CHE 3231

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COURSE LEARNING OUTCOMES

At the end of the module, you should be able
to:
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 and apply vapor-liquid equilibrium
relations based on cubic equations of state
and other EOS models.
3. Derive solution properties from vapor-liquid
equilibrium experimental data and
interpret phase equilibrium diagrams.
4. Solve for the equilibrium conversion of
single systems and analyze the effect of
SOLUTION operating single reaction systems and
analyze the effect of operating variables
THERMODYNAMICS on chemical reaction conversion; use
spreadsheets and numerical computing
software in vapor-liquid equilibrium
calculations, construction of phase-
equilibrium diagrams, and solving for
equilibrium conversion of multi-reaction
systems and apply concepts of chemical
reaction equilibrium to the selection of
reaction pathways in process
development and reactor design.

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 COURSE INTRODUCTION
This is a 3-unit course, in Chemical Engineering curriculum which is concerned with fluid
mixtures, teats topics in the unique domain of chemical engineering thermodynamics. It
provides a comprehensive exposition of the theory and application of solution
thermodynamics. Then it deals with topics in phase equilibria, including an extended
treatment vapor/liquid equilibrium, and adsorption and osmotic pressure. Finally, it covers
chemical-reaction equilibrium.

Each unit in this course is designed using the 5E constructivist model of learning, developed
by Rodger Bybee, that encourages students to engage, explore, explain, elaborate, and
evaluate their knowledge of topics covered therein. It means that at the end of each unit,
each module, and the course as a whole, you will be assessed on your progress in attaining
the course learning outcomes. Outcomes-based education dictates that only when you can
demonstrate the course learning outcomes by the end of this course, can you be given a
passing mark.

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 MODULE 1
VAPOR/LIQUID EQUILIBRIUM: INTRODUCTION

At the end of the module, you should be able to:

• Describe the behavior of VLE and how to simplify the VLE problem.
• Derive and simplify equations of VLE.
• Apply simplified VLE equations to obtain data for P-XY, T-XY, and X-Y diagrams.
• Apply Raoult's law and Henry's law to solve simple thermodynamic problems.
• Carry out bubble and dew point calculations for a given mixture.
• Carry out flash calculation in order to determine the vapor/liquid fraction as well as
the mixture composition of each phase at specified conditions using available K-
values etc.

Introduction

In this module we first discuss the nature of equilibrium, and then consider two rules that give
the number of independent variables required to determine equilibrium states. There follows
a qualitative discussion of vapor/liquid phase behavior. Then we introduce the two simplest
formulations that allow calculation of temperatures, pressures, and phase compositions for
systems in vapor/liquid equilibrium. The first, known as Raoult’s law, is valid only for systems at
low to moderate pressures and in general only for systems comprised of chemically similar
species. The second, known as Henry’s law, is valid for any species present at low
concentration, but presented here is also limited to systems at low to moderate pressures. A
modification of Raoult’s law that removes the restriction to chemically similar species is also
introduced. Finally, calculations based on equilibrium ratios or K-values are considered.

Unit 1 The Nature of Equilibrium

UNIT LEARNING OUTCOMES

• Understand that equilibrium implies absence of driving forces for net changes in
the macroscopic state of a system.
• Review the basic measures of composition.

ENGAGE

Equilibrium is a condition in which no changes 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.

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 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.

To learn more, let us watch the video entitled “Thermodynamic Equilibrium” using the link
https://www.youtube.com/watch?v=TgHsSTnMHa0.

EXPLORE
The Thermodynamic Concept of Equilibrium

Intuitively, the concept of equilibrium conveys the message that something “balances out.”
Equilibrium describes a state of vanishing driving forces or gradients, where everything
remains as it is. If a system is in equilibrium, it retains its current state because there are no
driving forces causing anything to change.

If two materials have the same temperature, we say that they are in thermal equilibrium. No
exchange of heat takes places because there are no thermal gradients. For instance, a
liquid and a vapor phase are in thermal equilibrium when:

Tl = Tv (1.1)

We achieve mechanical equilibrium if two substances are found at the same pressure. No
bulk movement of fluids takes place because there are no pressure gradients. A liquid and
a vapor phase are in mechanical equilibrium when:

Pl = Pv (1.2)

For a thermodynamic system to be in equilibrium, all intensive (temperature, pressure) and

extensive thermodynamic properties (U, G, A, H, S, etc) must be constants. Hence, the total
change in any of those properties ( d ) must be zero at equilibrium.

Now we would like to have a concept of thermodynamic equilibrium for a vapor-liquid

equilibrium. Let us consider a closed, heterogeneous vapor-liquid system. Any changes in a
total property of the system will be the result of the changes of that property in the liquid
phase plus the changes of that property in the vapor phase.

d(total) = d(liquid) + d( vapor) (1.3)

In this case, liquid and vapor by themselves are not closed systems; they can exchange
matter between themselves but not with the surroundings. To elaborate more upon the
concept of equilibrium, let’s look at the equation, dG = VdP − SdT +  i dni . Because it is
i
written in terms of changes in pressure and temperature, two measurable laboratory

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 quantities, it is the “friendliest” of all fundamental equations. We write it for both of the
phases:
d(liquid) = (VdP − SdT )l +   l dnl (1.4a)
i i
i

dG ( vapor) = (VdP − SdT ) v +  iv dniv (1.4b)

i
In (1.3), for  = G , we get:
dG (total) = dG (liquid) + dG ( vapor) (1.5)

