ChE 408 | PRELIMINARY MODULE

Module Introduction

This module discusses the preliminary topics including the general Vapor/Liquid Equilibrium and the Theory of Solution
Thermodynamics.

This subject deals with a lot of correlation, may it be taken from a certain reference of from Perry’s Handbook. Majority of the
discussions that will be presented here are taken from Introduction to Chemical Engineering Thermodynamics by J.M Smith, H. Van Ness,
et.al. Should you want to know more about the topic, one can look for this book for further reading.

All modules are also uploaded in the respective Google Classroom. Other videos from YouTube will be linked for further
references. This will also aid you in understanding the concept even more. Exams have a hard copy version, though it is advised to take
the online exam for you to easily check your work and review your mistakes. Assessment will be made after every module.

Intended Learning Outcome

The following are the learning outcomes that will be acquired by the students after finishing the course:
1. Apply the concepts of physical chemistry and techniques in calculus to derive other thermodynamic property relations from
fundamental property relations, calculate changes in the thermodynamic properties of homogeneous mixtures, derive the phase
equilibrium relation and chemical equilibrium relations;
2. Identify and solve vapor-liquid equilibrium problems for both ideal and non-ideal solutions;
3. Apply vapor-liquid equilibrium relations based on cubic equations of state and other EOS models;
4. Derive solution properties from vapor-liquid equilibrium experimental data;
5. Interpret phase equilibrium diagrams;
6. Solve for the equilibrium conversion of single reaction systems and analyze the effect of operating variables on chemical reaction
conversion;
7. Use spreadsheets and numerical computing software in vapor-liquid equilibrium calculations, construction of phase equilibrium
diagrams and solving for the equilibrium conversion of multi-reaction systems.transfer.
8.
These are based on CMO No. 19 s.2017 for Chemical Engineering Course.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

Vapor/Liquid Equilibrium: Introduction

A. The Nature of Equilibrium

Equilibrium is a condition in which no changes occur in the macroscopic properties of an isolated system with time.
At equilibrium, all potentials that may cause change are exactly balanced, so no driving force exists for any change in
the system. An isolated system consisting of liquid and vapor phases* in intimate contact eventually reaches a final state
wherein no tendency exists for change to occur within the system. The temperature, pressure, and phase compositions
reach final values which thereafter remain fixed. The system is in equilibrium. Nevertheless, at the microscopic level,
conditions are not static. The molecules comprising a phase at a given instant are not the same molecules that later
occupy the same phase. Molecules constantly pass from one phase to the other. However, the average rate of passage
of molecules is the same in both directions, and no net interphase transfer of material occurs. In engineering practice,
the assumption of equilibrium is justified when it leads to results of satisfactory accuracy. For example, in the reboiler
for a distillation column, equilibrium between vapor and liquid phases is commonly assumed. For finite vaporization rates
this is an approximation, but it does not introduce significant error into engineering calculations.
*A phase is a region of material with chemical uniformity.

1. Miscible, Immiscible and Partially Miscible Mixture

In a miscible mixture its components are mixed at a molecular level, e.g., molecular oxygen and nitrogen in
the atmosphere, and salt and water in the oceans. Typically, most gas phase mixtures are miscible, since the
intermolecular distances are far apart. In immiscible mixtures the intermolecular forces between like molecules
are too strong to allow a dissimilar molecule sandwiched between similar molecules. Partially miscible fluids are
miscible in a mixture until a critical mole fraction beyond which they become immiscible. For instance, salt can
be dissolved in water up to a certain concentration beyond which it settles, and it is possible to have a mixture
consisting of a salt–water solution and pure salt. Slurries are mixtures that contain additional species called
surfactants, which act as a bridge between the (usually two) immiscible species. For instance, the introduction
of surfactants into an oil–water mixture forms a slurry that is physically mixed, but is unmixed at the molecular
level.

2. Phase Systems and Equilibrium

Water exists as a liquid at 20ºC at pressures in excess of 2.34 kPa. This is the saturation pressure or bubble
point of water at 20ºC. During an isothermal process, a vapor bubble forms as the pressure equals the saturation
pressure. As the pressure is further lowered, all of the water will exist as superheated vapor. Therefore, at a
specified temperature, water can exist as a compressed liquid (𝑃>𝑃 𝑠𝑎𝑡 ), as a two–phase mixture (𝑃 = 𝑃 𝑠𝑎𝑡 ), or
as superheated vapor (𝑃 < 𝑃 𝑠𝑎𝑡 ). In the compressed liquid or superheated states, the water exists in a single
phase and two independent properties, say (𝑇, 𝑃), are required to specify the state, i.e., there are two degrees
of freedom present. In the saturated liquid or vapor region, one independent property, e.g., temperature,
specifies 𝑃 𝑠𝑎𝑡 (conversely, the pressure specifies 𝑇 𝑠𝑎𝑡 ). In a mixture consisting of two components (say,
methanol and water) an additional parameter related to the component concentration, e.g., the mole fraction is
required to describe the state of the system. Methanol is highly volatile and has a higher 𝑃 𝑠𝑎𝑡 as compared to
water at the same temperature. Therefore, a mixture may have different compositions in the corresponding
liquid and vapor phases.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

a. Single-Component System (Unary System)

To start, the following terms must be given their thermodynamic meanings.

Vapor Pressure: The pressure that the vapor phase of a fluid exerts over its own liquid at equilibrium at a
given temperature.

Dew Point: The pressure and temperature condition at which an infinitesimal quantity of liquid (a droplet)
exists in equilibrium with vapor. It represents the condition of incipient liquid formation in an initially gaseous
system. Notice that it can be also visualized as a “liquid system” where all but an infinitesimal quantity of
liquid has been vaporized.

Bubble Point: The pressure and temperature condition at which the system is all liquid, and in equilibrium
with an infinitesimal quantity (a bubble) of gas. This situation is, in essence, the opposite of that of the dew
point.

Once a saturation pressure has been selected, there is one (and only one) saturation temperature
associated with it. This is only true for a single component system. In other words, this is the only
temperature (at the given pressure), at which liquid and gas phase will co-exist in equilibrium. The rule that
governs the uniqueness of this point, for a single-component system, is called the Gibbs Phase Rule.
The vapor curve, shown in the figure below, represents the transition between the vapor and liquid
states for a pure component. If we cool the liquid system, it makes sense to expect ice to form (a solid
phase). In fact, there is a line that defines the liquid-solid transition; it is called the solidification (or melting)
curve. Furthermore, even though it is counter-intuitive, it is possible to go from solid to vapor without going
through a liquid state, if the pressure is low enough. This is known as the sublimation curve. Thus, the figure
below represents a more complete phase diagram for a pure-component system.
The triple point is the meeting point of the vapor pressure, solidification and sublimation curves; hence,
it represents the only condition at which all three phases of a pure substance (solid, liquid and gas) can co-
exist in equilibrium.

An example of typical phase diagram of a single-component system.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

At the critical point, gas and liquid are in equilibrium without any interface to differentiate them; they are
no longer distinguishable in terms of their properties. As we recall, the only location on the 𝑃-𝑇 diagram
where liquid and gas can be found together in equilibrium is along the vapor pressure curve. Hence, the
critical point is clearly the maximum value of temperature and pressure at which liquid and vapor can be at
equilibrium. This maximum temperature is called the critical temperature (𝑇𝑐 ); the corresponding maximum
pressure is called the critical pressure (𝑃𝑐 ).

An example of supercritical fluid (water) coming

from ocean’s hydrothermal vents.

Taken from P. Rona / OAR/National Undersea

Research Program (NURP); NOAA - NOAA Photo
Library

b. Two-Component System (Binary System)

Consider a two-component mixture consisting of water (normal boiling point 100ºC) and methanol (normal
boiling point 65ºC) in a piston–cylinder–weight assembly immersed in an isothermal bath. Suppose the molal
concentration of water is 60% and, consequently, 40% for methanol and the mixture temperature is 20ºC. At a
pressure of 200 kPa there is no phase change for this mixture. The same holds true for any methanol–water
mixture of arbitrary composition at the same temperature and pressure. If the pressure is decreased to 6.2 kPa
(while the mixture temperature is still 20ºC), a vapor bubble appears, but inside the vapor bubble the mole
fraction of water vapor at steady state is 0.23 (so that the mole fraction of methanol is 0.77) even though the
liquid water content is 60%. This is an example of phase equilibrium between a liquid mixture and a vapor
bubble. Upon decreasing the pressure to 5.0 kPa additional vapor is formed, the composition of which can be
determined by developing phase equilibrium criteria, as will be discussed thoroughly in the future. During
evaporation, it is possible to maintain the liquid at constant composition by introducing appropriate amounts of
the component(s) into the piston–cylinder–weight assembly.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

Illustration of a two-phase binary system under a piston pressure.

Taken from Advanced Thermodynamics by K. Annamali, et. al.

For a binary mixture, pressure and temperature fix the equilibrium vapor and liquid compositions. Thus,
experimental data are often presented in the form of tables of vapor mole fraction 𝑦 and liquid mole fraction 𝑥
for one constituent over a range of temperature 𝑇 for a fixed pressure 𝑃 or over a range of pressure for a fixed
temperature.
For application to distillation (a nearly isobaric process), binary-mixture data are often plotted, for a fixed
pressure, as 𝑦 versus 𝑥, with a line of 45° slope included for reference, and as 𝑇 versus 𝑦 and 𝑥, as shown in
Figs. 13-3 to 13-8 of Perry’s Chemical Engineers Handbook (9 th Ed.). In some binary systems, one of the
components is more volatile than the other over the entire composition range. This is the case in Figs. 13-3 and
13-4 [Perry’s Chemical Engineers Handbook (9th Ed.)] for the benzene-toluene system at pressures of both
101.3 and 202 .6 kPa (1 and 2 atm), where benzene is more volatile than toluene.
For other binary systems, one of the components is more volatile over only a part of the composition range.
Two systems of this type, ethyl acetate–ethanol and chloroform-acetone, are shown in Figs. 13-5 to 13-7.
[Perry’s Chemical Engineers Handbook (9th Ed.)]
Figure 13-5 [Perry’s Chemical Engineers Handbook (9th Ed.)] shows that chloroform is less volatile than
acetone below a concentration of 66 mol% chloroform and that ethyl acetate is more volatile than ethanol below
a concentration of 53 mol% ethyl acetate. Above these concentrations, volatility is reversed. Such mixtures are
known as azeotropic mixtures, and the composition in which the reversal occurs, which is the composition in
which vapor and liquid compositions are equal, is the azeotropic composition, or azeotrope. The azeotropic
liquid may be homogeneous or heterogeneous (two immiscible liquid phases). Non-azeotrope-forming mixtures
such as benzene and toluene in Figs. 13-3 and 13-4 [Perry’s Chemical Engineers Handbook (9 th Ed.)] can be
separated by simple distillation into two essentially pure products. By contrast, simple distillation of azeotropic
mixtures will at best yield the azeotrope and one essentially pure species. The distillate and bottoms products
obtained depend on the feed composition and whether a minimum-boiling (positive) azeotrope is formed as
with the ethyl acetate–ethanol mixture in Fig. 13-6 [Perry’s Chemical Engineers Handbook (9 th Ed.)] or a
maximum-boiling (negative) azeotrope is formed as with the chloroform-acetone mixture in Fig. 13-7 [Perry’s
Chemical Engineers Handbook (9th Ed.)]. For example, if a mixture of 30 mol% chloroform and 70 mol% acetone
is fed to a simple distillation column, such as that shown in Fig. 13-1 [Perry’s Chemical Engineers Handbook (9th

