Vapour-Liquid Equilibrium 391

Wohl's equation, van Laar cquation, Margules cquation, and UNIFAC method arc discussed.
Some simple methods are discussed to test the thermodynamic consistency of VLE data. In
addition, criteria or phasc cquilibrium of single and multiple componcnts are discussed.
Diagrams are cflicient tools to understand the processes clearly. Various diagrams--boiling point
diagram, Py, P-T diagram, ctc,-havc becn claboratcly discussed. Raoult's law is valid for
a system at low to moderate pressure. But the deviation from Raoult's law measures the non
ideality of the solution. Different types of azcotropcs are shovwn in graphical presentations along
with the principle of its formation. Astepwisc methodology for decducing the dew point, bubble
point and flash has becn discussed.

CRITERIA OF EQUILIBRIUM
Thermodynamics is very much concerned with the equilibrium state of the system. The term
equibrium is used to imply astate of balance of asystem. Equilibrium is a static condition in
which no changes occur in the macroscopic properties of a system with time. Consider that a
system is undergoing a change in a given state. If there is no change in the state of the system,
then the system is considered to be in a state of thermodynamic equilibrium. Hence, a system
is said to be in the equilibrium state if the system has no tendency to undergo any further change,
1.c., the propertics like pressure, temperature, and composition are uniform in magnitude
throughout the system.
It is needless to mention that in the equilibrium state there are no unbalanced driving forces
within the system, and so the system cannot exchange energy in the form of heat as well as work
with the surroundings.
The Clausius inequality plays an important role in cstablishing the thermodynamic criteria of
cquilibrium, and it can be substantiated by the following discussion.
Consider that asystem is placed in the surroundings and exchanging hcat with the reservoir
at temperature T and producing work as shown in Fig. 10..

Reservoir at
T

d)

System dW = PdW

Fig. 10.1 Demonstration on exchanging of heat between system and reservoir.

It can be written for either a finite or an infinitesimal change.

From the first law of thermodynamics
dQ = dU+ dW =dU + PdV (10.1)
 Vapour-Liquid Equilibrium 10

LEARNING OBJECTIVES
After reading this chapter, you will be able to
Know about the general criteria of equilibrium of a system
Establish the criterion for phase equilibrium
Introduce the phase rule for a non-reacting system and discuss Duhem's theorem
Develop the condition of phase equ1l1br1um for single-component systems
Discuss the phase equilibrium for mult1-component systems
Understand the vapour-liqu1d equilibrium diagram (P-T-xy) for binary mixtures
Discuss the deviations from Raoult's law as well as non-ideal solutions
Understand the formation of differcnt types of azcotropes
Explain the vapour-liquid equilibrium at low pressure and discuss the excess free encrgy
model
Deduce different equations such as Wohl's, Margules, and van Laar, and the UNIQUAC
and UNIFAC methods for the estimation of activity coefficients
Highlight the vapour-liquid cquilibrium at high pressure
Derive the equations for the calculation of dew point, bubble point and flash
" Test the thermodynamic consistency of vapour-liquid cquilibrium (VLE) data
The operations most commonly performed in the chemical, petroleum, and allied industries
and encountered by the process engincers involve distillation, absorption, adsorplion, lcaching,
extraction, drying, etc. These opcrations involve transfer of components from one phase to
another at different temperatures and pressures. More precisely, these are concerned with the
coexistence of vapour and liquid phases. The design and analysis of thcsc operations requircs the
knowledge of phase cquilibrium and an availability of vapour-liquid equilibrium (VLE) data. Most
of the times, accurate daa arc not available and so assignments arc complctod with fragmcntary
data. Therefore, an engincer often needs to use important corelations to check the correctness of
the data. Such correlations arc prcsentcd and derived in this chapter with the heip of the principle
of phase cquilibrium. For the cstimation of activity cocefficients at low to moderate pressurc.
390
 392 Introduction to Chemical Engineering Thernodynamics

From the second law of thermodynamics

dS dQ or dÌ TaSs 0 (10.2)
T
Combining Eq. (10.)with (10.2). we have
dU + PdV - Tas s0 (10.3)
This inequality applies to cvery incremental change of the system bctwcen cquilibrium states,
and it dictates the direction of change that leads towards equilibrium. This is uscd for developing
several cquilibrium criteria under various constraints. Each set of constraints considered
coTFesponds to a physically realistic or conmmonly encountered situation. The criteria are:
vCase I: Isolated System
By definition, an isolated svstem is incapable of exchanging heat, mass, or work with its
surroundings. Therefore, d) = 0 and dW = 0. Substituting these, we get, from the first law of
thermodynamics (Eq. (10.1), dU = 0. Since it is an isolated system, it would be of constant
volume, i... dV = 0.
Hence, from Eq. (10.3). we have
dSyr S0 (10.4)
This cquation nccessarily implies that cntropy can never decrcasc for any process occurring
in a system at constant / and V. This is constant for a reversible process and increases for an
ireversible proccss, which always lcads the system toward an cquilibrium state. Entropy will
have maximum value at cquilibrium, when it will not be possible for any further spontaneous
process to occur.
Case II: System at Constant T and V
VFor aclosed system undergoing a process at constant temperature and volume, the cquation of
incquality becomes
dU TdS < 0 (10.5)
Now, the definition of Helmholtz free energy or work function is given by
A= U- TS

dA = dU- TaS - SdT

dU = dA + Tas + SdT (10.6)