Hence,

dG (total) = (VdP − SdT )l + (VdP − SdT )v +  il dnil +  iv dniv (1.6)
i i
Since at equilibrium all extensive properties, such as G, must remain constant, dG (total) must
be zero. For this to hold true, and by inspection of equation (1.6), the conditions for
thermodynamic equilibrium are:

dP = 0 [Mechanical Equilibrium] (1.7)

dT = 0 [Thermal Equilibrium] (1.8)

 il dnil +  iv dniv = 0 [  i criteria for equilibrium] (1.9)

i i
It can be also proven that, at equilibrium, the total free energy of the system (G (total)) must
take a minimum value; this reinforces the fact that dG(total)=0 at equilibrium. The minimum
Gibbs energy criterion for equilibrium is a restatement of the second law of thermodynamics,
from which we know that the entropy of a system in equilibrium must be at its maximum,
considering all of the possible states for equilibrium.

It is somehow reasonable that for a true equilibrium condition there should be neither
pressure nor temperature gradients (equations 1.7 and 1.8). This is because equilibrium is, at
the very least, a state of lack of gradients. But what is equation (1.9) trying to tell us? To
demystify equation (1.9), we recall that we are dealing with a closed system, hence, the
total amount of moles per species:
n (total) = n (l ) + n ( v ) (1.10)

must be constant (we do not allow for chemical reactions within the system). Thus we write:

dnitotal = dni(l ) + dniv = 0 (1.11)

Therefore,
dni( v ) = −dni(l ) (1.12)

(1.12) into (1.9)

( )
 i(l ) − iv dni( v ) = 0
i
(1.13)

For equation (1.13) to hold true,

i(l ) = i( v ) for all i = 1, 2, … nc (1.14)

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 We have then arrived at the criteria for vapor-liquid equilibria for a system at constant
pressure and temperature: the chemical potential of every species must be the same in both
phases. We may generalize this finding to any number of phases, for which the chemical
potential of every species must be the same in all phases. The chemical potential being the
driving force which moves a species from one phase to the other, equation (1.14) is
physically reasonable. If the chemical potential of a species in one phase is the same as that
in the other, there is zero driving force and thus a zero net transfer of species at equilibrium.

Measures of Composition

◾ The three most common measures of composition are mass fraction, mole fraction, and
molar concentration.
◾ Mass of mole fraction is defined as the ratio of the mass or number of moles of a
particular chemical species in a mixture or solution to the total mass of number of moles
of the mixture or solution:

(1.15)

(1.16)

◾ Molar concentration is defined as the ratio mi of the

m mole fraction of a particular chemical
i =
species in a mixture or solution to itsxmolar = i
volume:
 m m
(1.17)
ni ni
xi = =
n n
◾ For flow processes, convenience suggests its expression as a ratio of rates:

(1.18)
xi
Ci =
◾ The molar mass of a mixture or solution is, byVdefinition, the mole-fraction-weighted sum
of the molar masses of all species present:

(1.19)
n
Ci = i
q

EXPLAIN
M =of equilibrium,
To be able to translate your understanding xi M i 
do the following activity.
i
Activity 1: A System under Thermodynamic Equilibrium
Self-Assessment No. 1

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 Give an example of a thermodynamic system at equilibrium. Using the thermodynamic
concept of equilibrium, explain how equilibrium (a state of vanishing forces or gradients)
is established on this system.

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ELABORATE AND EVALUATE

You are now able to describe a system under equilibrium. It is now time for you to test your
comprehension whether or not you can identify a given system is under thermodynamic
equilibrium.

Activity 2: Identifying Systems under Thermodynamic Equilibrium

Self-Assessment No. 2

Given the following systems below. Identify whether or not the following are under
thermodynamic equilibrium. If the given system is not under thermodynamic equilibrium,
identify which condition/s it does not satisfy to to establish thermodynamic equilibrium.
a. A balloon bursts. The compressed gas inside rapidly expands.
b. The gas in a cylinder with a movable piston. Temperature and pressure inside are
uniform and the restraining force on the piston is just sufficient to keep it from moving.
c. A cold bottle of water was brought out from the refrigerator and kept outside until the
temperature of the bottle and the surrounding air is almost the same.
d. A certain mass of hot oil kept in a metallic container sealed from all sides.

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Unit 2 The Phase Rule: Duhem’s Theorem

UNIT LEARNING OUTCOMES

• State and apply phase rule for nonreacting systems.
• State and apply Duhem’s theorem for nonreacting systems.

ENGAGE

A phase is defined as any homogeneous and physically distinct part of a system bounded
by a surface and is mechanically separable from other parts of the system. A system
consisting of only one phase is said to homogeneous. A system consisting more than one
phase is said to be heterogeneous. When various phases are in equilibrium with one another
in a heterogeneous system, there can be no transfer of energy or mass from one phase to
another. This means that at equilibrium, the various phases must have the same temperature
and pressure and their respective compositions must remain constant all along. The
homogeneous reactions can be studied using the law of mass action. For heterogeneous
reversible reactions, the phase rule given by Williard Gibbs is used. On the other hand,

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 Duhem’s Theorem is similar to the phase rule. It is applied to closed systems in equilibrium, in
which intensive and extensive states are kept as constant.