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

Ed.)], operating at 101 .3 kPa (1 atm), the distillate could approach pure acetone and the bottoms could
approach the maximum-boiling azeotrope.
An example of heterogeneous-azeotrope formation is shown in Fig. 13-8 [Perry’s Chemical Engineers
Handbook (9th Ed.)] for the water–normal butanol system at 101.3 kPa . At liquid compositions between 0 and 3
mol% butanol and between 40 and 100 mol% butanol, the liquid phase is homogeneous. Phase splitting into
two separate liquid phases (one with 3 mol% butanol and the other with 40 mol% butanol) occurs for any overall
liquid composition between 3 and 40 mol% butanol. A minimum-boiling heterogeneous azeotrope occurs at
92°C (198°F) when the vapor composition is equal to the overall composition of the two co-existing equilibrium
liquid phases at 25 mol% butanol.
For mixtures containing more than two species, an additional degree of freedom is available for each
additional component. Thus, for a four-component system, the equilibrium vapor and liquid compositions are
fixed only if the pressure, temperature, and mole fractions of two components are set. Representation of
multicomponent vapor-liquid equilibrium data in tabular or graphical form of the type shown earlier for binary
systems is either difficult or impossible. Instead, such data, as well as binary-system data, are commonly
represented in terms of 𝐾 values (vapor-liquid equilibrium ratios), which are defined by

𝑦𝑖
𝐾=
𝑥𝑖

and are correlated empirically or theoretically in terms of temperature, pressure, and phase compositions in the
form of tables, graphs, and equations. The 𝐾 values are widely used in multicomponent distillation calculations,
and the ratio of the 𝐾 values of two species, called the relative volatility,

𝐾𝑖
𝑎𝑖𝑗 =
𝐾𝑗

is a convenient index of the relative ease or difficulty of separating components i and j by distillation. Rarely is
distillation used on a large scale if the relative volatility is less than 1.05, with 𝑖 more volatile than 𝑗.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

B. The Phase Rule. Duhem’s Theorem

The phase rule for nonreacting systems, results from the application of a rule of algebra. Thus, the number of
variables that may be independently fixed in a system at equilibrium is the difference between the total number of
variables that characterize the intensive state of the system and the number of independent equations that can be written
relating those variables.
The intensive state of a 𝑃𝑉𝑇 system containing 𝑁 chemical species and 𝜋 phases in equilibrium is characterized by
its temperature 𝑇, pressure 𝑃, and 𝑁 − 1 mole fractions for each phase. The number of these phase-rule variables is
2 + (𝑁 − 1)(𝜋). The masses or amounts of the phases are not phase-rule variables because they have no influence on
the intensive state of the system.
An independent phase-equilibrium equation may be written connecting intensive variables for each of the 𝑁 species
for each pair of phases present. Thus, the number of independent phase-equilibrium equations is (𝜋 − 1)(𝑁). The
difference between the number of phase-rule variables and the number of independent equations connecting them is
the number of variables that may be independently fixed. Called the degrees of freedom of the system 𝐹, the number
is:
𝐹 = 2 + (𝑁 − 1)(𝜋) − (𝜋 − 1)(𝑁)
Upon reduction, this becomes the phase rule:
𝐹 = 2−𝜋+𝑁 Eq. 1

For reacting system, this equation becomes Eq. 1.1

𝐹 =2−𝜋+𝑁−𝑟

where 𝑟 is the number of independent chemical reactions. In this section, we will only focus on the non-reacting system
which translates to 𝑟 = 0.

Duhem’s theorem is another rule, similar to the phase rule, that applies to the extensive state of a closed system at
equilibrium. When both the extensive state and the intensive state of the system are fixed, the state of the system is said
to be completely determined, and it is characterized not only by the 2 + (𝑁 − 1)𝜋 intensive phase-rule variables but also
by the 𝜋 extensive variables represented by the masses (or mole numbers) of the phases. Thus, the total number of
variables is:
2 + (𝑁 − 1) 𝜋 + 𝜋 = 2 + 𝑁𝜋

For a closed system formed from specified amounts of the chemical species present, a material-balance equation
can be written for each of the 𝑁 chemical species, providing 𝑁 more equations. These, in addition to the (𝜋 − 1)𝑁 phase-
equilibrium equations, represent a number of independent equations equal to:
(𝜋 − 1)𝑁 + 𝑁 = 𝜋𝑁
The difference between the number of variables and the number of equations is therefore:
2 + 𝑁𝜋 − 𝜋 𝑁 = 2

On the basis of this result, Duhem’s theorem is stated as follows:

For any closed system formed from known amounts of prescribed chemical species, the equilibrium state is
completely determined when any two independent variables are fixed.

The two independent variables subject to specification may in general be either intensive or extensive. However,
the number of independent intensive variables is given by the phase rule. Thus, when 𝐹 = 1, at least one of the two
variables must be extensive, and when 𝐹 = 0, both must be extensive.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

[Examples] Equilibrium, Phase Rule, and Duhem’s Theorem

1. Consider a closed vessel of fixed volume containing equal masses of water, ethanol, and toluene at 70°C. Three
phases (two liquid and one vapor) are present.

(a) How many variables, in addition to the mass of each component and the temperature, must be specified to fully
determine the intensive state of the system? How would you classify the system?

(b) How many variables, in addition to the mass of each component and the temperature, must be specified to fully
determine the extensive state of the system? How would you classify the system?

(c) The temperature of the system is increased to 72°C. What, if any, intensive or extensive coordinates of the
system remain unchanged? How would you classify the system?

2. Consider a binary (two-species) system in vapor/liquid equilibrium. Enumerate all of the combinations of intensive
variables that could be fixed to fully specify the intensive state of the system.

For problems 3 through 7, refer to the diagram below of the 𝑃𝑥𝑦 VLE of ethanol(1)/ethyl acetate(2) at 70°C.

3. What type of azeotropy is exhibited by the figure above? Label the parts.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

4. The pressure above a mixture of ethanol and ethyl acetate at 70°C is measured to be 78 kPa. What are the possible
compositions of the liquid and vapor phases?

5. Consider an ethanol(1)/ethyl acetate(2) mixture with x1 = 0.80, initially at 70°C and 80 kPa. Describe the evolution
of phases and phase compositions as the pressure is gradually increased to 100 kPa.

6. What is the composition of the azeotrope for the ethanol(1)/ethyl acetate(2) system? Would this be called a high-
boiling or low-boiling azeotrope?

7. Consider a closed vessel initially containing 1 mol of pure ethyl acetate at 70°C and 86 kPa. Imagine that pure
ethanol is slowly added at constant temperature and pressure until the vessel contains 1 mol ethyl acetate and 9
mol ethanol. Describe the evolution of phases and phase compositions during this process. Comment on the
practical feasibility of carrying out such a process. What sort of device would be required? How would the total
system volume change during this process? At what composition would the system volume reach its maximum
value?

For problems 8 through 12, refer to the diagram below of the 𝑇𝑥𝑦 VLE of chloroform(1)/tetrahydrofuran
(2) at 120 kPa.

8. What type of azeotropy is exhibited by the figure above? Label the parts.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

9. A mixture of chloroform and tetrahydrofuran is heated in a closed system at 120 kPa to a temperature of 75°C, and
two phases are observed to be present. What are the possible compositions of the liquid and vapor phases?

10. Consider a chloroform(1)/tetrahydrofuran(2) mixture with 𝑥1 = 0.20, initially at 70°C and 120 kPa. Describe the
evolution of phases and phase compositions as the temperature is gradually increased to 80°C.

11. Consider a closed vessel initially containing 1 mol of pure tetrahydrofuran at 74°C and 120 kPa. Imagine that pure
chloroform is slowly added at constant temperature and pressure until the vessel contains 1 mol tetrahydrofuran
and 9 mol chloroform. Describe the evolution of phases and phase compositions during this process. Comment on
the practical feasibility of carrying out such a process. What sort of device would be required? How would the total
system volume change during this process? At what composition would the system volume reach its maximum
value?

For problems 10 through 12, refer to the diagram below of the 𝑥𝑦 VLE of ethanol(1)/ethyl acetate(2) and for
chloroform(1)/tetrahydrofuran(2), both at a constant pressure of 1 bar.

12. Label the two systems and the corresponding phases.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

13. What is the composition of the vapor phase in equilibrium with a liquid-phase ethanol(1)/ethyl acetate(2) mixture of
the following compositions at P = 1 bar?
(a) 𝑥1 = 0.1
(b) 𝑥1 = 0.2
(c) 𝑥1 = 0.3
(d) 𝑥1 = 0.45
(e) 𝑥1 = 0.6
(f) 𝑥1 = 0.8
(g) 𝑥1 = 0.9

14. What is the composition of the liquid phase in equilibrium with a vapor-phase ethanol(1)/ethyl acetate(2) mixture of
the following compositions at P = 1 bar?
(a) 𝑦1 = 0.1
(b) 𝑦1 = 0.2
(c) 𝑦1 = 0.3
(d) 𝑦1 = 0.45
(e) 𝑦1 = 0.6
(f) 𝑦1 = 0.8
(g) 𝑦1 = 0.9

15. What is the composition of the vapor phase in equilibrium with a liquid-phase chloroform(1)/tetrahydrofuran(2)
mixture of the following compositions at P = 1 bar?
(a) 𝑥1 = 0.1
(b) 𝑥1 = 0.2
(c) 𝑥1 = 0.3
(d) 𝑥1 = 0.45
(e) 𝑥1 = 0.6
(f) 𝑥1 = 0.8
(g) 𝑥1 = 0.9

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

C. Vapor/Liquid Equilibrium: Qualitative Behavior

Vapor/liquid equilibrium (VLE) is the state of coexistence of liquid and vapor phases. In this qualitative discussion,
we limit consideration to systems comprised of two chemical species because systems of greater complexity cannot be
adequately represented graphically.
For a system comprised of two chemical species (𝑁 = 2), the phase rule becomes 𝐹 = 4 − 𝜋. Because there must
be at least one phase (𝜋 = 1), the maximum number of phase-rule variables that must be specified to fix the intensive
state of the system is three: 𝑃, 𝑇, and one mole (or mass) fraction. All equilibrium states of the system can therefore be
represented in three-dimensional 𝑃-𝑇-composition space. Within this space, the states of pairs of phases coexisting at
equilibrium (𝐹 = 4 − 2 = 2) define surfaces. A schematic three-dimensional diagram illustrating these surfaces for VLE
is shown below.