Comparing it with Eq. (10.3), we have
dA s -PdV - SdT (10.7)
For the process occurring at constant T and P, Eq. (10.7) becomes
dAry S0 (10.8)
The above equation indicates that the spontaneous process taking place at constant TandV
is accompanied by decrcasc in work function or Helmholtz frce cncrgy at cquilibrium.
 Vapour-Liquid Equilibrium 393

Case IIl: Svstem at Constant T and P

By definition, Gibbs free encrgy or Gibbs funclion is
G= H- 73
or

dG = dH - TaS - SdT (10.9)

From the definition of cnthalpy
H= U+ PV
or

dH = dU+ PdV+ VdP (10.10)

Substituting Eq. (10.10) into (10.9), we get
dG = dð+ PdV +VdP - TaS -SdT

dU = dG - PdV - VaP + TdS + SdT (10.11)

Comparing it with Eq. (10.3), we have
dG < VdP - SdT (10.12)
At constant temperature and pressure, Eq. (10.12) becomes
dG,p S0 (10.13)
Equation (10.13) implies that for the spontaneous process occurring at constant I and P,
Gibbs free energy is minimum at equilibrium.

10,2 CRITERION FOR PHASE EQUILIBRIUM

We have discussed so far the criteria of thermodynamic equilibrium of a system. It enables us
to determine the criterion of phase equilibrium. Consider a closed binary system comprising two
phases--vapour and liquid. If the system is in thermal and mechanical equilibrium, then another
important equilibrium is phase equilibrium, which needs to be taken into consideration because
the individual phases are free to exchange mass and energy between them. For instance, a small
amount of water left in aglassevaporates, a wet T-shirt hanging in an open area eventuallydries,
and the aftershave in an open bottle quickly disappcars. Thesce examples suggest that there is a
driving force between the two phases of a substance that forces the mass to transform from one
phase to another phase. The magnitude of this force depends on the relative concentrations of
the two phases. At constant temperature and pressure, when two componcnts are mixed
the state differentials can occur at equilibrium without producing any
well.
change in Gibbs frec
energy. It leads to a more general criterion of equilibrium fora multicomponent system, for which
dG = -SdT +VaP +)G,dn, (10.14)
At constant temperature, pressure and composition, Eq. (10.14) becomes
dGrp = 0 (10.15)
394 Introduction to Chemical Engmcerng
Thernodynamics
This is the actual criterion of phase
cquilibrium.
For the case of vapour-liquid cquilibrium, Gibbs frec cncrgy can be expressed as
(G= G + (

di = dGY + dG' = 0 (10.16)

where
G = Gibbs frcc cncrgy of saturatcd vapour phasc
G=Gibbs free cnergy of saturated liquid phase.

10.3 PHASE RULE FOR NON-REACTING SYSTEMS

AND DUHEM'S THEOREM
A single-componcnt two-phasc system may exist in equilibrium at different
tcmperatures or
pressurcs. Howevcr, oncc thc temperature is fixed, the system is locked in cquilibrium state and
all intensive properties of cach phase (except their relative amounts) are fixed. The
the phascs do not belong to the phase-ule variables. because thev have no
masses of
influence on the
intcnsive state of the systcm. Tempcrature., pressure, and composition arc considercd phasc rule
variables. Thercforc. a single-component two-phase system has one independent property, which
mav be either temperature or pressure.
The number of independent variables associated with a
multi-component, expressed asnon
reacting system is given by Gibbs phasc rule developed in 1875, and it can bemulti-phase
F=C-P + 2
where (10.17)
F =Number of degrees of freedom of the systems or number of
C = Number of independent variables
components
P = Number of phascs.
2is included in the equation to account for the fact
that the two intensive variables T and P must be Water vapour
specified to describe the state of equilibrium. T= 100°C
T= 150°C
For a single-component two-phase syslem, as
shown in Fig. 10.2. C= I and P= 2. Therefore.
the number of degrees of frecdom of the
systems or the number of independent variables, ELiquid water
F= l- 2 + 2 = I. That is, one independent
intensive property is required to be specificd. Fig. 10.2 Demonstration of single-component two
Thus, at the triplc point, F = | -3 + 2 = 0. It phase system having one independent
implies that none of the properties of a pure variable.
substance at the triple point can be varied.
We can derive Eq. (10.17) from the knowledge of criterion of phasce
cquilibrium. Lct us
consider a multi-componcnt system comprising C componcnts and P phases. So far as the
composition variables are concerned, in every phase the ( componcnts would have C different
concentrations. But in a closed system, if we arbitrarily choose concentration of C-l components.
the last one is fixcd by the remainder. Hence, there will be C-l
compositions in every phasc.
 Vapour-Liquid Equilibrium 395

For, all the P phases, the number of composition variables = P(C- 1)

In add1tion to this, two variables-temperature and pressure-are there.
Thus, the total number of variables
= P(C - I) + 2

Now, we consider the relation betwcen the phase variables. From the phase equilibrium
rclation, we gather that the chemical potential of componcnt is the same in allthe phascs u, b,
and c