EXPLORE
Phase Rule

The intensive state of a PVT system consisting N chemical species and  phase in
equilibrium is characterized by its temperature T, pressure P, and N −1 mole fractions1 for
each phase. The number of phase-rule variables is 2 + ( N − 1)( ) . The masses or amounts
of the phases are not phase-rule variables because they have no influence on the intensive
state of the system.

As will become clear later in this unit, 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 ( − 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)( ) − ( − 1)( N )

Upon reduction, this becomes the phase rule:

F = 2 − + N (1.20)
Example Problem No. 1
How many phase-rule variables must be specified to fix the thermodynamic state of each of
the following systems?
a. Liquid water in equilibrium with its vapor.
b. Liquid water in equilibrium with a mixture with water vapor and nitrogen.
c. A three-phase system of saturated aqueous salt solution at its boiling point with
excess salt crystals present

Solution:
(a) The system contains a single chemical species existing as two phases ( one liquid and
one vapor), and
F = 2 −  + N = 2 − 2 +1 = 1
This result is in agreement with the fact that for a given pressure water has but one boiling
point. Temperature or pressure, but not both, may be specified for a system comprised of
water in equilibrium with its vapor.

(b) Two chemical species are present. Again there are two phases, and
F = 2 − + N = 2 − 2 + 2 = 2

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 The addition of an inert gas to a system of water in equilibrium with its vapor changes the
characteristic of the system. Now temperature and pressure may be independently varied,
but once they are fixed the system described can exist in equilibrium only at a particular
composition of the vapor phase. (if nitrogen is considered negligibly soluble in water. The
liquid phase is pure water.)

(c) The three phase ( = 3 ) are crystalline salt, the saturated aqueous solution, and vapor
generated at the boiling point. The two chemical species ( N = 2 ) are water and salt. For
this system,
F = 2 − + N = 2 − 3 + 2 =1

Activity 1: Application of Phase Rule

Self-Assessment No. 3

How many phase rule variables must be specified to fix the thermodynamic state of each
of the following systems?
a. A sealed flask containing a liquid ethanol-water mixture in equilibrium with its vapor.
b. A sealed flask containing a liquid ethanol-water mixture in equilibrium with its vapor
and nitrogen.
c. A sealed flask containing ethanol, toluene, an water as two liquid phases plus vapor.

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Duhem’s Theorem

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) intensive phase-rule
variables but also by the  extensive variables represented by the masses (or mole
numbers) of the phases. This the total number of variables is:
2 + ( N − 1) +  = 2 + N
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 ( − 1) N phase-equilibrium equations, represent
a number of independent equations equal to:
( − 1) N + N = N
The difference between the number of variables and the number of equations is therefore:
2 + N − N = 2
On the basis of this result, Duhem’s theorem is stated as follows:

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 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 r
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.

Activity 2: Application of Duhem’s Theorem

Self-Assessment No. 4

Consider a closed vessel of fixed volume containing equal masses of water, ethanol, and
toluene at 70 oC. 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?
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?
c. The temperature of the system is increased to 72 oC. What, if any, intensive or
extensive coordinates of the system remain unchanged?

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EXPLAIN

Activity 3: Intensive State of a Binary System in VLE

Self-Assessment No. 5

Consider a binary (two-species) system in vapor/liquid equilibrium. Enumerate and

explain all the combinations of intensive variables that could be fixed to fully specify the
intensive state of the system.

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ELABORATE AND EVALUATE

Activity 4: Duhem’s Theorem in the Industry

Assignment No. 1

As a would-be chemical engineer in the future, give an example situation where Duhem’s
Theorem can be applied in the industry. Enumerate all possible variables that must be
specified to fully determine the intensive and extensive states of the system. Also,
enumerate all possible changes that would affect the intensive and extensive
coordinates.

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 To be submitted in Google classroom on:

Unit 3 Vapor/Liquid Equilibrium: Qualitative Behavior

UNIT LEARNING OUTCOMES

• Identify dew point and bubble point surfaces, the critical locus, and pure
species vapor-pressure curves that make up a vapor/liquid envelope when
presented in a PTxy diagram.
• Interpret and apply Pxy, Txy, PT, and yx diagrams representing vapor/liquid
equilibrium of binary mixtures.

ENGAGE

Vapor/liquid equilibrium (VLE) is paramount in engineering applications such as distillation,

environmental modeling, and general process design. Understanding the interactions of
components in a mixture is very important in designing, operating and analyzing such
separators. VLE data is useful for determining how liquid mixtures will separate. Because the
liquids have different boiling points, one liquid will boil into a vapor and rise in the column,
while the other will stay as a liquid and drain through the unit. The process is very important
in a variety of industries.

Phase diagram is a graphical representation of the physical states of a substance under

different conditions of temperature and pressure. A typical phase diagram has pressure on
the y-axis and temperature on the x-axis. As we cross the lines or curves on the phase
diagram, a phase change occurs. In addition, two states of the substance coexist in
equilibrium on the lines or curves.

VLE is probably best understood from phase diagrams. In this unit, we’ll be exploring the
qualitative behavior of VLE through phase diagrams.

EXPLORE
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 of systems of greater complexity cannot be adequately represented graphically.

= 2 ), the phase rule becomes

For a system comprised of two chemical species ( N
F = 4 −  . Because there must be at least one phase (  = 1 ), the maximum number of
phase-rule variables that must 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 pair

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 of phases coexisting at equilibrium ( F = 4 − 2 = 2 ) define surfaces. A schematic three-
dimensional diagram illustrating these surfaces for VLE is shown in Fig. 1.1.