Fig 1.0. 𝑃𝑇𝑥𝑦 diagram for vapor/liquid equilibrium.

This figure shows schematically the 𝑃-𝑇-composition surfaces that contain the equilibrium states of saturated vapor
and saturated liquid for species 1 and 2 of a binary system. Here, species 1 is the “lighter” or more volatile species. The
lower surface contains the saturated-vapor states; it is the 𝑃-𝑇-𝑦1 surface. The upper surface contains the saturated-
liquid states; it is the 𝑃-𝑇-𝑥1 surface. These surfaces intersect along the lines 𝑅𝐾𝐴𝐶1 and 𝑈𝐵𝐻𝐶2 , which represent the
vapor pressure-vs.-𝑇 curves for pure species 1 and 2. Moreover, the lower and upper surfaces form a continuous
rounded surface across the top of the diagram between 𝐶1 and 𝐶2 , the critical points of pure species 1 and 2; the critical
points of the various mixtures of the two species lie along a line on the rounded edge of the surface between 𝐶1 and 𝐶2 .
This critical locus is defined by the points at which vapor and liquid phases in equilibrium become identical. Because of

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

this geometric feature of an open end (at low 𝑇 and 𝑃) and three closed edges formed by the critical locus and the pure
component vapor pressure curves, the pair of surfaces is often called the “phase envelope.” No stable single phase
exists at points inside the phase envelope. When 𝑇, 𝑃, and the overall composition correspond to a point inside the
envelope, separation into vapor and liquid phases occurs. These have compositions that fall on the lower and upper
surface, respectively, at the system 𝑇 and 𝑃.
The subcooled-liquid region lies above the upper surface of the figure; the superheated-vapor region lies below the
lower surface. The interior space between the two surfaces is the region of coexistence of both liquid and vapor phases.
If one starts with a liquid at conditions represented by point 𝐹 and reduces the pressure at constant temperature and
composition along vertical line 𝐹𝐺, the first bubble of vapor appears at point 𝐿, which lies on the upper surface. Thus, 𝐿
is called a bubblepoint, and the upper surface is called the bubblepoint surface. The state of the vapor bubble in
equilibrium with the liquid at 𝐿 is represented by a point on the lower surface at the temperature and pressure of 𝐿. This
point is indicated by 𝑉. Line 𝐿𝑉 is an example of a tie line, which connects points representing phases in equilibrium.
As the pressure is further reduced along line 𝐹𝐺, more liquid vaporizes until at 𝑊 the process is complete. Thus, 𝑊
lies on the lower surface and represents a state of saturated vapor having the mixture composition. Because 𝑊 is the
point at which the last drops of liquid (dew) disappear, it is called a dewpoint, and the lower surface is called the dewpoint
surface. Continued reduction of pressure produces expansion of the vapor in the superheated vapor region.
Because of the complexity of three-dimensional diagrams, the detailed characteristics of binary VLE are usually
depicted by two-dimensional graphs that display what is seen on various planes that cut the three-dimensional diagram.
The three principal planes, each perpendicular to one of the coordinate axes, are illustrated in the previous figure. Thus,
a vertical plane perpendicular to the temperature axis is outlined as 𝐴𝐸𝐷𝐵𝐿𝐴. The lines on this plane form a 𝑃-𝑥1 -𝑦1
phase diagram at constant 𝑇. If the lines from several such planes are projected on a single parallel plane, a diagram
like the one on the next page is obtained. It shows 𝑃-𝑥1 -𝑦1 plots for three different temperatures. The one for 𝑇𝑎
represents the section of Fig. 1.0. indicated by 𝐴𝐸𝐷𝐵𝐿𝐴. The horizontal lines are tie lines connecting the compositions
of phases in equilibrium. The temperatures 𝑇𝑏 and 𝑇𝑑 lie between the two pure-species critical temperatures identified
by 𝐶1 and 𝐶2 in Fig. 1.0. The curves for these two temperatures therefore do not extend all the way across the diagram.
The mixture critical points are denoted by the letter 𝐶. Each is a tangent point at which a horizontal line touches the
curve. This is so because all tie lines connecting phases in equilibrium are horizontal, and the tie line connecting identical
phases (the definition of a critical point) must therefore be the last such line to cut the diagram.
A horizontal plane passing through Fig. 1.0 perpendicular to the 𝑃 axis is identified by 𝐾𝐽𝐼𝐻𝐿𝐾. Viewed from above,
the lines on this plane represent a 𝑇-𝑥1 -𝑦1 diagram. When lines for several pressures are projected on a parallel plane,
the resulting diagram is that shown in Fig. 2.0 (𝑏). This figure is analogous to Fig. 2.0 (𝑎), except that it represents phase
behavior for three constant pressures, 𝑃𝑎 , 𝑃𝑏 , and 𝑃𝑑 . The one for 𝑃𝑎 represents the section of Fig. 1.0 indicated by
𝐾𝐽𝐼𝐻𝐿𝐾. Pressure 𝑃𝑏 lies between the critical pressures of the two pure species at points 𝐶1 and 𝐶2 . Pressure 𝑃𝑑 is
above the critical pressures of both pure species; therefore, the 𝑇-𝑥1 -𝑦1 diagram appears as an “island.” Similar 𝑃-𝑥1 -
𝑦1 behavior [Fig. 2.0 (𝑎)] is unusual. Note that on the 𝑃-𝑥1 -𝑦1 plot, the upper curve represents the saturated liquid and
the lower curve represents the saturated vapor, but for the 𝑇-𝑥1 -𝑦1 , the upper curve represents saturated vapor and the
lower curve represents saturated liquid. To avoid confusion, one must keep in mind the fact that vapors form at high 𝑇
and low 𝑃.

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Fig. 2.0. (𝑎) 𝑃𝑥𝑦 diagram for three temperatures. (𝑏) 𝑇𝑥𝑦 diagram for three pressures.
Saturated liquid (bubble line); - - - - Saturated vapor (dew line)

Other possible plots include vapor mole fraction 𝑦1 vs. liquid mole fraction 𝑥1 for either the constant-𝑇 conditions of
Fig. 2.0 (𝑎) or the constant-𝑃 conditions of Fig. 2.0 (𝑏). Such plots reduce the dimensionality of the representation further
by representing the coexisting phases by a single curve, with no information about 𝑇 or 𝑃, rather than as a pair of curves
bounding a two-dimensional region. Thus, they convey less information than a 𝑇-𝑥1 -𝑦1 or 𝑃-𝑥1 -𝑦1 plot, but are more
convenient for rapidly relating phase compositions at a fixed 𝑇 or 𝑃.
The third plane identified in Fig. 1.0, vertical and perpendicular to the composition axis, passes through points
𝑆𝐿𝑀𝑁 and 𝑄. When projected on a parallel plane, the lines from several planes form a diagram such as that shown in
Fig. 3.0. This is the 𝑃𝑇 diagram; lines 𝑈𝐶2 and 𝑅𝐶1 are vapor-pressure curves for the pure species, identified by the
same letters as in Fig. 1.0. Each interior loop represents the 𝑃𝑇 behavior of saturated liquid and of saturated vapor for
a system of fixed overall composition. The different loops are for different compositions. Clearly, the 𝑃𝑇 relation for
saturated liquid is different from that for saturated vapor of the same composition. This is in contrast to the behavior of
a pure species, for which the bubble and dew lines coincide. At points 𝐴 and 𝐵 in Fig. 3.0, saturated-liquid and saturated-
vapor lines intersect. At such points a saturated liquid of one composition and a saturated vapor of another composition
have the same 𝑇 and 𝑃, and the two phases are therefore in equilibrium. The tie lines connecting the coinciding points
at 𝐴 and at 𝐵 are perpendicular to the 𝑃𝑇 plane, as illustrated by the tie line 𝐿𝑉 in Fig. 1.0.

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Fig. 3.0. PT diagram for several compositions Fig 4.0. Portion of a PT diagram in the critical region

1. Critical Points of Binary Mixtures and Retrograde Condensation

The critical point of a binary mixture occurs where the nose of a loop in Fig. 3.0 is tangent to the envelope
curve. Put another way, the envelope curve is the critical locus. One can verify this by considering two closely
adjacent loops and noting what happens to the point of intersection as their separation becomes infinitesimal. Figure
3.0 shows that the location of the critical point on the nose of the loop varies with composition. For a pure species
the critical point is the highest temperature and highest pressure at which vapor and liquid phases can coexist, but
for a mixture it is in general neither. Therefore, under certain conditions a condensation process occurs as the result
of a reduction in pressure.
Consider the enlarged nose section of a single 𝑃𝑇 loop shown in Fig. 4.0. The critical point is at 𝐶. The
points of maximum pressure and maximum temperature are identified as 𝑀𝑃 and 𝑀𝑇, respectively. The interior
dashed curves indicate the fraction of the overall system that is liquid in a two-phase mixture of liquid and vapor. To
the left of the critical point 𝐶 a reduction in pressure along a line such as 𝐵𝐷 is accompanied by vaporization of
liquid from bubblepoint to dewpoint, as would be expected. However, if the original condition corresponds to point
𝐹, a state of saturated vapor, liquefaction occurs upon reduction of the pressure and reaches a maximum at point
𝐺, after which vaporization takes place until the dewpoint is reached at point 𝐻. This phenomenon is called
retrograde condensation. It can be important in the operation of deep natural-gas wells where the pressure and
temperature in the underground formation may be at conditions represented by point 𝐹. If the pressure at the
wellhead is that of point 𝐺, the product stream from the well is an equilibrium mixture of liquid and vapor. Because
the less-volatile species are concentrated in the liquid phase, significant separation is accomplished. Within the
underground formation itself, the pressure tends to drop as the gas supply is depleted. If not prevented, this leads
to the formation of a liquid phase and a consequent reduction in the production of the well. Repressuring is therefore
a common practice; that is, lean gas (gas from which the less-volatile species have been removed) is returned to
the underground reservoir to maintain an elevated pressure.
A 𝑃𝑇 diagram for the ethane(1)/n-heptane(2) system is shown in Fig. 5.0, and a 𝑦1 -𝑥1 diagram for several
pressures for the same system appears in Fig. 6.0. By convention, one typically plots as 𝑦1 and 𝑥1 the mole fractions

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of the more volatile species in the mixture. The maximum and minimum concentrations of the more volatile species
obtainable by distillation at a given pressure are indicated by the points of intersection of the appropriate 𝑦1 -𝑥1 curve
with the diagonal, for at these points the vapor and liquid have the same composition. They are in fact mixture critical
points, unless 𝑦1 = 𝑥1 = 0 or 𝑦1 = 𝑥1 = 1. Point 𝐴 in Fig. 6.0 represents the composition of the vapor and liquid
phases at the maximum pressure at which the phases can coexist in the ethane/n-heptane system. The composition
is about 77 mol-% ethane and the pressure is about 87.1 bar. The corresponding point on Fig. 5.0 is labeled 𝑀.
A complete set of consistent phase diagrams for this system has been prepared by Barr-David.