Therefore., for P - l phases and C components, thc total number of phase cquilibrium
relations would be (P - 1)C So. the degrces of frccdom of the system is given by
F= P(C- I) + 2 - C(P - 1)) =C-P+ 2
Duhem's theorem is another kind of rule analogous to the Gibbs phase rule, but it deals also
with thc cxtensive propcrty of thc system. It applics to a closcd systcm at cquilibrium for which
thccxtensive state as well as the intensive state of the system is fixed. The state of
such a system
is known as completely determ1ned state and is characterized by both intensive (2 + (C- 1)]and
Cxtensivc (C) phasc-rule variables. Hcrc. the extensive variables are conccrned with thc masscs
or mole numbers. Hence. the total number of variables can be
expressed as
2 + (C - 1)P + P= 2+ CP (10.18)
whcrc thc second term (C - 1)P reprcscnts intensive variablcs and the third
term Prcprcscnts
extensive variables (mass).
Since the theorem is applied to a closed system formed from specified
amounts of the
chemical species, a material balance can be represented for each of the C chemical species. The
number of independent phase-cquilibrium equations nced to be taken into account with C
Consequently, the total number of cquations specics.

- (P - I)C + C = PC (10.19)
Then, the difference between the number of variables and the number of
by using Eqs. (10.18) and (10.19) as cquations is given
(2 + CP) -PC = 2
(10.20)
Based on Eg. (10.20), Duhem's theorcm states: For any closed
agiven mass ofprescribed chemical species, the system formed initially from
cny wo independent variables are fixed.
equilibrium state is completely determined when
Equalion (10.20) implies that only two independent variables (either
arc rcquircd to be spccificd to definc the statc extensive or
of thc systcm. Hence, the conclusionsintensive)
phasc rule can be summarizcd as follows: from thc
The number of indepcndent intensive variables is
provided by the phase rule.
When F= 1, at least onc of the two variables must be
" When F= 0, both must be extensive.
extensive.
396 Inyduction to Chemical Engincering
Thernodynamics
10.4 PHASE EQUILIBRIUM FOR SINGLE-COMPONENT SYSTEM
The cquilibrium criterion for a systcm consisting of two phases of a pure substancc such as
water is casily devcloped by considering a mixture of saturated liquid and saturated vapour in
equil1brium at a constant tenperature and pressure, as shown in Fig. 10.2.
The total Gibbs function of this mixture based on the criterion of cquilibrium to thc system
Is given by
dG = dG + dG (10.21)
= G' dn + Gdn' = 0 (10.22)
(as dG = dG + dG=) G, dn, = G dn + G dn at constant temperature and
pressure)
where
G = Gibbs function of saturated vapour
phase
G=Gibbs function of saturated liquid phase.
Since dn' + dn' = 0, then dn' = -dn. Substituting this into Eq. (10.22). wc
gct
(G- G) dn = 0
G' = G (10.23)
Equation (10.23) docs ncccssarily mean that thc (wo phascs of a purc substance arc in
equilibrium when the Gibbs free energy component in them are the same.
Similar conclusions can be drawn for two other different phascs
Consider a closed containcr consisting of saturatcd vapour and saturatcdhaving one component.
liquid. If the proccss
is allowed to take place at constant temperature and pressure, then thc
mass will be transferred
from one phase to another phase. Therefore, the change in Gibbs free energy for this
process would bc reversible
G = H- TASY
and (10.24)
G= H TAS! (10.25)
Since the process 0ccurs at constant pressure, we put AH= Q= TAS
into Egs. (10.24) and
(10.25) and comparc them to obtain
G= G!
Hence, it is supported well by Gibbs function equation. I can be
fugacity as expresscd in terms of

as Gibbs frcc cnergy is rclatcd to the (10.26)

fugacity of the pure componcnt by
G= G' + RT In f
where G is constant. (10.27)
The above criteria can also be applied to more than two
phascs.
 Vapour-Liquid Equilibrium 397

EXAMPLE 10.1 Applying the criterion for cquilibrium, derive the Clausius-Clapeyron cquation.
Solution: The Clausius-Clapeyron cquation can bederived by applying cquilibrium criterion.
We know hat for a binary mixture comprising two componcnts P andQ at cquilibrium, the
differential form of Gibbs frec energy is given by
dGP = dG! (i)
From the thermodynamic fundamental relation, we have
dG = VdP SdT (iü)
Hence. Eq. (i) can bc exprcssed as

or

(vP - v)dP = (S - SeydT

dP AS
dT AV
(iii)
For the componcnts P and Q. wc may also write in the following form of Gibbs cncrgy:
G= G2
or

G= H - 7_!
and similarly
G = H - T^O
So
H- Ts = H?-TS!
AH = H - H° = T(S - S) = TAS (iv)
Substituting Eq. (iv) into (), we get
dP AS AH AH
dT AV TAV (v)
T(V,- V)
Sincc V, > V, and vapour is assumed to bchave idcally, Eq. (v) yiclds
dP AH AH PAH
dT RT? (vi)
TV,
Or

1 dP AH
P dT RT? (vi)
or

d In P AH
dT RT (viii)
398 Introduction to Chemical Engineenmg Themodynamics

For small temperaturc ranges, the cnthalpy change of thc process can be trcated further as a
constant. Then on integration, Eq. (vii) yiclds

(ix)

This cquation is called the Clausius-Clapeyron equation and is used to determine the variation
of pressure, wih tempcrature.

