Chemical Engineering

Thermodynamics II
Course Code: CEE4205
(2 Credits)
Course Content

• The Euler’s equation, Gibbs-Duhem equation

• Phase equilibria
• Partial Quantities
• Chemical equilibrium – multicomponent
systems
• Non-ideal systems
Learning Objectives

The objectives the course are to:

1. Identify equilibrium that exists between or within different states
of matters.
2. Be acquainted with types & areas of application of phase
equilibrium.
3. Study vapor-liquid equilibrium: Raoult’s law, modified Raoult’s law
and vapor-liquid equilibrium diagram.
4. Conversant with dew and bubble point calculations.
Expected Learning Outcomes
Having completed this course, students will be able to:
1. Understand equilibrium that exists b/w and within different state of
matter.
2. Know the various types of phase equilibrium and their industrial
applications.
3. Describe the phase equilibrium curves, construct and describe vapor-
liquid equilibrium problems.
4. Perform the dew and bubble point calculations for the vapor-liquid
equilibrium and use of DePriester chart to determine equilibrium
ratios for light hydrocarbons @ low and heavy temperature ranges.
Phase Equilibria

• Phase equilibrium is the study of the equilibrium which

exists between or within different states of matter, namely
solid, liquid and gas.
• Equilibrium is defined as a stage when the chemical
potential of any component present in the system stays
steady with time. Or is a static condition in which no
changes occur in the macroscopic properties of a system
with time. This implies a balance of all potentials that may
cause change.
Phase Equilibria

• Phase is a region where the intermolecular interaction

is spatially uniform. In other words, the physical and
chemical properties of the system are the same
throughout the region. Within the same state, a
component can exist in two different phases, such as
the allotropes of an element. Also, two immiscible
compounds in the same liquid state can coexist in two
phases.
Phase Equilibria

• Phase equilibrium has a wide range of applications in

industries, including:
• Producing different allotropes of carbon.
• Lowering the freezing point of water by dissolving salt
(brine).
• Purification of components by distillation.
• Usage of emulsions in food production, pharmaceutical
industry, etc.
Phase Equilibria

• Solid-solid phase equilibrium has a special place in

metallurgy and is used to make alloys of different
physical and chemical properties.
• For instance, the melting point of alloys of copper and
silver is lower than the melting point of either copper
or silver.
Phase Equilibria - Phase diagrams

• Phase diagrams are used to understand the

relationship between different phases
• They are usually represented as the change in the
phase of a system as a function of temperature,
pressure, or composition of the components in a
system.
• The system exists in a phase where the Gibbs free
energy of the system is least.
Phase Equilibria - Phase diagrams
• At equilibrium, the temperature, pressure, and
chemical potential of constituent component
molecules in the system have to be the same
throughout all the phases.
• Figure 1 gives a general schematic of a phase diagram
of a single component system.
Phase Equilibria - Phase diagrams

Figure 1: Phase diagram for one-component system

Phase Equilibria - Phase diagrams
• The curves shown in
Figure 1 represent the
coexistence of two
phases.
• The melting curve is the
curve in the phase diagram
along which the solid and
liquid phase of a system
stays in equilibrium.
Phase Equilibria - Phase diagrams
• The liquid and gas phases
remain in equilibrium
along the vaporization
curve.
• The sublimation curve
represents the equilibrium
stage between the solid
and gas phase.
Phase Equilibria - Phase diagrams
• The triple point is a point
on the graph where all the
three states coexist and is
unique for every
component.
Phase Equilibria - Phase diagrams
• If α and β are any two phases in which a component can
exist, by using the first and second law of thermodynamics
the slope of any of the curves in figure 1 can be represented
by
• … (1)
Where
o P and T are the pressure and temperature of the component, respectively.
o ΔS and ΔV are the changes in molar entropy and molar volume, respectively of
the component when it changes its phase from α to β at equilibrium.
Phase Equilibria - Types of Equilibrium
• The four kinds of equilibrium studied in detail are:
(1) Liquid-vapor
(2) Liquid-liquid
(3) Solid-liquid
(4) Solid-solid (alloys or allotropic forms)
• An increase in the number of components, chemical
reactions, surfactants, and deviation from ideal behavior
causes the enhanced complexity of phase diagrams.
Vapor-Liquid Equilibrium (VLE)
Raoult’s Law : The two major assumptions required to reduce
VLE calculations to Raoult’s law are:
(1)The vapor phase is an ideal gas.
(2)The liquid phase is an ideal solution.
• The first assumption means that Raoult’s law can be apply
only for low to moderate pressures.
• The second implies that it can have approximate validity only
when species that comprise the system are chemically
similar.
Vapor-Liquid Equilibrium (VLE)
• The mathematical expression which reflect the two listed
assumptions and which therefore gives quantitative
expression to Raoult’s law is:
• … (2)