Fig 5.0. Ethane/n-heptane 𝑃𝑇 diagram. (Adapted from F. H. Barr-David, “Notes on phase relations of binary
mixtures in the region of the critical point, AIChE Journal, Vol 2, Issue 3, September 1956, pp. 426–427.)

The 𝑃𝑇 diagram of Fig. 5.0. is typical for mixtures of nonpolar substances such as hydrocarbons. A 𝑃𝑇
diagram for a very different kind of system, methanol(1)/benzene(2), is shown in Fig. 7.0. The nature of the curves
in this figure suggests how difficult it can be to predict phase behavior for species so dissimilar as methanol and
benzene, especially at conditions near the mixture critical point.

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Fig. 6.0. Ethane/n-heptane 𝑦𝑥

diagram. (Adapted from F. H. Barr-
David, “Notes on phase relations of
binary mixtures in the region of the
critical point, AIChE Journal, Vol 2,
Issue 3, September 1956, pp. 426–
427.)

Figure 7.0. Methanol/benzene 𝑃𝑇 diagram. (Adapted

from J. M. Skaates and W. B. Kay, “The phase
relations of binary systems that form azeotropes,”
Chemical Engineering Science, Vol 19, Issue 7, July
1964, pp. 431–444.)

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2. Low-Pressure Vapor/Liquid Equilibrium Examples

Although VLE in the critical region is of considerable importance in the petroleum and natural-gas industries, most
chemical processing is accomplished at much lower pressures. Figures 8.0 and 9.0 display common types of 𝑃𝑥𝑦 and
𝑇𝑥𝑦 behavior at conditions well removed from the critical region.
Figure 8.0 (𝑎) shows data for tetrahydrofuran(1)/carbon tetrachloride(2) at 30°C. When the liquid phase behaves as
an ideal solution, and the vapor phase behaves as an ideal-gas-state mixture, then the system is said to follow Raoult’s
law. This is the simplest model of vapor/liquid equilibrium. For a system that obeys Raoult’s law, the 𝑃-𝑥1 or bubblepoint
curve is a straight line connecting the vapor pressures of the pure species. In Fig. 8.0 (𝑎), the bubblepoint curve lies
below the linear 𝑃-𝑥1 relation characteristic of Raoult’s-law behavior. When such negative departures from linearity
become sufficiently large, relative to the difference between the two pure-species vapor pressures, the P-x1 curve
exhibits a minimum, as illustrated in Fig. 8.0 (𝑏) for the chloroform(1)/tetrahydrofuran(2) system at 30°C. This figure
shows that the 𝑃-𝑦1 curve also has a minimum at the same point. Thus, at this point where 𝑥1 = 𝑦1 the dewpoint and
bubblepoint curves are tangent to the same horizontal line. A boiling liquid of this composition produces a vapor of
exactly the same composition, and the liquid therefore does not change in composition as it evaporates. No separation
of such a constant-boiling solution is possible by distillation. The term azeotrope is used to describe this state.
The data for furan(1)/carbon tetrachloride(2) at 30°C shown by Fig. 8.0 (𝑐) provide an example of a system for which
the 𝑃-𝑥1 curve lies above the linear 𝑃-𝑥1 relation. The system shown in Fig. 8.0 (𝑑) for ethanol(1)/toluene(2) at 65°C
exhibits positive departures from linearity large enough to cause a maximum in the 𝑃-𝑥1 curve. This state is a maximum-
pressure azeotrope. Just as for the minimum-pressure azeotrope, the vapor and liquid phases in equilibrium have the
identical composition.
Appreciable negative departures from 𝑃-𝑥1 linearity reflect liquid-phase intermolecular attractions that are stronger
between unlike than between like pairs of molecules. Conversely, appreciable positive departures result for solutions
for which liquid-phase intermolecular interactions between like molecules are stronger than between unlike ones. In this
latter case the forces between like molecules may be so strong as to prevent complete miscibility, and the system then
forms two separate liquid phases over a range of compositions, as described later in this chapter.
Because distillation processes are carried out more nearly at constant pressure than at constant temperature, 𝑇-𝑥1 -
𝑦1 diagrams of data at constant 𝑃 are of great practical interest. The four such diagrams corresponding to those of Fig.
8.0 are shown for atmospheric pressure in Fig. 9.0. Note that the dewpoint (𝑇-𝑦1 ) curves lie above the bubblepoint (𝑇-
𝑥1 ) curves. Moreover, the minimum-pressure azeotrope of Fig. 8.0 (𝑏) appears as a maximum-temperature (or
maximum-boiling) azeotrope on Fig. 9.0 (𝑏). An analogous correspondence exists between Figs. 8.0 (𝑑) and 9.0 (𝑑). The
𝑦1 -𝑥1 diagrams at constant 𝑃 for the same four systems are shown in Fig. 10.0. The point at which a curve crosses the
diagonal line of the diagram represents an azeotrope, for at such a point 𝑦1 = 𝑥1 . Such 𝑦𝑥 diagrams are useful for
qualitative analysis of distillation processes. The greater the separation between the 𝑦𝑥 curve and the diagonal line, the
easier the separation. Examination of Fig. 10.0 immediately shows that complete separation of both
tetrahydrofuran/carbon tetrachloride mixtures and furan/carbon tetrachloride mixtures by distillation is possible, and
that the separation of the furan/carbon tetrachloride mixture will be much easier to accomplish. Likewise, the diagram
shows that the other two systems form azeotropes and cannot be completely separated by distillation at this pressure.

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Figure 8.0. 𝑃𝑥𝑦 diagrams at constant 𝑇: (𝑎) tetrahydrofuran(1)/carbon tetrachloride(2) at 30°C; (𝑏)
chloroform(1)/tetrahydrofuran(2) at 30°C; (𝑐) furan(1)/carbon tetrachloride(2) at 30°C; (𝑑)
ethanol(1)/toluene(2) at 65°C. Dashed lines: 𝑃𝑥 relation for Raoult’s law.

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Figure 9.0. 𝑇𝑥𝑦 diagrams at 101.3 kPa: (𝑎) tetrahydrofuran(1)/carbon tetrachloride(2); (𝑏) chloroform
(1)/tetrahydrofuran(2); (𝑐) furan(1)/carbon tetrachloride(2); (𝑑) ethanol(1)/toluene(2).

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Figure 10.0. 𝑦𝑥 curves at 101.3 kPa: (𝑎) tetrahydrofuran(1)/carbon tetrachloride(2);

(𝑏) chloroform(1)/tetrahydrofuran(2); (𝑐) furan(1)/carbon tetrachloride(2); (𝑑) ethanol(1)/toluene(2).

3. Evaporation of a Binary Mixture at Constant Temperature

The 𝑃-𝑥1 -𝑦1 diagram of Fig. 11.0 describes the behavior of acetonitrile(1)/nitromethane(2) at 75°C. The line
labeled 𝑃-𝑥1 represents states of saturated liquid; the subcooled-liquid region lies above this line. The curve labeled
𝑃-𝑦1 represents states of saturated vapor; the superheated- vapor region lies below this curve. Points lying between
the saturated-liquid and saturated-vapor lines are in the two-phase region, where saturated liquid and saturated
vapor coexist in equilibrium. The 𝑃-𝑥1 and 𝑃-𝑦1 lines meet at the edges of the diagram, where saturated liquid and
saturated vapor of the pure species coexist at the vapor pressures 𝑃1𝑠𝑎𝑡 and 𝑃2𝑠𝑎𝑡 .
To illustrate the nature of phase behavior in this binary system, we follow the course of a constant-
temperature expansion process on the 𝑃-𝑥1 -𝑦1 diagram. We imagine that a subcooled liquid mixture of 60 mol-%
acetonitrile and 40 mol-% nitromethane exists in a piston/cylinder arrangement at 75°C. Its state is represented by
point 𝑎 in Fig. 11.0. Withdrawing the piston slowly enough reduces the pressure while maintaining the system at
equilibrium at 75°C. Because the system is closed, the overall composition remains constant during the process,
and the states of the system as a whole fall on the vertical line descending from point 𝑎. When the pressure reaches
the value at point 𝑏, the system is saturated liquid on the verge of vaporizing. A minuscule further decrease in
pressure produces a bubble of vapor, represented by point 𝑏′. The two points 𝑏 and 𝑏′ together represent the
equilibrium state. Point 𝑏 is a bubblepoint, and the 𝑃-𝑥1 line is the locus of bubblepoints.
As the pressure is further reduced, the amount of vapor increases and the amount of liquid decreases, with
the states of the two phases following paths 𝑏′𝑐 and 𝑏𝑐′, respectively. The dotted line from point 𝑏 to point 𝑐
represents the overall states of the two-phase system. Finally, as point 𝑐 is approached, the liquid phase,
represented by point 𝑐′, has almost disappeared, with only droplets (dew) remaining. Point 𝑐 is therefore a dewpoint,

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and the 𝑃-𝑦1 curve is the locus of dewpoints. Once the dew has evaporated, only saturated vapor at point 𝑐 remains,
and further pressure reduction leads to superheated vapor at point 𝑑.
During this process, the volume of the system would first remain nearly constant in the subcooled liquid
region from point 𝑎 to point 𝑏. From point 𝑏 to point 𝑐, the volume would increase dramatically, but not
discontinuously. For a pure substance, the phase transition would occur at a single pressure (the vapor pressure),
but for a binary mixture it occurs over a range of pressures. Finally, from point 𝑐 to point 𝑑 the volume would be
approximately inversely proportional to pressure. Similarly, the heat flow required to maintain constant temperature
during pressure reduction would be negligible in the subcooled liquid region and small in the superheated vapor
region, but would be substantial between points 𝑏 and 𝑐, where the latent heat of vaporization of the mixture must
be supplied.