Figure 1.1: PTxy diagram for vapor/liquid equilibrium.

➢ Fig. 1.1 shows the P-T-composition surfaces which contain the equilibrium states of
saturated vapor and saturated liquid for a binary system. 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 RKAC1 and UBHC2
which represents the vapor pressure-vs.-T curves for the pure species 1 and 2.

➢ However, 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.

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 ➢ The subcooled-liquid region lies above the upper surface of Fig. 1.1; the superheated
vapor region lies below the lower surface. The interior space between the two surfaces
is the region of coexistence of both liquid an d vapor phases.

➢ If one starts with a liquid at F and reduces at constant temperature and composition
along the vertical line FG, The first bubble of vapor appears at point L, which lies on the
upper surface. Thus, L is a bubblepoint, and the upper surface is the bubblepoint surface.

➢ The state of the vapor bubble in equilibrium with the liquid at L must be represented by
a point on the lower surface at the temperature and pressure of L. This point is indicated
by V. Line VL is an example of a tie line, which connects points representing phases in
equilibrium.

➢ As the pressure is further reduced along line line FG, more and more liquid vaporizes until
at W the process is complete. Thus W lies on the under surface and represents a state of
saturated vapor having the mixture composition. Since W is the point at which the last
drops of liquid (dew) disappear, it is a dewpoint, and the lower surface is the dewpoint
surface.

➢ Because the complexity of Fig. 1.1, 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 principal planes, each perpendicular to one of the
coordinate axes, are illustrated in Fig. 1.1. Thus a vertical plane perpendicular to the
temperature axis is outlined as AEDBLA.

➢ The lines in 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 Fig. 1.2(a). It shows
P-x1-y1 plots for three different temperatures.

➢ The on for Ta, represents the section of Fig. 1.1 indicated by AEDBLA. The horizontal lines
are tie lines connecting the compositions of phases in equilibrium. The temperature Tb
lies between the two pure-species critical temperatures identified by C1 and C2 in Fig.
1.1, and temperature Td is above both critical temperatures. The curves for these two
temperatures therefore do not extend all the way across the diagram. However, The first
passes through one mixture critical point, and the second through two such points.

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 Figure 1.2: (a) Pxy diagram for three temperatures. (b) Txy diagram for three pressures
Saturated liquid (bubble line); Saturated vapor (dew line)

➢ All three of these critical points are denoted by 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 passed through Fig. 1.1 perpendicular to the P axis is identified by C1
and C2 in Fig. 1.1, and temperature Td is above both critical temperatures.

➢ A horizontal plane passed through Fig. 1.1 perpendicular to the P axis is identified by
KJIHLK. Viewed from the top, 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
appears as in Fig. 1.2(b). This figure is analogous to Fig. 1.2(a), except that it represents
values for three constant pressures, Pa, Pb, and Pd.

Figure 1.3: PT diagram for several compositions Figure 1.4: Portion of a PT diagram in the critical
region

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 ➢ Other possible plots are vapor mole fraction y1 vs. liquid mole fraction x1 for either the
constant-T conditions of Fig. 1.2(a) or the constant-P conditions of Fig. 1.2(b). The third
plane identified in Fig. 1.1, vertical and perpendicular to the composition.

➢ The critical point of a binary mixture occurs where the nose of a loop in Fig. 1.3 is tangent
to the envelope curve. Put another way, the envelope curve is the critical locus. Fig. 1.3
illustrates that the location of the critical point on the nose of the loop varies with
composition. For a pure species, the critical points 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 P-T loop shown in Fig. 1.4. The critical point
is at C. The points of maximum pressure and maximum temperature are identified as MP
and MT. The interior dashed curved 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 reached 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 well where the pressure and
temperature in the underground formation are at conditions represented by point F. If
the pressure at the wellhead is that of point G, considerable liquefaction of the product
stream is accomplished along with partial separation of heavier species of the mixture.

➢ 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; I.e., a lean gas (gas from which the heavier species have been removed) is
returned to the underground reservoir to maintain an elevated pressure.

EXPLAIN

15
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 Figure 1.5: Pxy diagram for VLE of Figure 1.6: Txy diagram for VLE of
chloroform(1)/tetrahydrofuran(2) at 50 oC chloroform(1)/tetrahydrofuran(2) at 120 kPa

Activity 1: Application of Pxy and Txy Diagrams (1)

Self-Assessment No. 6

1. The pressure above a mixture of chloroform and tetrahydrofuran at 50 oC is measured

to be 62 kPa. What are the possible compositions of the liquid and vapor phases?
2. Consider chloroform(1)/tetrahydrofuran(2) mixture with x1 = 0.80, initially at 50 oC and
70 kPa. Describe the evolution of phases and phase compositions as the pressure is
gradually reduced to 50 kPa.
3. A chloroform and tatrahydrofuran mixture is heated in a closed system at 120 kPa to
a temperature of 70 oC, and two phases are observed to be present. WHat are the
possible compositions of the liquid and vapor phases?
4. Consider a chloroform(1)/tetrahydrofuran(2) mixture with x1 = 0.80, initially at 70 oC
and 120 kPa. Describe the evolution of phases and phase compositions as the
temperature is gradually increased to 80 oC.