• where:
• xi= liquid-phase mole fraction; yi= vapor-phase mole fraction;
• =vapor pressure of pure species i at the temperature of the system.
• The product yiP on the left side is known as the partial pressure of species i.
Vapor-Liquid Equilibrium (VLE)
• Raoult’s law states that partial vapor pressure exerted by a
component in an ideal solution is the product of its mole
fraction and vapor pressure of a pure component.
• Thereby, total vapor pressure exerted by an ideal solution
with k components, P is given by
• … (3)
• Where Pi is the vapor pressure of the pure component and xi
is the respective mole fraction.
Vapor-Liquid Equilibrium (VLE)
• For instance, if in a brine solution (two-component mixture),
one component (common salt) has negligible vapor at the
specified temperature.
• The mixture’s vapor pressure is simply a product of the mole
fraction of water and vapor pressure of water at the
specified temperature.
Vapor-Liquid Equilibrium (VLE)
• Raoult’s law is only valid for ideal solutions, assuming no
intermolecular interaction between components.
• In most cases dealt with in industries, ideal solutions are
uncommon.
• Modified Raoult’s law is used for non-ideal solutions;
accordingly, the total pressure exerted, P is expressed as
• ... (4)
• ϒ is the activity coefficient for the ith component.
Vapor-Liquid Equilibrium Diagram

Figure 2: Vapor-Liquid equilibrium diagram for ethanol-water system

Vapor-Liquid Equilibrium Diagram
• Figure 2 shows the phase diagram for ethanol-water
mixtures.
• Similar graphs are used in distilleries to calculate the desired
temperatures for specific outlet compositions.
• It contains a vapor curve and a liquid curve that is used to
estimate the vapor or liquid compositions.
• The vapor curve is also called the dew point curve, while the
liquid curve is called the bubble point curve.
Vapor-Liquid Equilibrium Diagram
• The curves meet each other at
their lowest point.
• If the electric boiler heater boils
the ethanol-water mixture
further, it will have the same
composition in the vapor phase.
• Therefore, the maximum ethanol
concentration obtained by a
simple distillation process in an
ethanol-water mixture is 95.5%.
Vapor-Liquid Equilibrium Diagram
• Azeotropes are mixtures that have the lowest and highest
boiling points on the phase diagram.
• Azeotropes cannot be purified further.
• Azeotropes have higher or lower boiling points than their
constituent components, depending on whether the
mixtures have a positive or negative deviation from Raoult’s
law, respectively.
• Ethanol-water is an example of azeotropic mixture.
Vapor-Liquid Equilibrium Diagram
• In the case of three-
component or three-phase
systems, triangular graphs
with three endpoints of the
triangle represent the three
pure components (phases).
VLE - Dew-point and Bubble-point Calculations with Raoult’s Law

These are of four classes:

• Bubble (vapor) Pressure (P): Calculate {yi} and P, given {xi} and T

• Dew (liquid) Pressure (P): Calculate {xi} and P, given {yi} and T

• Bubble (vapor) Temperature (T):Calculate {yi} and T, given {xi} & P

• Dew (liquid) Temperature (T): Calculate {xi} and T, given {yi} and P
 Example 1:
• Binary system acetonitrile (1)/nitromethane (2) conforms
closely to Raoult’s law. Vapor pressures for the pure species
are given by the following Antoine equations:

