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The Phase-Equilibrium Problem

1. The document discusses phase equilibria, which involves the transfer of substances between phases until equilibrium is reached. Common examples include the exchange of oxygen and carbon dioxide between lungs and air. 2. Equilibrium phase compositions depend on variables like temperature, pressure, and chemical makeup. Phase equilibrium thermodynamics aims to relate these intensive properties at equilibrium. 3. Key concepts include homogeneous phases with uniform properties, and the Gibbs phase rule relating the number of intensive variables and phases. Thermodynamics equations must be applied to quantitatively relate conditions like temperature and composition between phases.

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209 views13 pages

The Phase-Equilibrium Problem

1. The document discusses phase equilibria, which involves the transfer of substances between phases until equilibrium is reached. Common examples include the exchange of oxygen and carbon dioxide between lungs and air. 2. Equilibrium phase compositions depend on variables like temperature, pressure, and chemical makeup. Phase equilibrium thermodynamics aims to relate these intensive properties at equilibrium. 3. Key concepts include homogeneous phases with uniform properties, and the Gibbs phase rule relating the number of intensive variables and phases. Thermodynamics equations must be applied to quantitatively relate conditions like temperature and composition between phases.

Uploaded by

thchou
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CHAPTER 1

The Phase-Equilibrium Problem


 Our lives are linked with materials that consists of a
variety of chemical substances. Many of the things we
do are concerned with the transfer of substances from
one mixture to another.

 For example, in our lungs, we take oxygen from the


air and dissolve it in our blood, while carbon dioxide
leaves the blood and enters the air.

 In our coffee maker, water-soluble ingredients are


leached from coffee grains into water; and when some-
one stains his tie with gravy, he relies on cleaning fluid
to dissolve and remove the greasy spot.
Lung
 In each of the common daily experiences, as well as
in many others in physiology, home life, industry, and
so on, there is a transfer of a substance from one
phase to another.

 When two phases are brought into contact, they tend


to exchange their constitutes until the composition of
each phase attains a constant value; when that state
is reached, we say that the phases are in equilibrium.

The equilibrium compositions of two phases are often


very different from one another, and it is precisely this
difference that enables us to separate mixtures by
distillation, extraction, and other phase-contacting
operations.
Extraction

Caffeine C8H10N4O2

Methylene chloride
Supercritical CO2
The final, or equilibrium, phase compositions depend on
several variables, such as temperature and pressure,
and on the chemical nature and concentrations of the
substances in the mixture.
Phase-equilibrium thermodynamics seeks to establish
the relations among the various properties (in particular,
temperature, pressure, and composition) that ultimately
prevail when two or more phases reach a state of equi-
librium wherein all tendency for further change has
ceased.
Phase-equilibrium thermodynamics is of special interest
in chemical engineering because so many operations in
the manufacture of chemical products consist of phase
contacting:Extraction, adsorption, distillation, leaching,
and absorption.
A typical chemical plant

Stages I and III : separation operation


Stage II : chemical reaction
1.1 Essence of the Problem

To relate quantitatively the variables that describe the


state of equilibrium of two or more homogeneous phases
that are free to interchange energy and matter.
Homogeneous phase : any region in space where the
intensive properties are everywhere the same.

Intensive properties : properties that are independent


of the mass, size, or shape of the phase : such as
temperature, density, pressure, and composition.

The number of intensive properties that must be


specified to fix unambiguously the state of equilibrium
is given by the Gibbs Phase Rule :
DF = C – P + 2 (1)
DF: number of independent intensive properties
C : number of components
P : number of phases
How to apply Gibbs phase rule?

For a two-component, two-phase system, the number


of Independent intensive properties is two.
DF  C  P  2
 2-2 2
2
In such a system the intensive properties of interest
usually are x1, x1, T and P. Two of these, any two,
must be specified before the remaining two can be
found.
1.2 Application of Thermodynamics to
Phase-Equilibrium Problems

To solve problems of the type, we must make transition from what we have
(the abstract thermodynamic equation of equilibrium) toward what we want
(quantitative information about temperature, pressure and compositions).
In any problem concerning the equilibrium distribution of
some component i between phases  and , we know
 
i  i (2)

To solve the problem, it is convenient to introduce some


auxiliary functions such as fugacity and activity

 y P  x f
i i i i i
0
(3)

We must then establish two relations

i  F (T , P, y1 , y2 ,...)
 i  F (T , P, x1 , x2, ...)
Much of this utility comes from the concept of ideality. If
we define mixtures with certain properties as ideal
mixtures, we then find, as a result of our choice of auxi-
liary functions, that the equation of equilibrium can be
simplified further.

For example, for a mixture of ideal gases, i=1


for ideal liquid mixtures at low pressures i=1
fi0=Pisat
 y P  x f
i i i i i
0

yi P  xi Pi sat

Raoult’s Law

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