105PHASE EQUILIBRIUM FOR MULTI-COMPONENT SYSTEM

In engineering practice, we come across many multi-componcnt systems which have two or
more phases. A multi-component multi-phase system at a given temperature and pressure will
be in cquilibrium when there is no driving force between the different phases of cach componcnt.
Therefore. for phase equilibrium, the specific Gibbs function or chemical potential of cach
component must be the same in all phases.
For a closed heterogencous system consisting of twophases (a, b) in equilibrium, the change
in frce encrgy can be written as
dG = VdP - SdT+ (10.28)

At constant temperature and pressure. Eq. (10.28) becomes

dG - dn, (10.29)
From the criterion for phase cquilibrium, we have
dG = 0 (10.30)
Comparing Eq. (10.30) with (10.29). we get
udn, =0
i
Hence, we may write

(10.31)
i
or

(10.32)
i

Sincc dn, = dn + dn = 0, then dn = -dn. Substituting this into Eq. (10.32), we get
(10.33)

(i= 1, 2, 3, .... N) (10.34)

 Vapour-Liquid Equulibrium 399

Hence, it can be concluded that for mul1ple phases at the same temperature and pressure,
Ine chemical potential of a component in every phase must be tlhe same under equilibrium
condtions.
Chemical potential is related to fugacity of a componcnt as
M, = G, + RT In

Thercfore, the criterion for cquilibrium would be

(i= 1, 2, 3, ..., N) (10.35)

\10.6 VAPOUR-LIQUID EQUILIBRIUM DIAGRAM FOR BINARY MIXTURE

Vapour-iquidequilibrium is a condition where cither
a liquid is in cquilibrium with its vapour or a state of
coexistence of liquid and vapour phases exists Vapour
where thec rate of evaporation (liquid changing to T, P, y;
vapour) is cqual to the rate of condcnsation (vapour
changing to liquid).
Let us considcr a binary liquid mixture of
benzenc and toluenc existing in (wo phascs shown in Liquid
T, P, x,
Fig. 10.3. In accordance with the phase rule, the
degree of frccdom or the number of indepcndent
variables of the system would be 2 as per the
Schematic representation of vapour
expression F=C-P+ 2 = 2- 2+2 = 2, Since we Fig. 10.3 liquid equilibrium for benzene-toluene
know that temperature, pressure, and composition
system.
(x, y) of a binary system arc considered phase rule
the
variables, any two of them can be independently varied. For the benzenctoluene system,
vapour
volatility of benzene (1) is considered to be more than that of toluene (2). That is, the
pressure of benzenc is higher than that of toluenc. On heating, the liquid (x) is converted into
componcnt 1. If the
vapour (), and the vapour is enriched with greater amounts of volatile
composition
process takes place at constant pressurc, the pressurc is fixed and thc liquid phase
(x;) can be varied independently as it is given. Therefore, two degrees of freedom are used. The
altered.
remaining properties are temperature and vapour phase composition (Vi), which can beSimilarly,
Hence, at constant pressurc, temperature versus composition (vapour) plot is obtaincd.
at constant temperature, pressure versus composition (vapour) plot, and at constant temperature
or pressure, vapour phase composition versus liquid phase composition can be obtained.
Thereforc, the VLE of a binary system can be better represcntcd by the following thrce kinds
of diagrams:
Temperature-Composition (T-xy) diagram;
Pressure-Composition (P-y) diagram;
Pressure-Temperature (P-T) diagram.
400 Introduçtion to Chemical Engineering Thermodynamics

Temperature-Composition (T-x-y) Diagram

represcnted on a
The vapour-liquid cquilibrium ofa binary mixture at constant pressure can be
against composition of liquid
1--y diagram in which temperaturc (along the ordinatc) is plottcdboiling point diagram and is shown
and vapour (along the abscissa). This diagram is known as the temperature. The
values change with
in Fig. 10.4. It is used to understand hov the cquilibrium depicted
pressurc of 101.32 kPa is
boil1ng point diagram for a benzenc-toluene system at a total
which boils at 80.1°C, is more volatile
in the figure. It can be scen from the plot that benzenc, the saturated vapour curve, which is
than toluene, which boils at 110.6°C. The upper curve is
saturated liquid curve, known as the bubble
called the dew point cuve, and the lower curve is the
becomes purely one component, where
point cunve. These two curves meet where the mixture
x=0, pure componcnt 1). The temperaturcs
X =0 (and x = 1, pure component 2) or x1=1 (and of the two pure components.
at those two points correspond to the boiling points
120
Pressure = Constant

110 Dew point curve

Vapour
(°C)
Temperature,

100
Vapour-liquid mixture
Liquid + Vapour

90

Bubble point curve

80
Liquid

70 1.0
0.2 0.4 0.6 0.8

Mole fraction of benzene in liquid x or vapour y.

mixture.
Fig. 10.4 Temperature-composition diagram of binary VLE
region, where the mixture
The region bounded by these two curves is called the wo-phase
point curve is known as sub-cooled
is partly liquid and partly vapour. The region below the bubblepoint curvc is superheated region
region (sub-cooled liquid) and the rcgion above the dew mixture which consists
(superheated vapour). Any point above the upper curve represcnts a
represents a completcly liquid mixture.
entirely of vapour and any point below the lower curve =0.42, which
composition x
Point x, on the lower curve, represents a completely liquid mixture of
 Vapour-Liquid Equilibrium 401

will start to boil at 90°C, and the composition of the vapour in equilibrium is y; = 0.75,
represented by point y, that is, v, > x,. So the points x and y, which lie on the same horizontal
line, represcnt cquilibrium compositions at a temperature of 95°C. For systems which follow
Raoult's law, the boiling point diagram can be drawn from the pure component vapour pressure
data. Thcse two curves meet where the mixture becomes purely one componcnt, wherc x =0
(and x = l, pure component 2) or x, = 1 (and x, = 0, pure component 1). The temperatures
at those two points correspond to the boiling points of the two pure components.