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ELABORATE AND EVALUATE

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 Figure 1.7: Pxy diagram for VLE of ethanol(1)/ethyl Figure 1.8: Txy diagram for VLE of ethanol(1)/ethyl
acetate (2) at 70 oC acetate (2) at 100 kPa

Activity 2: Application of Pxy and Txy Diagrams (2)

Assignment No. 2

1. Consider a closed vessel initially containing 1 mol of pure ethyl acetate at 70 oC 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 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 volume?
2. Consider a closed vessel initially containing 1 mol of pure ethyl acetate at 74 oC and
100 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 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 volume?

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17
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 Unit 4 Simple Models for Vapor/Liquid Equilibrium
(Raoult’s Law, Henry’s Law, and Modified Raoult’s Law)

UNIT LEARNING OUTCOMES

• Apply Raoult’s Law and Henry’s Law to solve simple thermodynamic problems.
• Carry out bubble and dew point calculation for a given mixture.

ENGAGE

The preceding unit has described what is observed through experimental observation. When
thermodynamics is applied to vapor/liquid equilibrium, the goal is to find by calculation the
temperatures, pressures, and compositions of phases in equilibrium. Indeed,
thermodynamics provides the mathematical framework for the systematic correlation,
extension, generalization, evaluation, and interpretation of data. Moreover, it is the means
by which the predictions of various theories of molecular physics and statistical mechanics
may be applied to practical purposes. None of this can be accomplished without models
for the behavior of systems in vapor/liquid equilibrium. The two simplest are Raoult’s law and
Henry’s law.

EXPLORE
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 applied for low to moderate
pressure.

◾ The second assumption implies that it can have approximate validity only when the
species that comprise the system are chemically similar.

The mathematical expression which reflects the two major assumptions and which gives the
quantitative expression t Raoult’s law is:

yi P = xi Pi sat (i = 1, 2, …, N) (1.21)

where:
xi = liquid-phase mole fraction
yi = vapor-phase mole fraction
Pisat = vapor pressure species i at the temperature of the system
yiP = partial pressure of species i

18
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 ◾ The simple model for VE represented by Eq. 1.21 provides a realistic description of the
actual behavior for relatively small class of systems.

◾ A limitation of Raoult’s law is that it can be applied only to species for which vapor
pressure is known and this requires that the species must be “subcritical”, I.e., that the
temperature of application be below the critical temperature of the species.

◾ An important useful feature of Raoult’s law is that it is valid for any species present at a
mole fraction approaching unity, provided only that the vapor phase is an deal gas.
Chemical similarity of the constituent is not a requirement.

◾ For generality, we consider a system containing N chemical species. Then by phase rule,
for a VLE situation, the degrees of freedom are 2 N, the phase rule variables being xi, yi,
T, and P.

◾ The Raoult’s law provide N constraining relations connecting these variables. Thus, for
solving the VLE problem, N variables need to be specified, so that the values of the other
N variables may be determined.

Dewpoint and Bubblepoint 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:

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

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

Because  i yi = 1 , Eq. 1.21 maybe summed over all species to yield:

P =  xi Pi sat (1.22)
i

This equation finds direct application in bubblepoint calculations, where the vapor-phase
composition is unknown.
For binary system with x2 = 1 − x1 ,
P = P2sat + ( P1sat − P2sat ) x1 (1.23)
Eq. 1.21 may also be solved for xi and summed over all species. With i xi = 1 , this yields:
1
P= (1.24)
yi
 sat
i P
i
An equation applied in dewpoint calculations, where liquid-phase compositions are not
known.
Example Problem No. 1

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 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. T , K
2945.47
ln P1sat = 14.2724 −
T − 49.15
2972.64
ln P2sat = 14.2043 −
T − 64.15
a. Prepare a graph showing P vs. x1 and P vs. y1 for a temperature of 75 oC (348.15 K).
b. Prepare a graph showing T vs. x1 and T vs. y1 for a pressure of 70 kPa.
Solution:
(a)
BUBB P calculations:
➢ Calculate P1sat and P2sat using Antoine equations:
At 348.15 k (75 oC), P1sat = 83.2069 kPa P2sat = 41.9827 kPa
➢ Calculate P using equation for binary system:
Let x1 = 0.6
P = 41.9827 + (83.2069 - 41.9827)*0.6 = 66.7172 kPa
➢ Calculate value of y1 using Raoult’s Law expression:
y1 = [(0.6)(83.2069)]/66.7172 = 0.7483

It means that at 75 oC and 66.7172 kPa, a liquid mixture of 60% mol acetonitrile and
40% mol nitromethane is in equilibrium with a vapor mixture of 74.8295% mol
acetonitrile and 25.1705% mol nitromethane.

The results of calculations for 75 oC (348.15 K) at a number of values of x1:

x1 y1 P, kPa
0 0.0000 41.9827
0.1 0.1805 46.1051
0.2 0.3313 50.2275
0.3 0.4593 54.3500
0.4 0.5692 58.4724
0.5 0.6646 62.5948
0.6 0.7483 66.7172
0.7 0.8222 70.8396
0.8 0.8880 74.9621
0.9 0.9469 79.0845
1.0 1.0000 83.2069

DEW P calculations
➢ Calculate P using Eq. 1.24

20
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 ➢ Let y1 = 0.6 and T = 75 oC, calculate P:
P = 1/[(0.6/83.2069)+(0.4/41.9827)] = 59.7419 kPa
➢ Calculate value of x1 using Raoult’s Law expression:
x1 = [(0.6)(59.7419)]/83.2069 = 0.4308 *liquid-phase composition