Figure 11.0. 𝑃𝑥𝑦 diagram for acetonitrile (1)/nitromethane (2) at 75°C.

4. Evaporation of a Binary Mixture at Constant Pressure

Figure 12.0 is the 𝑇-𝑥1 -𝑦1 diagram for the same system at a constant pressure of 70 kPa. The 𝑇-𝑦1 curve
represents states of saturated vapor, with states of superheated vapor lying above it. The 𝑇-𝑥1 curve represents
states of saturated liquid, with states of subcooled liquid lying below it. The two-phase region lies between these
curves.

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With reference to Fig. 12.0, consider a constant-pressure heating process leading from a state of subcooled
liquid at point 𝑎 to a state of superheated vapor at point 𝑑. The path shown on the figure is for a constant overall
composition of 60 mol-% acetonitrile. The temperature of the liquid increases as a result of heating from point 𝑎 to
point 𝑏, where the first bubble of vapor appears. Thus, point 𝑏 is a bubblepoint, and the 𝑇-𝑥1 curve is the locus of
bubblepoints.
As the temperature is further increased, the amount of vapor increases and the amount of liquid decreases,
with the states of the two phases following paths 𝑏′𝑐 and 𝑏𝑐′, respectively. The dotted line from point 𝑏 to point 𝑐
represents the overall states of the two-phase system. Finally, as point 𝑐 is approached, the liquid phase,
represented by point 𝑐′, has almost disappeared, with only droplets (dew) remaining. Point 𝑐 is therefore a dewpoint,
and the 𝑇-𝑦1 curve is the locus of dewpoints. Once the dew has evaporated, only saturated vapor at point 𝑐 remains,
and further heating leads to superheated vapor at point 𝑑.
The change in volume and the heat flows in this process would be similar to those for the constant-
temperature evaporation described previously, with a dramatic volume change as the two-phase region is traversed.
Above and below the two-phase region, the heat flow and temperature change would be related by the heat
capacities of the vapor and liquid, respectively. Within the two-phase region, the apparent heat capacity would be
much higher, as it would include both a sensible heat component, required to increase the temperature of both
phases, and a larger latent-heat component, required for transfer of material from the liquid to the vapor phase.

Figure 12.0. 𝑇𝑥𝑦 diagram for acetonitrile(1)/nitromethane (2) at 70 kPa

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D. Simple Models of Vapor/Liquid Equilibrium

Because of the practical importance of distillation as a means of separating and purifying chemical species, VLE is
the most studied type of phase equilibrium. Approaches developed for analyzing VLE also provide the foundation for
most analyses of liquid/liquid equilibrium (LLE), vapor/liquid/liquid equilibrium (VLLE), and combined phase and reaction
equilibrium.
The analysis of VLE problems begins by developing a general formulation of such problems in terms of vapor-phase
fugacity coefficients and liquid-phase activity coefficients. For VLE at low pressure, where the gas phase approaches
the ideal-gas state, simplified versions of this formulation are applicable. For those conditions, activity coefficients can
be obtained directly from experimental VLE data. These can then be fit to mathematical models. Finally, the models can
be used to predict activity coefficients and VLE behavior for situations where experiments have not been performed.
The following models will deal on VLE calculations in simplest terms.

1. Raoult’s Law

Figure 13.0 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, it
reduces to its simplest possible form of VLE model, Raoult’s law:

𝑦𝑖 𝑃 = 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡 (𝑖 = 1, 2,3, … 𝑁) Eq. 2

where 𝑥𝑖 is a liquid-phase mole fraction, 𝑦𝑖 is a vapor-phase mole fraction, and 𝑃𝑖𝑠𝑎𝑡 is the vapor pressure of pure
species 𝑖 at the temperature of the system. The product 𝑦𝑖 𝑃 is the partial pressure of species 𝑖 in the vapor phase.
Note that the only thermodynamic function to survive here is the vapor pressure of pure-species 𝑖, suggesting its
primary importance in VLE calculations.
The ideal-gas-state assumption means that Raoult’s law is limited in application from low to moderate pressures.
The ideal-solution assumption implies that Raoult’s law can have approximate validity only when the species that
comprise the system are chemically similar. Just as the ideal-gas state serves as a standard to which real-gas
behavior may be compared, the ideal solution represents a standard to which real-solution behavior may be
compared. Liquid-phase ideal-solution behavior is promoted when the molecular species are not too different in
size and have the same chemical nature. Thus, a mixture of isomers, such as
ortho-, meta-, and para-xylene, conforms very closely to ideal-solution behavior.
So do mixtures of adjacent members of a homologous series, as for example, n-
hexane/n-heptane, ethanol/propanol, and benzene/toluene. Other examples are
acetone/acetonitrile and acetonitrile/nitromethane. Figures 11.0 and 12.0 for the
latter system are constructed to represent Raoult’s law.
The simple model of VLE provides a realistic description of actual behavior
for a relatively small class of systems. Nevertheless, it 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 each
species to be “subcritical,” i.e., at a temperature below its critical temperature.
Raoult’s law cannot be applied to situations for which the temperature exceeds
the critical temperature of one or more species in the mixture

Fig. 13.0. Schematic representation of VLE. The temperature 𝑇 and pressure 𝑃 are uniform throughout the vessel
and can be measured with appropriate instruments. Vapor and liquid samples may be withdrawn for analysis, and
this provides experimental values for mole fractions in the vapor {𝑦𝑖 } and mole fractions in the liquid {𝑥𝑖 }.

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Bubblepoint and Dewpoint Calculations with Raoult’s Law

Although VLE problems with other combinations of variables are possible, engineering interest centers on
dewpoint and bubblepoint calculations, of which there are four types:

BUBL P: Calculate {𝑦𝑖 } and 𝑃, given {𝑥𝑖 } and 𝑇

DEW P: Calculate {𝑥𝑖 } and 𝑃, given {𝑦𝑖 } and 𝑇
BUBL T: Calculate {𝑦𝑖 } and 𝑇, given {𝑥𝑖 } and 𝑃
DEW T: Calculate {𝑥𝑖 } and 𝑇, given {𝑦𝑖 } and 𝑃

In each case the name indicates the quantities to be calculated: either a BUBL (vapor) or a DEW (liquid)
composition and either 𝑃 or 𝑇. Thus, one must specify either the vapor-phase or the liquid-phase composition and
either 𝑃 or 𝑇, thus fixing 1 + (𝑁 − 1) or 𝑁 intensive variables, exactly the number of degrees of freedom 𝐹 required
by the phase rule for vapor/liquid equilibrium.

Because ∑𝑖𝑦𝑖 = 1, this yields to:

𝑃 = ∑ 𝑥𝑖 𝑃𝑖𝑠𝑎𝑡
Eq. 3
𝑖

This equation finds direct application in bubblepoint calculations, where the vapor-phase composition is
unknown.
For a binary system with 𝑥2 = 1 − 𝑥1 ,

𝑃 = 𝑃2𝑠𝑎𝑡 + (𝑃1𝑠𝑎𝑡 − 𝑃2𝑠𝑎𝑡 )𝑥1 Eq. 4

and a plot of 𝑃 vs. 𝑥1 at constant temperature is a straight line connecting 𝑃2𝑠𝑎𝑡 at 𝑥1 = 0 with 𝑃1𝑠𝑎𝑡 at 𝑥1 = 1. The 𝑃𝑥𝑦
diagram of Fig. 11.0 for acetonitrile(l)/nitromethane(2) shows this linear relation.

[Examples] Raoult’s Law

Direction. Use the Perry’s Handbook to solve/find the values, unless otherwise specified.

Example 1:
Calculate the bubble point pressure of a pure liquid water at 300°C.

Example 2:
Calculate the dew point temperature of a pure water vapor that starts to condense at 78 kPa.

Example 3:
At 200 kPa, determine the dew point temperature of pure water vapor, bubble point temperature of pure liquid
water, and its boiling point.

Example 4:
Assuming the validity of Raoult’s law, do the following calculations for the benzene(1)/toluene(2) system:
(a) Given 𝑥1 = 0.33 and 𝑇 = 100°C, find 𝑦1 and 𝑃.
(b) Given 𝑦1 = 0.33 and 𝑃 = 120 kPa, find 𝑥1 and 𝑇.
(c) Given 𝑇 = 105°C and 𝑃 = 120 kPa, find 𝑥1 and 𝑦1 .
(e) For part (c), if the overall mole fraction of benzene is 𝑧1 = 0.33, what molar fraction of the two-phase system is
vapor?

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ChE 408 | PRELIMINARY MODULE

(g) Why is Raoult’s law likely to be an excellent VLE model for this system at the stated (or computed) conditions?

Example 5:
Assuming Raoult’s law to apply to the system n-pentane(1)/n-heptane(2), what are the values of 𝑥1 and 𝑦1 at 𝑡 =
55°𝐶 and 𝑃 = 0.5(𝑃1𝑠𝑎𝑡 + 𝑃2𝑠𝑎𝑡 )?

Example 6:
Of the following binary liquid/vapor systems, which can be approximately modeled by Raoult’s law? For those that
cannot, why not?
(a) Benzene/toluene at 1(atm).
(b) n-Hexane/n-heptane at 25 bar.
(c) Hydrogen/propane at 200 K.
(d) Iso-octane/n-octane at 100°C.
(e) Water/n-decane at 1 bar.

Example 7:
A solution consists of 40% methanol (species 1) and 60% water (species 2). Assume that methanol is completely
miscible in water and that the solution behaves according to Raoult’s Law. The saturation pressure correlations
for the pure components are:
4719.2
ln 𝑃1𝑠𝑎𝑡 (𝑚𝑚 𝐻𝑔) = 20.61 −
𝑇, 𝐾
5205.2
ln 𝑃2𝑠𝑎𝑡 (𝑚𝑚 𝐻𝑔) = 20.60 −
𝑇, 𝐾

If the temperature is maintained at 20ºC, at what pressure will a vapor bubble begin to form?
At this pressure and at 20°C, determine the quality W, i.e., the ratio of moles of vapor in the vapor-liquid mixture,
and the vapor-phase composition.
At 20°C, what is the pressure at which virtually the entire liquid has vaporized? Determine the liquid composition
and the quality at this pressure.

Example 8:
A methanol(1)/ethanol(2) system is analyzed at a total system pressure of 1 atm. Using the Antoine’s equation, and
assuming the system behaves according to Raoult’s Law, determine the point (temperature) and the fractions of the
rest of the system where the first bubble will appear when
(a) 𝑥1 = 0.65
(b) 𝑦2 = 0.23
Is the temperature when the first bubble appears the same as the temperature when the first drop of condensate
appears?