Pressure-Composition (P-x-y) Diagram

Al constant tempcrature the vapour-liquid eguilibrium of a binary mixture can be illustrated on
a P-x-ydiagram (sce Fig. 10.5)with pressure along the ordinate and the composition of liquid
and vapour along the abscissa. Considering again the benzene-toluene system, benzene (species
1) is the lighter or morc volatile of the two, so at saturatcd condition the vapour pressurc of
benzene is higher than that of tolucnc (spccies 2), i.e.. P}t > P.

Temperature = Constant
R P vs xcurve

Liquid Bubble point

pressure
Pressure
Liquid + Vapour

Dew point pressure

Pvs y curve
Vapour
P§at

Mole fraction of benzene in liquid x or vapour y1

Fig. 10.5 Pressure-composition diagram of binary VLE mixture.

The uppcr curve is the saturated liquid curve, which is called the P versus x curve, and the
lower curve is the saturatcd vapour curve and is known as the P versus y curve. The space
betwecn the two curves is the region of coexistence of both liquid and vapour phases is called
the two-phase region. Here the mixture is partly saturated liquid and partly saturated vapour. The
vapour is richer in the more volatile component, i.e., benzene. Consequently. at any pressure.
402 Introduction to Chemical Engineering Thermodynamics

yË >x.In Fig. 10.5, the horizontal lines such as P). VT and SW arccalled tie Imes. They conncct
the vapour and liquid phases in equilibrium. Now, on lowering the pressure at constant
temperature, the liquid mixture starts forming the vapour bubble and therefore the pressure al
which the bubble formation takes place is known as the bubble point pressure. The point S' in the
line RSTU represents the bubble point pressure. The condition of the binary vapour-liquid
equil1brium mixture is represented by the line RSTU. On further reduction in pressure, the entire
liquid is gradually transformed into vapour and a drop of liquid is left. This pressure is called the
dew point pressure, reprcscnted by the point T. The pressure is reduced further and at thc point
U, the vapour is converted into supcrheated vapour.

10.5.3 Pressure-Temperature (P-D) Diagram

The pressure-temperature diagram for a vapour-liguid cquilibrium of a binary mixture of given
composition is shown in Fig. 10.6, in which pressure along thc ordinate is plotted against
temperature along the abscissa. For a pure substance, the critical point is defined as the highest
temperature and pressurc at which liquid and vapour can co-exist in equilibrium. At the critical
point. liquid and vapour are indistinguishable. The properties of saturated liquid and vapour are
identical. Hence, above the critical point, condensation of a pure substance is impossible. But for
a binary or multicomponent mixture, it is not corroborated in Fig. 10,6. It can be seen from the
figure that the critical temperalure and pressure do not correspond to the highest pressure and
temperature, but the saturatcd liquid linc merges with the saturated vapour linc. Thercfore. for

Maxcondenbar
Critical point

B
Retrograde region
Bubble-point curve H
Liquid
Pressure
=0.2 0.4 0.6 0.8 0.9E

Constant quality lines

Vapour
Dew point curve
Maxcondenthernm
Temperature
Fig. 10.6 Pressure-temperature diagram of binary VLE mixture.
 Vapour-L.iquid Equilibrium 413

10.10 AZEOTROPE FORMATION

boiling point diagram. It cnablcs us o
We havc discusscd alrcady about thc importance of the
change in cquilibrium with respect to
understand how the compositions of liguid and vapour minimum
diagram. T--valso shows a maximum or
temperature at constant pressurc. Like P-x composition of thc liquid and
boiling points. the
temperaturc. At these maximum or minimum azcotropc. The tCrm
vapour-liguid mixture is callcd an
vapour phases arc identical. Such a without changing.
azeotrope stems from a Greek word meaning boiling components in such a ratio that
its
more purc
An azcotrope 1s a mixturc of two ordistillation., This is becausc when an azcotropc 1s
simple original mixture of liquids.
composition cannot be changcd by ratio of constituents as the
vapour has the same constant boiling
boiled, the resulting boiling, azeotropes are also known as
unchanged by
hs ne Composition is there
mictures. azeotropes are formed when
components A and B, and B
For a binary mixture comprising
ideality and the vapour pressures of the componcnts A
deviation from
1s alarge positivc
different. azeotrope is either
are not much
characteristic boiling point. The boiling point of an grcater than thc
Each azeotrope has a positive azcotropc), or
than the boiling points of any of its constituents (a
less
constituents (a negative azeotrope). preceding examples, are called
boiling point of any of its constituents, such as the two azeotropes.
Azeotropes consisting of two three constituents are called lernary
consisting of
binary azeotropes. Those constituents are also known.
Azeotropes ef more than three