(b)
➢ Calculate T1sat and T2sat at given pressure using Antoine equations:
For P = 70 kPa, T1sat = 342.9946 K/69.8446 oC T2sat = 362.7336 K/89.5836 oC
➢ Select T1sat < T < T2sat, calculate P1sat and P2sat for these temperature. For example take T =
78 oC (351.15 K):
At 351.15 K (78 oC), P1sat = 91.7611 kPa P2sat = 46.8368 kPa
➢ Lets evaluate x1 using equation for binary system:
x1 = (70 - 46.8368)/(91.7611 - 46.8368) = 0.5156
➢ Calculate the value of y1 using Raoult’s Law expression:
y1 = [(0.5156)(91.7611)]/70 = 0.6759

The results of this and similar calculations for P = 70 kPa are as follows:
T, oC x1 y1

69.8446 1.0000 1.0000

72 0.8596 0.9247

74 0.7378 0.8485

76 0.6233 0.7656

78 0.5156 0.6759

80 0.4142 0.5789

82 0.3184 0.4741

84 0.2280 0.3614

86 0.1424 0.2401

88 0.0613 0.1098

89.5836 0.0000 0.0000

BUBBL T calculations
For x1 = 0.6 and P = 70 kPa, T is determine by the iteration.
➢ Equation 1.22 is written as

21
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 P
P2sat = where  = P1sat / P2sat (1)
x1 + x2
➢ Subtract P2sat from ln P1sat a given by Antoine equations
2945.47 2972.64
ln  = 0.0681 − + (2)
t + 224.00 t + 209.00
➢ Iterate as follow
◾ Assume a t, oC ( an arbitrary intermediate t )
◾ Calculate α at the t assumed with (2)
◾ Calculate P2sat with (1)
◾ Calculate t from Antoine equations for species 2
2972.64
t= − 209.00
14.2043 − ln P2sat
◾ Compare the t calculated and the t assumed
◾ If t calculated ≠ t assumed, start new iteration using the t calculated

The result is t = 76.42 oC (349.57 K). From Antoine equation, P1sat = 87.17 kPa and by
Raoult’s Law expression, y1 = 0.7472

DEW T calculations
➢ With α = P1sat/P2sat, Eq. 1.24 is written as
P1sat = P( y1 + y2 )
➢ The iteration steps are as before, but are based on P1sat, with
2945.47
t= − 224.00
14.2724 − ln P1sat

The result is t = 79.58 oC (352.73 K). From Antoine equation, P1sat = 96.53 kPa and by
Raoult’s Law expression, x1 = 0.4351

Activity 1: Application of Raoult’s Law

Self-Assessment No. 7

Assuming the validity of Raoult’s law, do the following calculations for

benzene(1)/toluene(2) system:
a. Given x1 = 0.33 and T = 373.15 K, find y1 and P.
b. Given y1 = 0.33 and T = 373.15 K, find x1 and P.
c. Given x1 = 0.33 and P = 120 kPa, find y1 and T.
d. Given y1 = 0.33 and P = 120 kPa, find x1 and T.
e. Given T = 387.15 K and P = 120 kPa, find x1 and y1.
f. For part (e), if the overall mole fraction of benzene is z1 = 0.33, what molar fraction of
the two-phase system is vapor?
g. Why is Raoult’s law likely to be an excellent VLE model for this system at the stated
(or computed) conditions?
B
ln P sat / kPa = A −
T +C

22
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 Benzene: A = 13.8594, B = 2773.78, C = -53.08
Toluene: A = 14.0098, B = 3103.01, C = -53.36

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Henry’s Law

◾ Raoult’s law cannot be applied to a species whose critical temperature is less than the
equilibrium temperature of the system.

◾ Henry’s law is applied for:

➢ Very low pressure that the vapor phase may be assumed an ideal gas
➢ Very dilute solute in the liquid phase

Henry’s law states that the partial pressure of the species in the vapor-phase is
directly proportional to liquid-phase mole fraction.
y P = x H where Hi is Henry’s constant
i i i
(1.25)

Table 1.1: Henry’s Constant for Gases Dissolved in Water at 25 oC

Gas H / bar
Acetylene 1,350
Air 72,950
Carbon dioxide 1,670
Carbon monoxide 54,600
Ethane 30,600
Ethylene 11,550
Helium 126,600
Hydrogen 71,600
Hydrogen sulfide 550
Methane 41,850
Nitrogen 87,650
Oxygen 44,380

Example Problem No. 2

Assuming that carbonated water contains only CO2 and H2O, determine the compositions
of the vapor and liquid phases in a sealed can of “soda” and the pressure exerted on the
can at 283.15 K (10 oC). Henry’s constant for CO2 in water at 283.15 K (10 oC) is about 990
bar.

Solution:

Take species 1 as the CO2 and species 2 as the water, Henry’s law for species 1 and
Raoult’s law for species 2 are written:
y1P = x1H1 y2 P1 = x2 P2sat

23
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 These equations are added to give:
P = x1 H1 + x2 P2sat
Assume for the moment that the mole fraction of CO2 in the liquid is x1 = 0.0. With H1 = 990
bar and P2sat = 0.01227 bar [from steam tables at 283.15 K]
P = (0.01)(990) + (0.99)(0.01227) = 9.912 bar
This result is used in Henry’s law to determine a new value for x1. With y1 ≈ 1, Eq. 1.25 written
for species 1 becomes:
P 9.912
x1 = = = 0.0100
H1 990
Which confirms the original assumption. Then by Raoult’s Law, written for species 2,
x2 P2sat (0.99)(0.01227)
y2 = = = 0.0012
P 9.912
Whence y1 = 1 - y2 = 1 - 0.0012 = 0.9988, and the vapor phase is nearly pure CO2, as assumed.