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ChE 408 | PRELIMINARY MODULE

2. Henry’s Law

The Lewis/Randall rule applies to each species in an ideal solution at all conditions of temperature, pressure,
and composition. It shows that the fugacity of each species in an ideal solution is proportional to its mole fraction;
the proportionality constant is the fugacity of pure species 𝑖 in the same physical state as the solution and at the
same 𝑇 and 𝑃. The solid lines in both Figs. 14.0 and 15.0, representing experimental values of 𝑓̂𝑖𝑙 , become tangent
to the Lewis/Randall-rule lines at 𝑥𝑖 = 1. This is a consequence of the Gibbs/Duhem equation, as will be shown
presently. In the other limit, 𝑥𝑖 → 0, 𝑓̂𝑖𝑙 becomes zero. Thus, the ratio 𝑓̂𝑖𝑙 /𝑥𝑖 is indeterminate in this limit, and
application of l’Hôpital’s rule yields:

𝑓̂𝑖𝑙 𝑑𝑓̂𝑖𝑙
lim = lim = 𝐻𝑖
𝑥→0 𝑥𝑖 𝑥→0 𝑑𝑥𝑖

𝐻𝑖 is known as the Henry’s constant and the equation of the tangent line expresses Henry’s law:

𝑓̂𝑖𝑙 = 𝑥𝑖 𝐻𝑖 Eq. 5

Figure 14.0. Fugacities for methyl ethyl Figure 15.0. Composition dependence of
ketone(l)/toluene(2) at 50°C. The dashed lines liquid-phase fugacities for species 𝑖 in a binary
represent the Lewis/Randall rule. solution.

Applicable in the limit as 𝑥𝑖 → 0, it is also of approximate validity for small values of 𝑥𝑖 . For a system of air in
equilibrium with liquid water, the mole fraction of water vapor in the air is found from Raoult’s law applied to the
water with the assumption that the water is essentially pure. Thus, Raoult’s law for the water (species 2) becomes
𝑦2 𝑃 = 𝑃2𝑠𝑎𝑡 . At 25°C and atmospheric pressure, this equation yields:

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ChE 408 | PRELIMINARY MODULE

𝑃2𝑠𝑎𝑡 3.166
𝑦2 = = = 0.0312
𝑃 101.33

where the pressures are in kPa, and 𝑃2𝑠𝑎𝑡 comes from the steam tables.
Calculation of the mole fraction of air dissolved in the water is accomplished with Henry’s law, applied here for
a pressure low enough that the vapor phase is in its ideal-gas state. Values of 𝑖 come from experiment, and Table
13.2 lists values at 25°C for a few gases dissolved in water. For the air/water system at 25°C and atmospheric
pressure, Henry’s Law applied to air (species 1) with 𝑦1 = 1 − 0.0312 = 0.9688 yields:

𝑦𝑖 𝑃 (0.9688)(1.0133)
𝑥𝑖 = = = 1.35 × 10−5
𝐻𝐼 72950

This result justifies the assumption that the water approaches purity.

Henry’s law applies to a species as it approaches infinite dilution in a binary solution, and the
Gibbs/Duhem equation ensures validity of the Lewis/Randall rule for the other species as it approaches
purity.

For species whose critical 𝑇 is less than the application temperature, this is not appropriate. For example, air
dissolved in water at equilibrium (Air 𝑇𝐶 = 132.2 𝐾 = −140.95°𝐶 is much lower than 25°𝐶). Henry’s constant can be
found on Perry’s Handbook 9th Edition pages 2-89 to 2-90. Likewise, the thermodynamic properties for water can
be found at page 2-262.

[Examples] Henry’s Law

Direction: Use the Perry’s Chemical Engineers Handbook to obtain additional data otherwise specified.

Example 1:
Determine the Henry’s constant of ethane at 25°C in water.

Example 2:
Calculate the Henry’s constant and the mole fraction of helium at 30°C in water.

Example 3:
Assuming that carbonated water contains only CO 2(1) and H2O(2), determine the compositions of the vapor and
liquid phases in a sealed can of “soda” at 25°C if the pressure inside the can is 5 bar. Assume that this species
approach infinite dilution.

Example 4:
Rework example 3 using Raoult’s Law and compare the answers.

Example 5:
At 𝑦2 = 0.9966, determine if it is possible to compute for the bubble point temperature of methane-H2O system at a
total pressure of 1 atm. Assume methane approaches infinite dilution in water.

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ChE 408 | PRELIMINARY MODULE

Example 6:
A concentrated binary solution containing mostly species 2 (but 𝑥2 ≠ 1) is in equilibrium with a vapor phase
containing both species 1 and 2. The pressure of this two-phase system is 1 bar; the temperature is 25°C. At this
temperature, 𝐻1 = 200 bar and 𝑃2𝑠𝑎𝑡 = 0.10 bar. Determine good estimates of 𝑥1 and 𝑦1 .

Example 7:
Air, even more than carbon dioxide, is inexpensive and nontoxic. Why is it not the gas of choice for making soda
water and (cheap) champagne effervescent?

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ChE 408 | PRELIMINARY MODULE

E. Vapor/Liquid Equilibrium by Modified Raoult’s Law

Of the qualifications that lead to Raoult’s law, the one least often reasonable is the supposition of solution ideality
for the liquid phase. Real solution behavior is reflected by values of activity coefficients that differ from unity. When
𝛾𝑖 is retained in the equilibrium equation, the result is the modified Raoult’s law:

𝛾𝑖 𝑃𝑖𝑠𝑎𝑡
𝑦𝑖 𝑃 = 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 , 𝐾𝑖 = 𝑖 = 1,2, … , 𝑁 Eq. 6
𝑃

This means that we take into account the liquid-phase deviations from ideal solution behavior, producing a much
more reasonable and broadly applicable description of VLE behavior. This equation provides for entirely satisfactory
representation of the VLE behavior of a great variety of systems at low to moderate pressures. The activity coefficient
𝛾 in this section will be given in simpler terms rather than more complex correlations in the future discussions.
Because ∑ 𝑦𝑖 = 1, the equation can be rewritten to express the overall sum of species:

𝑃 = ∑ 𝑥𝑖 𝛾𝑖 𝑃𝑖𝑠𝑎𝑡 Eq. 7
𝑖

Alternatively, the pressure can be expressed in terms of 𝑦𝑖 :

1
𝑃= Eq. 8
∑𝑖 𝑦𝑖 /𝛾𝑖 𝑃𝑖𝑠𝑎𝑡

Bubblepoint and dewpoint calculations made with the modified Raoult’s law are only a bit more complex than
the same calculations made with Raoult’s law. In particular, bubblepoint pressure calculations are straightforward
because the specified liquid composition allows immediate evaluation of the activity coefficients. Dewpoint pressure
calculations require an iterative solution process because the unknown liquid-phase composition is required to
evaluate the activity coefficients. Bubblepoint and dewpoint temperature calculations are further complicated by the
temperature dependence of the activity coefficients, along with the temperature dependence of the vapor pressures,
but the same iterative or trial-and-error approaches used with Raoult’s law calculations can still be employed.

[Examples] Modified Raoult’s Law

Direction: Use the Perry’s Handbook to obtain additional data, otherwise specified.

Example 1:
For the system methanol(1)/methyl acetate(2), the following equations provide a reasonable correlation for the
activity coefficients:
ln 𝛾1 = 𝐴𝑥22 ln 𝛾2 = 𝐴𝑥12 where 𝐴 = 2.771 − 0.00523𝑇

In addition, the following Antoine equations provide vapor pressures:

3643.31 2665.54
ln 𝑃1𝑠𝑎𝑡 = 16.59158 − ln 𝑃2𝑠𝑎𝑡 = 14.25326 −
𝑇 − 33.424 𝑇 − 53.424
where 𝑇 is in K and the vapor pressures are in kPa. Assume the validity of Eq. 6., find:
(a) 𝑃 and {𝑦𝑖 } for 𝑇 = 318.15 K and 𝑥1 = 0.25
(b) 𝑇 and {𝑥𝑖 } for 𝑃 = 101.33 kPa and 𝑦1 = 0.40
(c) The azeotropic pressure and the azeotropic composition for 𝑇 = 318.15 K

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ChE 408 | PRELIMINARY MODULE

Example 2:
For the system acetone(1)/n-hexane(2), vapor pressures are given by the Antoine equation:
𝐵𝑖
ln 𝑃𝑖𝑠𝑎𝑡 /𝑘𝑃𝑎 = 𝐴𝑖 −
𝑇/𝐾 + 𝐶𝑖
with parameters

𝑖 𝐴𝑖 𝐵𝑖 𝐶𝑖
1 14.3145 2756.22 −45.090
2 13.8193 2696.04 −48.833

Activity coefficients are given by Wilson equation:

ln 𝛾1 = − ln(𝑥1 + 𝑥2 Λ12 ) + 𝑥2 𝜆
ln 𝛾2 = − ln(𝑥2 + 𝑥1 Λ21 ) − 𝑥1 𝜆

Λ12 Λ21 𝑉𝑗 −𝑎1𝑗

𝜆= − ; Λ𝑖𝑗 = 𝑒 𝑅𝑇
𝑥1 + 𝑥2 Λ12 𝑥2 + 𝑥1 Λ21 𝑉𝑖

with parameters from VL Data Collection of Gmehling et al.,

𝑎12 𝑎21 𝑉1 𝑉2
cal/mol cal/mol cm3/mol cm3/mol
985.05 453.57 74.05 131.61

(a) Find 𝑦1 and 𝑃, given 𝑥1 = 0.40 and 𝑇 = 325.15 K.

(b) Find 𝑥1 and 𝑃, given 𝑦1 = 0.40 and 𝑇 = 325.15 K.
(c) Find 𝑦1 and 𝑇, given 𝑥1 = 0.32 and 𝑃 = 80 kPa.
(d) Find 𝑥1 and 𝑇, given 𝑦1 = 0.60 and 𝑃 = 101.33 kPa.
(e) Find the azeotropic conditions (𝑇, 𝑃, 𝑥, and 𝑦).

Example 3:
A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium at temperature T. The overall
mole fraction of species 1 in the system is 𝑧1 = 0.65. At temperature 𝑇, ln 𝛾1 = 0.67𝑥22 ; ln 𝛾2 = 0.67𝑥12 ; 𝑃1𝑠𝑎𝑡 =
32.27 kPa; and 𝑃2𝑠𝑎𝑡 = 73.14 kPa. Assuming the validity of Eq. 7.

(a) Over what range of pressures can this system exist as two phases at the given T and 𝑧1 ?
(b) For a liquid-phase mole fraction 𝑥1 = 0.75, what is the pressure 𝑃 and what molar fraction of the system is
vapor?
(c) Show whether or not the system exhibits an azeotrope.