10.J8.1 Types of Azeotropes

classes. These arc:
Azcotropes can bc categorized into two negative and
deviation from ideal behaviour is
Maximum-boiling Azeotropes If the liquid and vapour
the curve in the plot of the total pressure against the azeotropic
large,
at a constant temperature passes through a minimum at the boiling
compositions behaviour is known as a maximum
azeotrope that exhibits such
point. An boiling point temperature at the azeotropic
azeotrope (shown in Fig. 10.10) because the constant.
is held
point is maximum if the total pressure
maximum boiling azcotrope or negative azeotrope is nitric acid at a
An example of water (by weight). HCI boils at
concentration of 20.2% hydrochloric acid and 79.8%
at 110°C, which is higher than cither
-84°C and water at 100°C, but the azeotrope boilsmaximum temperature at which any
of its constituents. Indeed, 110°C is the negative azcotrope boils at
hydrochloric acid solution can boil. It isgenerally true that a Negative azcotropes are
constituents.
a higher temperature than for any other ratio of its negative deviation from Raoult's
also callcd maximum boiling mixtures, i.e. they show
law In Y<0.
" Minimum-boiling Azeotropes If the deviation from
ideal behaviour is positive and
much different,
sufficiently large, and the vapour pressures of the components are not
at
the curve in the plot of the total pressure against the liquid and vapour compositions
414 Introduction to Chemical Engineerng Thernodvnamics

Vapour
pressure
Boiling
point

79.8% 100%
79.8% 100% 0%
0% Composition
Composition
azeotrope.
10.10 (a) T-X-ydiagram; (b) P-x-ydiagram for maximum boiling
Fig.
azeotropic point. An azcotrope
temperature passes through a maximum at thc It is depicted in
aconstant
such behaviour is known as minimum boiling azeotrope.
that shows
Fig. 10.1l.

Vapour
pressure

Boiling
point

59% 100%
0% 59% 100% 0%
Composition
Composition
boilingazeotrope.
Fig. 10.11 (a) T-x-y diagram; (b) P-x-y diagram for minimum
41% watcr (by
A well-known examplc of positive azcotropc is 59% pyridinc and
at 100°C, but the azeotrope boils at
weight). Pyridine boils at 92°C and water boils
78.1°C, which is lower than either of its constituents. Indccd, 78.1°C is the minimum
temperaturc at which any pyridinc-water solution can boil. It is gencrally truc that a
positive azcotrope boils at a lower temperature than for any other ralio of its constitucntls.
Positive azeotropes are also called minimum boiling mixtures, i.e., positive deviation from
Raoult's law In %> 0.
 Vapour-Lquid Equilibrium 415

EXAMPLE 10.7 For a binary Svstem. the cxcess Gibbs frcc energy of componcnts au
GE conponcnts Iand 2 are given
at 30°C is givcn by *O.025XN2. Thc vapour pressurcs of
RT
by 3800
3800
and In Pat = 14,01
In pSat = 13.71 -
T
Calculate the composition of the azcotrope.
where P and Pa are in bar and 7 is in K.
Solution: We know that at the azcotropic point
P= YPat = P
or

Y2
we get
Taking natural logarithm of both sides, 0.3 (i)
, = In Pat In PSat = |4.01 - 13.71 =
In Y - ln
GE and In Y = Axí.
Now, if = Ax. then In X= Ax; get
RT substituting this condition into the equation, we
Comparing it with the given equation and
(x3-x) = 0.3
Ax3- Axi = A(r-x) = 0.625
(ü)
0.3
0.625 [(x - ) (*, + x)]=
+ , = 1, Eq. (i)
becomes
Since for a binary solution, x; (as x, = l - x)
2x;) = 0.3
0.625 (x - x) = 0.625(1 -
or
0.3 = 0.48
(1 -2x;) =
0.625

X = 0.26
30°C is x = 0.26.
Therefore, the azeotropic composition at
PRESSURE:
10.11 VAPOUR-LIQUID EQUILIBRIUM AT LOW
MODEL
EXCESS GIBBS FREE ENERGY
cubic
liquid mixturc can be dctermincd by using the
The fugacity cocfficicnt of a componcnt in a properties. Similarly, excess properties,
equation of state and applying the concept of residual purposc. In this scction, various cxcess
another important concept, can be applied to serve the becn discussed. Thc advantage in using the
Gibbs frec encrgy models for binary solutions have Gibbs free energy is not a function of
models is that at low to moderate pressure, the excess
pressure and composition. With the help
pressure, while in general it is a function of temperature,
 Vape-gd Eguitrnan 431

For binary mixtures, the ratio of the K-alucs for the two componcnts is calledthe relatrve
volanlhy and is denoted by
K (10.93)
K

which is a mcasurc of the rclative case or difficulty of scparating the two componcts Large
Scale industrial distillation is rarcly undertaken if the relative volatility is less than I.05, with the
Volatilc componcnt being and the less solatile componcnt being . K-valucs arc widcly uscd in
the dcsign calculations of cotinuous distillation columns for dist1lling muiti-componcnt mixturcs.