Activity 2: Application of Henry’s Law

Self-Assessment No. 8

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 oC. At this temperature, H1 = 200 bar and P2sat = 0.10
bar. Determine good estimates of x1 and y1. State and justify all assumptions.

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Modified Raoult’s Law

▪ Applied for if vapor phase is an ideal gas but the liquid is not an ideal solution.
▪ Modified version of Raoult’s Law that can be stated as:
y P = x  P sat where ( i = 1, 2, …, N ) (1.26)
i i i i

▪ Activity coefficients,  i , are functions of temperature and liquid-phase composition, and

ultimately based on experiment.

Bubblepoint Calculations (xi is given)

N
P =  xi i Pi sat (1.27)
i =1

Dewpoint Calculations (yi is given)

1
P= N (1.28)
yi

i =1  i Pi
sat

Example Problem No. 3

24
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 For the system methanol(1)/methyl acetate(2), the following equations provide a
reasonable correlation for the activity coefficients.
ln  1 = Ax22 ln  2 = Ax12
where A = 2.771 − 0.00523T
In addition, the following Antoine equations provide vapor pressures:
3643.31
ln P1sat = 16.59158 −
T − 33.424
2665.54
ln P2sat = 14.25326 −
T − 53.424
where T is in Kelvin and the vapor pressures are in kPa. Assuming validity of Eq. 1.26,
calculate:
a. P and { yi } for T = 318.15 K and x1 = 0.25
b. P and { xi } for T = 318.15 K and y1 = 0.60
c. T and { yi } for P = 101.33 kPa and x1 = 0.85
d. T and { xi } for P = 101.33 kPa and y1 = 0.40
e. The azeotropic pressure and azeotropic composition for T = 318.15 K

Solution:
(a)

Activity 3: Application of Modified Raoult’s Law

Self-Assessment No. 9

A binary system of species 1 and 2 consists of vapor and liquid phases in equilibrium at
temperature T, for which

ln  1 = 1.8 x22 , ln  2 = 1.8 x12 , P1sat = 1.24 bar, P2sat = 0.89 bar

Assuming the validity of Eq. 1.26,

a) For what range of values of the overall mole fraction z1 can this two-phase system
exist with a liquid mole fraction x1 = 0.65?
b) What is the pressure P and vapor mole fraction y1 within this range?
c) What are the pressure and composition of the azeotrope at temperature T ?

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EXPLAIN

25
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 Activity 4: Simplifications: Raoult’s Law, Henry’s Law, and Modified Raoult’s Law (1)
Self-Assessment No. 10

1. Prove: An equilibrium liquid/vapor system described by Raoult’s law cannot exhibit

an azeotrope.
2. Of the following binary liquid/vapor systems, which can be approximately modeled
by Raoult’s law? For those that cannot, why not? Table B.1 (App. B) may be useful.
[Introduction to Chemical Engineering Thermodynamics 8Ed; Smith, Van Ness,
Abbott, Swihart]
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 oC
e. Water/n-decane at 1 bar
3. 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?
Table 1.1 may provide useful data.
4. Helium-laced gases are used as breathing media for deep-sea divers. Why?Table
1.1 may provide useful data.
5. For the system ethyl ethanoate(1)/n-heptane(2) at 343.15 K (70 oC)
ln  1 = 0.95 x22 , ln  2 = 0.95 x12 , P1sat = 79.80 kPa, P2sat = 40.50 kPa
Assuming validity of Eq. 1.26,
(a) Make a BUBBL P calculation for T = 343.15 K, x1 = 0.05.
(b) Make a DEW P calculation for T = 343.15 K, y1 = 0.05.
(c) What is the azeotrope composition and pressure at T = 343.15 K?

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ELABORATE AND EVALUATE

Activity 5: Simplifications: Raoult’s Law, Henry’s Law, and Modified Raoult’s Law (2)
Assignment No. 3

1. Assuming Raoult’s law to be valid, prepare a Pxy diagram for a temperature 363.15
K (90 oC) and Txy (T, oC) diagram for a pressure of 90 kPa for the following systems.
(a) benzene(1)/ethylbenzene(2)
(b) 1-chlorobutane(1)/chlorobenzene(2)
2. Assuming that carbonated water contains only CO2(1) and H2O(2), determine the
composition of the vapor and liquid phases in a sealed can of “soda”at 25 oC if the
pressure inside the can is 5 bar.
3. A liquid mixture of cyclohexanone(1)/phenol(2) for which x1 = 0.6 is in equilibrium
with its vapor at 417.15 K. Determine the equilibrium pressure P and vapor
composition y1 from the following information:
ln  1 = Ax22 , ln  2 = Ax12
At 417.15 K, P1sat = 75.20 kPa and P2sat = 31.66 kPa
The system forms an azeotrope at 417.15 K for which x1az = y1az = 0.294

26
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 To be submitted in Google classroom on:

27
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 Unit 5 VLE from K-Value Correlations

UNIT LEARNING OUTCOMES

• Carry out flash calculation in order to determine the vapor/liquid fraction as well
as the mixture composition of each phase at specified conditions using
available K-Values etc.

