’s Law

❑ Engineering interest for Raoult’s law centers around dewpoint and bubblepoint calculations; hence,
there are four classes for this:

BUBL P DEW P BUBL T DEW T

The pressure at which the
first bubble of gas comes
out from the liquid at a
given fixed temperature
The pressure at which the As this liquid is heated, a
first droplet of liquid temperature is reached at
appears at a specific which the first bubble of
fixed temperature vapor is formed at a given
fixed pressure.
As the vapor temperature
decreases at fixed
pressure, the dew point
temperature is reached,
at which the first drop of
liquid forms.

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 Modified Raoult’s Law

❑ For low to moderate pressures the Raoult’s law is usually reasonable.

❑ However, modifying Raoult’s law to properly evaluate the activity coefficient γi, and thus take into
account liquid-phase deviations from ideal solution behavior, produces a much more reasonable and
broadly applicable description of VLE behavior:

Activity Coefficient
A factor used to account for
deviation of a mixture of chemical
substances from ideal behavior.

❑ This equation provides for entirely satisfactory representation of the VLE behavior of a great variety of
systems at low to moderate pressures.

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 Henry’s Law

❑ By now, we all know that the application of Raoult’s law to species i requires a value for Pisat at the
temperature of application, and thus is not appropriate for a species whose critical temperature is less
than the temperature of application.

❑ For a species present as a very dilute solute in the liquid phase, Henry’s law then states that the
partial pressure of the species in the vapor phase is directly proportional to its liquid-phase
fraction. Thus,

𝑦𝑖 𝑃 = 𝑥𝑖 ℋ𝑖

Henry’s Constant

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 K-value Correlations

❑ A convenient measure of the tendency of a given chemical species to partition itself preferentially
between liquid and vapor phases is the equilibrium ratio Ki, defined as:

❑ This quantity is simply called a K-value.

❑ K-value adds nothing to the K-value for Raoult’s law:

thermodynamic knowledge of VLE.
However, it only measures the “lightness” of
a constituent species.
K-value for modified Raoult’s law:
❑ For Ki > 1 ⇒ species i exhibits a higher
concentration in the vapor phase (light).

❑ For Ki < 1 ⇒ species i has higher

concentration in the liquid phase (heavy).

Learning Unit 5: Properties of Mixtures 12

13.2. FUGACITY AND FUGACITY COEFFICIENT: PURE SPECIES
 Introduction

❑ In chemical thermodynamics, the fugacity(f) of a real gas is an effective pressure which replaces the
true mechanical pressure in accurate chemical equilibrium calculations.

❑ It is equal to the pressure of an ideal gas which has the same chemical potential as the real gas.

❑ For example, nitrogen gas (N2) at 0°C and a pressure of 100 atm has a fugacity of 97.03 atm. This means
that the chemical potential of real nitrogen at a pressure of 100 atm has the value which ideal nitrogen
would have at a pressure of 97.03 atm.

❑ In this section, we will be estimating the fugacity of species in

✓ Gaseous phase,
✓ Liquid phase, and
✓ Solid phase.

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 Introduction

❑ In general, fugacity (f) is calculated as follows:

Pressure units.

❑ And the related fugacity coefficient (Ф) by dividing with the pressure:

Dimensionless

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 Fugacity of a Pure Gaseous Species

❑ The fugacity of a pure gaseous species is mathematically defined as:

❑ At low pressures, where a gas can be described by the ideal gas equation of state:

the following expressions are valid (i.e., the fugacity of a species is just equal to the total pressure)

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 Fugacity of a Pure Gaseous Species

❑ At low to moderate pressures, the virial equation of state truncated after the second virial coefficient
may be used, if data for B(T) is available, as follows:

and

where

Learning Unit 5: Properties of Mixtures 17

 Fugacity of a Pure Gaseous Species

❑ At higher pressure, more complicated equation of state (or higher terms in the virial expansion) must be
used. Using the van der Waals equation we get:

alternatively;

where

Learning Unit 5: Properties of Mixtures 18

 Fugacity of a Pure Gaseous Species

❑ For hydrocarbons and simple gases, the Peng-Robinson equation of state provides more accurate
description, and may used as follows:

where

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 Fugacity of a Pure Liquid Species

❑ Fugacity of a pure liquid species can be computed in a number of ways, depending on the data
available.

❑ Using the Peng-Robinson equation of state:

❑ Poynting correction

Learning Unit 5: Properties of Mixtures 20

 Fugacity of a Pure Liquid Species

❑ Simple approximation for fL:

❑ Best approximation of fL:

❑ Another best approximation of fL:

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 Fugacity of a Pure Solid Species

❑ Since the sublimation (or vapor) pressure of a solid is generally small, so that the fugacity coefficient can
be taken equal to unity.

❑ At low pressures fugacity of a pure solid can be approximated by:

❑ And at moderate or high total pressure is

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13.2. FUGACITY AND FUGACITY COEFFICIENT OF SPECIES IN
GASEOUS, LIQUID, AND SOLID MIXTURES
 Fugacity for Gaseous Mixtures

❑ Several methods are commonly used for estimating the fugacity of a species in a gaseous mixture.

❑ However, the most appropriate method is based on the observation that some gaseous mixtures follow
Amagat’s law, that is:

Multiplying through by P/NRT gives

Compressibility
factor of the mixture
Compressibility factor
yi = Ni/N of the pure component
yi – gas-phase mole fraction
xi – liquid-phase mole fraction
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 Gaseous Mixtures – Lewis-Randall Rule

❑ Relates the fugacity of a species in a gaseous mixture only to its mole fraction and the fugacity of the pure
gaseous component at the same temperature and pressure. It is defined as:

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 Gaseous Mixtures – Virial Equation of State

❑ Gaseous fugacity from the virial equation of state can be computed as follows:

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 Other methods – Peng-Robinson Equation of State

❑ The equation can easily and quickly be solved using:

✓ MATHCAD,
✓ MathLab,
✓ Excel Solver,
✓ Polymath, or
✓ any other advanced mathematical software.

NOT TO BE EXAMINED

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 Fugacity for Liquid Mixtures

❑ The estimation of species fugacities in liquid mixtures is done in two different ways, depending on the data
available and the components of the mixture.

❑ For liquids involving only hydrocarbons and dissolved gases, such as nitrogen, hydrogen sulphide, and
carbon dioxide, simple equation of state may be used to describe the liquid-state behaviour. For example:
✓ Peng-Robinson equation of state, and
✓ Van der Waals mixing rules.

❑ Peng-Robinson Equation of State:

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 Fugacity for Solid Mixtures

❑ Fugacity of a species in many mixed solids is given by the following expression:

❑ Fugacity of a species in a true solid mixture:

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THANK YOU
Dr Major Mabuza (Deng: Chemical Engineering) – majorm@uj.ac.za
4137 – JOHN ORR – DOORNFONTEIN CAMPUS