F. Vapor/Liquid Equilibrium from K-Value Correlations

A measure of the distribution of a chemical species between liquid and vapor phases is the 𝐾 value, defined
as the equilibrium ratio:

𝑦𝑖
𝐾𝑖 = Eq. 9
𝑥𝑖

It has no thermodynamic content, but may make for computational convenience through elimination of one set
of mole fractions in favor of the other. It does characterize “lightness” of a constituent species. A “light” species,

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ChE 408 | PRELIMINARY MODULE

with 𝐾 > 1, tends to concentrate in the vapor phase, whereas a “heavy” species, with 𝐾 < 1, tends to concentrate
in the liquid phase. In practice, at least one 𝐾𝑖 ≥ 1, and at least one 𝐾𝑖 ≤ 1.
The defining equation for 𝐾 can be rearranged as 𝑦𝑖 = 𝐾𝑖 𝑥𝑖 . The sum ∑ 𝑦𝑖 = 1 then yields
∑ 𝐾𝑖 𝑥𝑖 = 1 Eq. 10
𝑖
With the alternative rearrangement 𝑥𝑖 = 𝑦𝑖 /𝐾𝑖 , the sum sum ∑ 𝑥𝑖 = 1 yields
𝑦𝑖
∑ =1 Eq. 11
𝐾𝑖
𝑖
Thus, for bubble point calculations, where the 𝑥𝑖 are known, the problem is to find the set of 𝐾 values that
satisfies the above equation, whereas for dew point calculations, where the 𝑦𝑖 are known, the problem is to find the
set of 𝐾 values that satisfies the latter.

Flash Calculation

The flash calculation is a very common application of VLE. Considered here is the 𝑃, 𝑇 flash, in which are
calculated the quantities and compositions of the vapor and liquid phases in equilibrium at known 𝑇, 𝑃, and overall
composition. This problem is determinate on the basis of Duhem’s theorem: For any closed system formed initially
from given masses of prescribed chemical species, the equilibrium state is completely determined when any two
independent variables are fixed. The independent variables are here 𝑇 and 𝑃, and systems are formed from given
masses of nonreacting chemical species.

𝑉 (moles)
𝑦 fraction

𝐹 (moles)
𝑧 fraction

Flash Drum

𝐿 (moles)
𝑥 fraction

Fig. 16.0. Overall material balance of a Flash Distillation operation

For 𝐹 moles fed of a system with overall composition represented by the set of mole fractions {𝑧𝑖 }, let 𝐿 represent
the moles of the system that are liquid (mole fractions {𝑥𝑖 }) and let 𝑉 represent the moles that are vapor (mole
fractions {𝑦𝑖 }). The material balance equations are

𝐿+𝑉 = 𝐹 and 𝑧𝑖 𝐹 = 𝑥𝑖 𝐿 + 𝑦𝑖 𝑉 𝑖 = 1,2, … , 𝑁 Eq. 12

Rearranging for 𝑥𝑖 and 𝑦𝑖 yields

𝑧𝑖 𝑧𝑖 𝐾𝑖
𝑥𝑖 = . 𝑦𝑖 =
𝑉 𝑉 Eq. 13
1 + ( ) (𝐾𝑖 − 1) 1 + ( ) (𝐾𝑖 − 1)
𝐹 𝐹

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ChE 408 | PRELIMINARY MODULE

Taking the difference in the sums results in the Rachford-Rice flash method

𝑧𝑖 (1 − 𝐾𝑖 )
∑ =0
𝑉 Eq. 14
𝑖 1 + ( ) (𝐾𝑖 − 1)
𝐹

The initial step in solving a 𝑃, 𝑇 flash problem is to find the value of 𝑉/𝐹 which satisfies the previous equation, and
then mole fractions are determined by the equations for 𝑥𝑖 and 𝑦𝑖 , respectively.

The 𝐾 value of a species is a complex

function of temperature, pressure, and
equilibrium vapor- and liquid-phase
compositions. However, for mixtures of
compounds of similar molecular structure and
size, the K value depends mainly on
temperature and pressure. For example,
several major graphical 𝐾 value correlations are
available for light-hydrocarbon systems. The
easiest to use are the DePriester charts [Chem.
Eng. Prog. Symp. Ser. 7, 49: 1 (1953)], which
cover 12 hydrocarbons (methane, ethylene,
ethane, propylene, propane, isobutane,
isobutylene, n-butane, isopentane, n-pentane,
n-hexane, and n-heptane). These charts are a
simplification of the Kellogg charts (Liquid-
Vapor Equilibria in Mixtures of Light
Hydrocarbons, MWK Equilibrium Constants,
Polyco Data, 1950) and include additional
experimental data. The Kellogg charts, and
hence the DePriester charts, are based
primarily on the Benedict-Webb-Rubin equation
of state [Chem. Eng. Prog. 47: 419 (1951); 47:
449 (1951)], which can represent both the liquid
and the vapor phases and can predict K values
quite accurately when the equation constants
are available for the components in question.

Fig. 17.0. Typical variation of 𝐾 values with total pressure

at constant temperature for a complex mixture. Light
hydrocarbons in admixture with crude oil . [Katz and
Hachmuth, Ind . Eng . Chem ., 29: 1072 (1937).]

A trial-and-error procedure is required with any 𝐾 value correlation that takes into account the effect of
composition. One cannot calculate 𝐾 values until phase compositions are known, and those cannot be known until
the 𝐾 values are available to calculate them. For 𝐾 as a function of 𝑇 and 𝑃 only, the DePriester charts provide good
starting values for the iteration. These nomographs are shown in Fig. 2-10 a and b of Perry’s Chemical Engineers
Handbook (9th Edition). The SI versions of these charts were developed by Dadyburjor [Chem. Eng. Prog. 74(4): 85
(1978)].

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ChE 408 | PRELIMINARY MODULE

The Kellogg and DePriester charts and their subsequent extensions and generalizations use the molar average
boiling points of the liquid and vapor phases to represent the composition effect. An alternative measure of
composition is the convergence pressure of the system, which is defined as that pressure at which the 𝐾 values for
all the components in an isothermal mixture converge to unity. It is analogous to the critical point for a pure
component in the sense that the two phases become indistinguishable. The behavior of a complex mixture of
hydrocarbons for a convergence pressure of 34 .5 MPa (5000 psia) is illustrated in Fig. 17.0.
Two major graphical correlations based on convergence pressure as the third parameter (besides temperature
and pressure) are the charts published by the Gas Processors Association (GPA, Engineering Data Book, 9 th ed .,
Tulsa, Okla ., 1981) and the charts of the American Petroleum Institute (API, Technical Data Book—Petroleum
Refining, New York, 1966) based on the procedures from Hadden and Grayson [Hydro-carbon Process., Pet. Refiner
40(9): 207 (1961)] . The former uses the method proposed by Hadden [Chem. Eng. Prog. Symp. Ser. 7, 49: 53
(1953)] for the prediction of convergence pressure as a function of composition.

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ChE 408 | PRELIMINARY MODULE

Fig. 18.0. The 𝐾 values (𝐾 = 𝑦/𝑥) in light-hydrocarbon systems. (𝑎) Low-temperature range. (𝑏) High-temperature
range. [DePriester, Chem. Eng. Prog. Symp., Ser. 7, 49, 1 (1953).]

The GPA convergence pressure charts are primarily for alkane and alkene systems, but they include charts for
nitrogen, carbon dioxide, and hydrogen sulfide. The charts may not be valid when appreciable amounts of
naphthenes or aromatics are present; the API charts use special procedures for such cases. Useful extensions of
the convergence pressure concept to more varied mixtures include the nomographs of Winn [Chem. Eng. Prog.
Symp. Ser. 2, 48: 121 (1952)], Hadden and Grayson [Hydro-carbon Process., Pet. Refiner 40(9): 207 (1961)], and
Cajander, Hipkin, and Lenoir [ J. Chem. Eng. Data 5: 251 (1960)].

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ChE 408 | PRELIMINARY MODULE

Analytical K Value Correlations

The widespread availability and use of digital computers for distillation calculations have given impetus to the
development of analytical expressions for 𝐾 values. McWilliams [Chem. Eng. 80(25): 138 (1973)] presents a
regression equation and accompanying regression coefficients that represent the DePriester charts of Fig. 2-10 of
Perry’s Handbook. Regression equations and coefficients for various versions of the GPA convergence pressure
charts are available from the GPA.
Preferred analytical correlations are less empirical and most often are theoretically based on one of two exact
thermodynamic formulations, as derived in the previous discussions. When a single pressure-volume-temperature
(𝑃-𝑉-𝑇 ) equation of state is applicable to both vapor and liquid phases, the formulation used is
̂ 𝑖𝐿
Φ
𝐾𝑖 = 𝑉 Eq. 15
̂𝑖
Φ
where the mixture fugacity coefficients Φ ̂ 𝑖𝐿 for the liquid and Φ
̂ 𝑖𝑉 for the vapor are derived by classical
thermodynamics from the 𝑃-𝑉-𝑇 expression. Consistent equations for enthalpy can be similarly derived.
Until recently, equations of state that have been successfully applied and have been restricted to mixtures of
nonpolar compounds, namely, hydrocarbons and light gases. These equations include those of Benedict-Webb-
Rubin (BWR), Soave (SRK) [Chem. Eng. Sci. 27: 1197 (1972)], who extended the remarkable Redlich-Kwong
equation, and Peng-Robinson (PR) [Ind. Eng. Chem. Fundam. 15: 59 (1976)]. The SRK and PR equations belong to
a family of so-called cubic equations of state. The Starling extension of the BWR equation (Fluid Thermodynamic
Properties for Light Petroleum Systems, Gulf, Houston, 1973) predicts 𝐾 values and enthalpies of the normal
paraffins up through n-octane, as well as isobutane, isopentane, ethylene, propylene, nitrogen, carbon dioxide, and
hydrogen sulfide, including the cryogenic region. Computer programs for 𝐾 values derived from the SRK, PR, and
other equations of state are widely available in all computer-aided process design and simulation programs. The
ability of the SRK correlation to predict 𝐾 values even when the pressure approaches the convergence pressure is
shown for a multicomponent system in Fig. 13-10 of Perry’s Handbook (9th Ed.). Similar results are achieved with
the PR correlation. The Wong-Sandler mixing rules for cubic equations of state now permit such equations to be
extended to mixtures of organic chemicals, as shown in a reformulated version by Orbey and Sandler [AIChE J.
41(3): 683–690 (1995)].
An alternative 𝐾 value formulation that has received wide application to mixtures containing polar and/or
nonpolar compounds is
̂ 𝑖𝐿
γ̂𝐿𝑖 Φ
𝐾𝑖 = Eq. 16
Φ̂ 𝑖𝑉
where different equations of state may be used to predict the pure-component liquid fugacity coefficient Φ
̂ 𝑖𝐿 and the
vapor-mixture fugacity coefficient, and any one of a number of mixture free-energy models may be used to obtain
the liquid activity coefficient γ̂𝐿𝑖 . At low to moderate pressures, accurate prediction of the latter is crucial to the
application of the said equation.
When either equation can be applied, the former is generally preferred because it involves only a single equation
of state applicable to both phases and thus would seem to offer greater consistency. In addition, the quantity Φ ̂ 𝑖𝐿 in
Eq. 16 is hypothetical for any components that are supercritical. In that case, a modification of Eq. 16 that uses
Henry’s law is sometimes applied.
For mixtures of hydrocarbons and light gases, Chao and Seader (CS) [AIChE J. 7: 598 (1961)] applied Eq. 16
by using an empirical expression for Φ ̂ 𝑖𝐿 based on the generalized corresponding-states 𝑃-𝑉-𝑇 correlation of Pitzer
et al., the Redlich-Kwong equation of state for Φ ̂ 𝑖𝑉 , and the regular solution theory of Scatchard and Hildebrand for
γ̂𝑖 . The predictive ability of the last-named theory is exhibited in Fig. 13-11 of Perry’s Handbook (9th Ed.) for the
𝐿