(a) Prepare a graph showing P vs. xi & P vs. yi for a temperature of 75oC.
(b) Prepare a graph showing t vs. xi & t vs. yi for a pressure of 75 kPa.
 Solution

• (a)Bubble point pressure calculations are required: the basis

is the binary-system form of Eq. (3) as:
• (E1)
• But
• (E2)
• Substituting (E2) in Eq. (E1), gives:
• (E3)
 Solution

• At 75oC, but the Antoine equations: and are 83.21 and 41.98
kPa respectively.
• Let x1 be 0.6, from Eq. (E3);
• The corresponding value of y1 is ten found from Eq. (4) as
follows:
•
 Solution

• These results mean that at 75oC a liquid mixture of 60 mol%

acetonitrile and 40 mol% nitromethane is in equilibrium with
a vapor containing 78.83 mol% acetonitrile at a pressure of
66.72 kPa.
• The results of calculations for 75oC at a number of values of
x1 are tabulated as follows:
 Solution

Table 1
x1 y1 P/kPa
0.0 0.0000 41.98
0.2 0.3313 50.23
0.4 0.5692 58.47
0.6 0.7483 66.72
0.8 0.8888 74.96
1.0 1.0000 83.21
 Solution

• The results in Table 1 are shown in Figure 3 by the P-x1-y1

diagram.
• This diagram is a phase diagram on which the straight line P-
x1 represents states of saturated liquid; the subcooled-liqiud
region lies above this line.
• The curve labelled P-y1 represents states of saturated vapor;
the superheated-vapor region lies below this curve.
Solution

Figure 3: P-x-y diagram for

acetonitrile (1)/nitro-methane (2) @
75oC as given by Raoult’s law
 Solution

• The point lying between the saturated liquid and the

saturated vapor lines are the two-phase region, where
saturated liquid and saturated vapor coexist at equilibrium.

• The P-x1 and P-y1 meet at the edges of the diagram, where
saturated liquid and saturated vapor of the pure species
coexist at the vapor pressures P1 and P2
 Solution

• (b) When pressure P is fixed, the temperature varies along

with x1 and y1.
• For a given pressure, the temperature range is bounded by
saturation temperatures t1 and t2, the temperatures at which the
pure species exert vapor pressures equal to P.
• For the present system, these temperatures are calculated from
the Antoine equations:
 Solution

• For P=70 kPa, =69.84oC and=89.58oC.

• The simplest way to prepare a t-x-y diagram is to select
values for t between these two temperatures,
• Calculate and for these temperatures, and evaluate x1 by Eq.
(E3), written:
 Solution

• For instance, at 78oC, and

•
• By Eq. (2),

• The results of this and similar calculations for P=70 kPa are as
follows:
 Solution

Table 2
x1 y1 t/oC
0.0000 0.0000 89.58 ()
0.1424 0.2401 86
0.3184 0.4742 82
0.5156 0.6759 78
0.7378 0.8484 74
1.0 1.0000 69.84 ()
 Solution

• Figure 4 is the t-x-y diagram showing these results.

• On this phase diagram drawn at constant pressure of 70 kPa,
the t-y1 curve represents states of saturated vapor, with state
of superheated vapor lying above it.
• The t-x1 curve represents states of saturated liquid, with state
of subcooled liquid lying below it.
• The two-phase region lies between these curves.
Solution