ENGAGE

A convenient measure of the tendency of a given chemical species to partition itself

preferentially between liquid and vapor phases is the equilibrium ratio, K, defined as:

yi (1.29)
Ki =
xi
This quantity is usually called simply a K-value. Although it adds nothing to thermodynamic
knowledge of VLE, it does serve as a measure of “lightness”of a constituent species, i.e., of
its tendency to favor the vapor phase. When Ki is greater than unity, species i exhibits a higher
concentration in the vapor phase; when less, a higher concentration in the liquid phase, and
is considered a “heavy”” constituent. Moreover, the use of K-values makes for
computational convenience, allowing elimination of one set of mole fractions { yi } or { xi } in
favor of the other

EXPLORE
Reference to Eq. 1.29 shows that the K-value for Raoult’s law is:
Pi sat
Ki = (1.30)
P
And reference to Eq. 1.26 shows that for modified Raoult’s law it is:
 i Pi sat
Ki = (1.31)
P
According to Eq. 1.29, yi = Ki xi ; because  i yi = 1 , then
 Ki xi = 1 (1.32)
i
Thus for bubblepoint calculations, where the xi are known, the problem is to find the set of
K-values that satisfies Eq. 1.32. Alternatively, Eq. 1.29 can be written xi = yi / Ki ; because
i xi = 1 , then
yi
K i
=1 (1.33)
i
Thus for dewpoint calculations, where the yi are known, the problem to find the set of K-
values that satisfies Eq. 1.33.

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.

28
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 Figures 1.9 and 1.10 show nomographs for K-values of light hydrocarbons as functions of T
and P, prepared by Dadyburjor. They do allow for a average effect of composition, but the
essential basis is Raoult’s law.

Example Problem No. 1

For a mixture of 10% mol methane, 20% mol ethane, and 70% mol propane at 283.15 K (10
oC), determine:

(a) The dew point pressure

(b) The bubble point pressure
The K-values are given by Fig. 1.9

Flash Calculations

An important application of VLE is the flash calculation. The name originates from the fact
that a liquid at a pressure equal to or greater than it bubblepoint pressure “flashes”or partially
evaporates when the pressure is reduced, producing a two-phase system of vapor and
liquid in equilibrium. We consider here only the P, T-flash, which refers to any calculations of
the quantities and compositions of the vapor and liquid phases making uo a two-phase
system in equilibrium at known T, P, and overall composition. This poses a problem known to
be determinate on the basis of Duhem’s theorem, because two independent variable ( T
and P ) are specified for a system of fixed overall composition, that is, a system formed from
given masses of nonreacting chemical species.

Considering a system containing one mole of nonreacting chemical scpecies with an overall
composition represented by the set of mole fractions { zi }. Let L be the moles of liquid, with
mole fractions { xi }. and let V be the moles of vapor, with mole fractions { yi }. The material-
balance equations are:
L +V = 1
zi = xi L + yiV ( i = 1, 2, …, N )
Combining these equations to eliminate L gives:
zi = xi (1 − V ) + yiV
Substituting xi = yi / Ki , and solving for yi yields:
zi K i
yi =
1 + V ( K i − 1)
Since  i yi = 1 , Eq. 1.? is summed over all species:
zi K i
 1 + V (K
i − 1)
=1
i

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 The initial step in solving a P, T-flash problem is to find the value of V which satisfies this
equation. Note that V = 1 is always a trivial solution.

EXPLAIN

Activity 1: Application of VLE from K-Value Correlations (1)

Self-Assessment No. 11

1. If a system exhibits VLE, at least one of the K-values must be greater than 1.0 and at
least one must be less than 1.0. Offer a proof of this observation.
2. Flash calculations are simpler for binary systems than for the general multicomponent
case, because the equilibrium compositions for a binary are independent of the
overall composition. Show that, for a binary system in VLE.
1− K2 K1 (1 − K 2 ) z1 ( K1 − K 2 ) − (1 − K 2 )
x1 = , y1 = ,V =
K1 − K 2 K1 − K 2 ( K1 − 1)(1 − K 2 )

To be submitted in Google classroom on:

ELABORATE AND EVALUATE

Activity 2: Application of VLE from K-Value Correlations (2)

Assignment No. 4

1. Assuming validity of the Dadyburjor charts, make the following VLE calculations for
the ethane(1)/propane(2)/isobutane(3)/isopentane(4) system:
(a) BUBL P, given x1 = 0.10, x2 = 0.20, x3 = 0.30, and T = 333.15 K (60 oC)
(b) DEW P, given y1 = 0.48, y2 = 0.25, y3 = 0.15, and T = 333.15 K (60 oC)
(c) BUBL T, given x1 = 0.14, x2 = 0.13, x3 = 0.25, and P = 15 bar
(d) DEW T, given y1 = 0.42, y2 = 0.30, y3 = 0.15, and P = 15 bar
2. An equimolar mixture of n-butane and n-hexane at pressure P is brought to a
temperature of 361.15 K (95 oC), where it exists as a vapor/liquid mixture in
equilibrium. If the mole fraction of -hexane in the liquid phase is 0.75, what is pressure
P (in bar), what is the molar fraction of the system that is liquid, and what is the
composition of the vapor phase?

To be submitted in Google classroom on:

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means, electronic, mechanical, photocopying, recording, or otherwise of any part of this document, without the prior written permission of SLU, is strictly prohibited.