10.12.1 Methodology for Bubble Point Calculations

Before going on to the discussion of the methodology for the cstimation which of bubblc point, it is
important to dcfine the term properly. Bubble point is dcfincd as the point at the first bubble
of vapour is formed upon heating a liquid consisting of two or more components at gIven
pressurc.
At the bubble point. the compositíion of thc liquid is the same as that of the ent1re system
We know that

K =

or

y, = Kx,
or
(10.94)

where

y, = Mole fraction of component i in the vapour phase and)y, = 1

x, =Mole fraction of componcnt in the liquid phase and)x, = 1.
Then. at the given mole fraction of one component in liquid or vapour phase, the mole
fraction of another can be oblaincd by the prcccding relation. Atconstant temperature. 10.13
assuming
and
the bubble point pressure, we get K, and K from the nomographs shown in Figures
10.14 and substitute the values in the cquation ,= ) Kx, We verify whether the summation
of the mole fractions of the componcnt in a particular phase is 1. If not so, then we assume
another bubble point pressure and repeat the procedure.
Stepwise Methodology at a Glance
" Step I: For a given Tor P, with the other not given, assume a value for the missing onc.
" Step II: At given x, find x For example, if x = 0.45, then x, = 0.55.
 152 Introduction toCheical Engneering Thermodynamics
nomograph with respect to known 7 or P and
Step III: Get K and K, values from the
assumed Tor P
Step IV: Using the relation y, = Kx, get y, and y2
verify that it cquals I or not.
Step V: Sum up the values of v, and y and P or T and repcat the proccdurc until thc
another
Step V: Ify, + y # l, then assume the ctual bubble point valuc
summation becomes 1. The satisfying T or P is
LuluulLmlL TTTTTTTTT,

TTTTTT
20

110
TT
10
150

000

Lulludenulualulalul L
....
L...
Lunuhduautmaluuu

10
n-Nonane

(kPa)
Pressure
Luluhumuua
deadwludulal n-Octane

n-Heptane
20

(°C)
Temperature
n-Hexane 30

LuwlukuLual TTTTTT
n-Pentane
1500
Isopentanc
TT
Cthane
2000

Ethylenc Propane
Propylene -50
3000 n-Butane

4000 Isobutane
5000 Methane 60
6000

70

Fig. 10.13 K-values for the systems of light hydrocarbons at low temperature range.
 Methane Ethylene
Ethane
Propylene
Propane Isobutane
Isopentanen-Heptane
n-Pentane
T-Nonane
Vapour-Liquud Equilitbrium 433
n-Butane n-Hexane
n-Octanen-Decane

uuuhuuluu

(kPa)
Pressure
m d uTTT
Ethylene ludlulaLLw
TTrT (°C)
Temperature
T

600

700
Lmmmuuual
Methane
..?.
1000
..
TITTTTTT
1500
RLLuulunL
40

2000 n-Decane
2500 Luulul
3000
3500 Propylene
u 20
A000 Ethane Propane n-Octanen-Nonane
rr
Isobutane
s000
tSopentane
n-Butane
n-Pentane n-Heptane
10

n-Hexane

range.
Fig. 10.14 K-values for the systems of light hydrocarbons at high temperature

EXAMPLE 10.14 A piston-cylinder assembly contains a binary liquid mixture which

comprises 40% cthane by mole and 60% propane by mole at 1.5 MPa. Applying K-mcthod.
vapour
calculate the temperature at which vaporization begins and the composition of the first
bubble formed.
 Introduction to Chemical Engineering Themodynanics
Solution: We are given that
Mole fraction of cthane in the vapour phasec, x = 0.4
Molc fraction of propanc in the vapour phasc, x) 0.6
Vapour pressure, P= 15 MPa.
Hence. we assume that temperature T = 10°C.
The corrcsponding values of Kfor cthanc and propane oblaincd from Fig. 10.5 arc K, = 1.3
and K, = 0.5.
Now, we know thaty, = K,x, Putting the valucs of K, and x into the relation, wc have
y, =K,x, = 1.8 x 0.4 = 0.72
Similarly
' = K, = 0.5 × 0.6 = 0.30
Hence
'it =0.72+ 0.30 = 1.02

1.e.. y, > L0.

and K, = 0.5.
assume another value of T 9°C We get from Fjg. 10.5 that K, = 1.75
So. we
Putting the values of K, and x, into the relation y, = K,x,, we get
y, = K,= 1.75 x 0,4 = 0.70
Similarly
½= Kzx) = 0.5 x 0.6 = 0.30
Hencc
V) + = 0.70 + 0.30 = l0

1.e..,
Xy, = 1.0.
Thereforc, the bubble tempcraturc is 9°C and
So, the assumed value of T= 9°C is corrcct.
y, = 0.70.
the conposition of the vapour bubble,

Ó.12.2 Methodology for Dew Point Calculations

drop of liquid (condensate) is formed upon
Dew point is defined as the point at which the first point
point is a saturalion point. When the dew
cooling the vapour at given pressure. The dew as the water vapour no longer
temperature falls below freezing it is often called the frost point, is associated with relative
The dew point
creates dew but instead creates frost by deposition. point is closer to the current air
humidity. A high relative humidity indicates that the dew currcnt temperature.
temperature: if the relative humidity is 100%, the dew point is cqual to thc in relative
will lead to a decrease
At aconstant dew point, an incrcase in tcmperature
humidity. At a given pressure, the dew point is independent of temperature and it indicates that
specific humidity of
the molc fraction of water vapour in the air, and thercforc determines thc is used to calculate
the air. The dew point is an important statistic for general aviation pilots, as it
base.
the likelihood of carburettor icing and fog, and to estimate the height of the cloud
 t