Figure 4: t-x-y diagram for acetonitrile

(1)/nitro-methane (2) @ 75oC as given by
Raoult’s law
Assignments/Exercises
(1)For the system methanol (1)/methyl acetate (2), the following equations
provide a reasonable correlation for the activity coefficients:
• where
• In addition, the following Antoine equations provide vapor pressures:
•
• where T is in kelvins and the vapor pressures are in kPa.
• Calculate the following:
• (a) P and {y1}, for T=318.15 K and x1=0.25.
• (b) P and {x1}, for T=318.15 K and y1=0.60.
Assignment
For the system methanol (1)/methyl acetate (2), the following equations
provide a reasonable correlation for the activity coefficients:
• ; where:
• In addition, the following Antoine equations provide vapor pressures:
•
• where T is in kelvins and the vapor pressures are in kPa.
• Calculate the following:
• (a) P and {y1}, for T=318.15 K and x1=0.25.
• (b) P and {x1}, for T=318.15 K and y1=0.60.
Vapor-liquid Equilibrium from K-Values
Correlations
• Equilibrium ratio (Ki) is a convenient measure of the
tendency of a given chemical species to partition itself
preferentially between liquid and vapor phases.
Mathematically:
• … (7)
• The quantity is usually called simply a K-value. This value
does serve as a measure of the “lightness” of a constituent
species, i.e. of the tendency to favor the vapor phase.
Vapor-liquid Equilibrium from K-Values
Correlations
• When Ki is greater than unity, species i exhibits a higher
concentration in the vapor phase.
• When Ki is less than unity, species I exhibits a higher
concentration in the liquid phase and it is considered heavy
constituent.
• In addition, the use of K-values makes computational
convenience, allowing elimination of one set of mole
fractions {yi} or {xi} in the favor of the other.
Vapor-liquid Equilibrium from K-Values
Correlations
• For Raoult’s law, K-value can be expressed as:
• … (8)
• and for the modified Raoult’s law, it is:
• … (9)
• According to Eq. (7), . Summation with yields
Vapor-liquid Equilibrium from K-Values
Correlations
• … (10)
• Thus for bubble point calculations where the xi are known,
the problem is to find set of K-values that satisfies Eq. (10).
Alternatively, Eq. (7) can be written, Summation with yields:
• … (11)
• Thus for the dew point calculations, where the yi is known,
the problem is to find the set of K-values that satisfies Eq.
(11).
Vapor-liquid Equilibrium from K-Values
Correlations
• Equations (8) and (9) together with Eq. (7) represent
alternative forms of Raoult’s law and modified Raoult’s law.
• The great attraction of Raoult’s law is that it expresses K-
values as functions of T and P, independent of the
compositions of the liquid and vapor phases.
• Where the assumptions which underlie Raoult’s law are
appropriate, this allows K-values to be calculated and
correlated as functions of T and P.
Vapor-liquid Equilibrium from K-Values
Correlations
• For mixtures of light hydrocarbons and other simple
molecules, in which the molecular force fields are relatively
uncomplicated, correlations of this kind have approximate
validity. Figures (5) and (6) show monograph for K-values of
light hydrocarbons as functions of T and P, prepared by
DePriester.
Vapor-liquid Equilibrium from K-Values
Correlations
• Example: For a mixture of 10 mol% methane, 20 mol% ethane and
70 mol% propane at 50oF, determine (i) the dew point pressure
and (ii) bubble point pressure using the DePriester chart.
• Solution:
• (i) When the system is at its dewpoint, only an insignificant
amount of liquid is present, and the given mole factions are of y i.
For the given temperature, the K-values depend on the choice of P,
and by trial we find the value for which Eq. (11) is satisfied. Results
for several values of P are given as follows:
Vapor-liquid Equilibrium from K-Values
Correlations
Vapor-liquid Equilibrium from K-Values
Correlations
• The results given in the last two columns show that Eq. (11)
is satisfied when P=126 psia. This is the dewpoint pressure,
and the composition of the dew is given by the values of
listed in the last column of the table.
• (ii)When the system is almost completely condensed, it is at
its bubblepoint, and the given mole fraction become values
of xi. In this case we find by trial the value of P for which the
K-values satisfies Eq. (10). Results for several values of P are
given in the following table:
Vapor-liquid Equilibrium from K-Values
Correlations
Vapor-liquid Equilibrium from K-Values
Correlations
• Eq. (10) is satisfied when P=385 psia. This is the bubblepoint
pressure. The composition of the bubble of the vapor is given
by as shown in the last column.