heptane-toluene system at 101.3 kPa (1 atm). Five pure-component constants for each species (𝑇𝑣 , 𝑃𝑣 , 𝜔, 𝛿, and
𝑣 𝐿 ) are required to use the CS method which, when applied within the restrictions discussed by Lenoir and Koppany
[Hydrocarbon Process. 46(11): 249 (1967)], gives good results. Revised coefficients of Grayson and Streed (GS)
(Paper 20-P07, Sixth World Pet. Conf. Frankfurt, June 1963) for the Φ ̂ 𝑖𝐿 expression permit the application of the CS
correlation to higher temperatures and pressures and give improved predictions for hydrogen. Jin, Greenkorn, and

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

Chao [AIChE J. 41: 1602 (1995)] present a revised correlation for the standard-state liquid fugacity of hydrogen,
applicable from 200 to 730 K. For mixtures containing polar substances, more complex predictive equations for γ̂𝐿𝑖
that involve binary-interaction parameters for each pair of components in the mixture are required for use in Eq. 16
as discussed before. Four popular expressions are the Wilson, NRTL, UNIFAC, and UNIQUAC equations. The
preferred expressions for representing activity coefficients are the NRTL and UNIQUAC equations. Extensive listings
of binary-interaction parameters for use in all but the UNIFAC equation are given by Gmehling and Onken [Vapor-
Liquid Equilibrium Data Collection, DECHEMA Chemistry Data ser., vol. 1 (parts 1–10), Frankfurt, 1977]. They
obtained the parameters for binary systems at 101 .3 kPa (1 atm) from best fits of the experimental 𝑇-𝑦-x equilibrium
data by setting Φ̂ 𝑖𝑉 and Φ
̂ 𝑖𝐿 to their ideal-gas, ideal-solution limits of 1.0 and 𝑃 𝑠𝑎𝑡 /𝑃, respectively, with the vapor
pressure 𝑃 𝑠𝑎𝑡 given by a three-constant Antoine equation, whose values they tabulate.
The Wilson equation is particularly useful for systems that are highly nonideal but do not undergo phase splitting,
as exemplified by the ethanol-hexane system, whose activity coefficients are shown in Fig. 13-12 of Perry’s
Handbook (9th Ed.).
Carboxylic acids (e.g., formic acid and acetic acid) tend to dimerize in the vapor phase according to the chemical
equilibrium expression

𝑃𝐷
𝐾𝐷 = = 10𝐴+𝐵/𝑇 Eq. 17
𝑃𝑀2

where 𝐾𝐷 is the chemical equilibrium constant for dimerization, 𝑃𝐷 and 𝑃𝑀 are partial pressures of dimer and
monomer, respectively, in torr, and 𝑇 is in Kelvin. Values of 𝐴 and 𝐵 for the first four normal aliphatic acids are found
on page 13-10 of Perry’s Chemical Engineers Handbook (9th Ed.).
As shown by Marek and Standart [Collect. Czech. Chem. Commun. 19: 1074 (1954)], it is preferable to correlate
and use liquid-phase activity coefficients for the dimerizing component by considering separately the partial
pressures of the monomer and dimer. For example, for a binary system of components 1 and 2, when only
compound 1 dimerizes in the vapor phase, the following equations apply if an ideal gas is assumed:

𝑃1 = 𝑃𝐷 + 𝑃𝑀 Eq. 18
𝑃𝑀 + 2𝑃𝐷
𝑦1 = Eq. 19
𝑃

These equations when combined with Eq. 17 lead to the following equations for liquid-phase activity coefficients
in terms of measurable quantities:

𝑃𝑦1 1 + (1 + 4𝐾𝐷 𝑃1𝑠𝑎𝑡 )0.5

𝛾1 = { }
𝑃1𝑠𝑎𝑡 𝑥1 1 + [1 + 4𝐾𝐷 𝑃𝑦1 (2 − 𝑦1 )]0.5 Eq. 20

𝑃𝑦1 2(1 − 𝑦1 ) + [1 + 4𝐾𝐷 𝑃𝑦1 (2 − 𝑦1 )]0.5

𝛾2 = 𝑠𝑎𝑡 { } Eq. 21
𝑃2 𝑥2 (2 − 𝑦1 ){1 + [1 + 4𝐾𝐷 𝑃𝑦1 (2 − 𝑦1 )]0.5 }

Detailed procedures, including computer programs for evaluating binary-interaction parameters from
experimental data and then using these parameters to predict K values and phase equilibria, are given in terms of
the UNIQUAC equation by Prausnitz et al. (Computer Calculations for Multicomponent Vapor-Liquid and Liquid-
Liquid Equilibria, Prentice-Hall, Englewood Cliffs, N.J., 1980) and in terms of the UNIFAC group contribution method
by Fredenslund, Gmehling, and Rasmussen (Vapor-Liquid Equilibria Using UNIFAC, Elsevier, Amsterdam, 1980) .
Both use the method of Hayden and O’Connell [Ind. Eng. Chem. Process Des. Dev. 14: 209 (1975)] to compute Φ ̂ 𝑖𝑉
in Eq. 16. When the system temperature is greater than the critical temperature of one or more components in the
mixture, Prausnitz et al. use a Henry’s law constant 𝐻𝑖,𝑀 in place of the product γ̂𝐿𝑖 Φ
̂ 𝑖𝐿 in Eq. 16. Otherwise Φ
̂ 𝑖𝐿 is
evaluated from vapor pressure data with a Poynting saturated-vapor fugacity correction. When the total pressure is

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY
ChE 408 | PRELIMINARY MODULE

less than about 202 .6 kPa (2 atm) and all components in the mixture have a critical temperature that is greater than
the system temperature, then Φ𝑖𝐿 = 𝑃𝑖𝑠𝑎𝑡 /𝑃 and Φ𝑖𝑉 = 1.0. Equation 16 then reduces to

γ̂𝐿𝑖 𝑃𝑖𝑠𝑎𝑡
𝐾𝑖 =
𝑃

which is referred to as a modified Raoult’s law 𝐾 value. If, furthermore, the liquid phase is ideal, then γ𝐿𝑖 = 1 .0 and

𝑃𝑖𝑠𝑎𝑡
𝐾𝑖 =
𝑃

which is referred to as a Raoult’s law K value that is dependent solely on the vapor pressure 𝑃𝑖𝑠𝑎𝑡 of the component
in the mixture. The UNIFAC method is being periodically updated with new group contributions; for example, see
Gmehling et al. [Ind. Eng. Chem. Res. 42: 183 (2003)].

[Examples] VLE from 𝑲-Values

Example 1:
Find the values of 𝐾 or 𝑥𝑖 . Use the DePriester Diagram.
(a) Estimate the 𝐾-value of propane at 100 psia and 160°F.
(b) Estimate 𝑇 where 𝐾-value of isobutane is 3.6 at 200 psia.
(c) What are the 𝐾-values of n-octane and propylene at 150 psia at 70°F?
(d) In a ternary system ethylene(1)/n-heptane(2)/n-pentane(3), suppose 𝑥1 = 0.13, what are the values of 𝑥2 and 𝑥3
if the system is in equilibrium at 400 psia and 220°F?

Example 2:
The system acetone(1)/acetonitrile(2)/nitromethane(3) at 80°C and 110 kPa has the overall composition 𝑧1 = 0.45,
𝑧2 = 0.35, 𝑧3 = 0.20. Assuming that Raoult’s law is appropriate to this system, determine 𝐿, 𝑉, {𝑥𝑖 }, and {𝑦𝑖 }.

Example 3:
A binary mixture of mole fraction 𝑧1 is flashed to conditions 𝑇 and 𝑃. For one of the following, determine the
equilibrium mole fractions 𝑥1 and 𝑦1 of the liquid and vapor phases formed, the molar fraction 𝑉 of the vapor formed,
and the fractional recovery 𝑅 of species 1 in the vapor phase (defined as the ratio for species 1 of moles in the vapor
to moles in the feed). Assume that Raoult’s law applies.
(a) Acetone(1)/acetonitrile(2), 𝑧1 = 0.75, T = 340 K, P = 115 kPa.
(b) Benzene(1)/ethylbenzene(2), 𝑧1 = 0.50, T = 100°C, P = 0.75(atm).
(c) Ethanol(1)/1-propanol(2), 𝑧1 = 0.25, T = 360 K, P = 0.80(atm).
(d) 1-Chlorobutane(1)/chlorobenzene(2), 𝑧1 = 0.50, T = 125°C, P = 1.75 bar.

Example 4:
A mixture containing equimolar amounts of benzene(1), toluene(2), and ethylbenzene(3) is flashed to conditions 𝑇
and 𝑃. For one of the following conditions, determine the equilibrium mole fractions {𝑥𝑖 } and {𝑦𝑖 } of the liquid and
vapor phases formed and the molar fraction of the vapor formed. Assume that Raoult’s law applies.
(a) T = 110°C, P = 90 kPa.
(b) T = 110°C, P = 100 kPa.
(c) T = 110°C, P = 110 kPa.
(d) T = 110°C, P = 120 kPa.

-End of Discussion-
References are stated in the syllabus.

MODULE I College of Engineering, Architecture, and Fine Arts

Engr. Monroe H. de Guzman, AAE BATANGAS STATE UNIVERSTIY