Vapour-Liquid Equilibrium 435

We know that

x, =
K
or

(10.95)

becomputed using the same method as the onc

Ihe dew point temperature or prcssure can
employed for the calculation of bubble point.
Stepwise Procedure
This consists of the following steps:
the other not given. assume the
value for the missing
Step l: For a given T or P. with
one.
example if y', = 0.4, then y, = 0.6.
Step I1: Atgiven y). find '». For known 7or P and
from the nomograph with respect to
Step IIl: Get K- and Ky-alues
assumed T or P.
and x, = get xË and x.
" Step IV: Using the relation x; K K,
x; and x, and verify whether it equals I or not.
Sum up the values of until the
Step V:
# 1. then assume another P or T and repeat the procedure
Step VI: If x,+ x, T or P is the actual bubblc
point valuc.
summation bccomcs 1. The corresponding
point are the same and are
single-component mixtures the bubble point and the dew sources of data
For along with the dew point are useful
referredoas the boiling point. Bubble point distillation systems.
equipment used in prOcess industries, such as
indesfgning different kinds of
cthanc and
per cent methane, 30mol per cent
ÉXAMPLE 10.15 A vapour mixture of 20mol K-factors, detcrmince the pressurc at which
30°C. Using
50mol pcr ccnt propanc is available at isothermally compressed and also calculate the
condensation begins if the mixture is
composition of the first drop of liquid forms.

Solution: We are givcn that

T = 30°C
V = 0.2, y, = 0.3, y, = 0.5, and
corresponding values of Kfor ethane and
We assume that pressure, P= 2.0 MPa. The
K, = 0.68.
propanc obtained from Fig. 10.5 are K = 8.5, K, = 2.0 and
Now, we know that
x, =
K,
436 Introduction to Chemical Engineering Thermodynarnics
Putting the values of K, and x into the relation, we have
0.2
00235
K, 8.5
Similarly
0.3
015
K, 2.0
0.5
0714
K, 0.7

Hence
0,887
X t , t x; = 0.0235 + 0.115 + 0.714 =
1.c..

Xx<1.0.
30°C. We get from Fig. 10.5 that
So. we assume another value of P = 2.15 MPa at
K, = 8.1, K, = 1.82 and K; = 0.62.

Put the valucs of K, and y into the relation x, = K,

0.2
= 0.0247
K 8.1

Similarly 0.5 = 0,8065

0.3
= 0.1648 and
1.82 K, 0.62
K,
Hence
0.8065 = 0.996 =1
X + + x, =0.0247 + 0. 1648 +
i.e.,
y- 1.0.
the dew pressure is 2.15 MPa
Sothe assumed value of P=2.15 MPa is correct. Thereforc,
and x, = 0.1648.
and he composition of the liquid drop, x =0.0247
methanc, 20 mol per cent cthane and
EXAMPLE 10.16 For a mixture of l0 mol per cent
Determine
V 70 mol per cent propane at 10°C.
(a) The dew point pressure.
(b) The bubble point pressure.
Get K-values from Fig, 10.5.
Solution: (a) Calculation of dew point pressure
and T= 10°C. We assume that the pressures
We are given that y) =0.1, y, =0.2 and y = 0.7 corresponding values of Kfor ethane
the
P=690 kPa, P, = 1035 kPa, and P, =870 kPa. Then
as follows:
and propane, obtained from Fig. 10.5, can be presented
 Vapour-Liquid Equilibrium 437

P, =690 kPa P,= 1035 kPa P; = 870 kPa

Species K, K K,
K, K K
Methane 0.10 20,0 0,005 13.2 0,008 16.0 0.006
Ethane 0.20 3.25 0,062 2.25 0.089 2.65 0,075
Propane 0.70 0.92 0.761 0.65 L.077 0.762 0,919
)K, -0828 SK, -1174 L= 1000

The assumed value P= 870kPa is correct as it satisfies the dew point cquation. Hence, the
dew pressure is obtaincd as 870 kPa. The composition of the dew drop is the cstimatcd valuc
listed in the last column.
(b) Calculation of bubble point pressure
When the svstem is almost condensed, it is at its bubble point and the given mole fractions of
,. Again, using trial and error method, we can determinc the bubble point pressure by assuming
that the pressure for whichthe corrcsponding K-valucs obtaincd from Fig. 10.5 satisfy the bubble
point equation.
P, = 2622 kPa P, = 2760 KPa P. =2656 kPa
Species K K, K, Kx, K Kx,
Methane 0.10 5.60 0.560 5.25 0.525 5.49 0.549
Ethane 0.20 1.11 0.222 1.07 0.214 110 0.220
Propane 0.70 0.335 0.235 0.32 0.224 0.33 0.231

SK*,= 1.017 SK*, = 0.963 Kx, =1.000

Assumcd value P = 2656 kPa is correct because it satisfics the bubble point cquation. Hence,
the bubble point pressure is 2656 kPa. The composition of the vapour bubble is the estimated
value shown in the last column.

0.12.3 Flash Calculations

Flash calculation is an important application of vapour-liquid equilibrium, in which estimation of
mole fractions of components in the liquid and vapour phases at given temperature, pressure and
mole fraction of the component in the feed strcam is done. Consider that a binary mixturc consisting
of components A and flows through a flash vaporizer at the rate of F mol/h as illustrated in
Fig. 10.15. After vaporization, the mixture is separated into vapour and liquid streams at equilibrium.
Then the total material balance for the system gives
F= V+ L

where
F= Total number of moles of feed
V=Number of moles of vapour stream
L = Number of moles of liquid strcam.
438 Introduction to Chemical Engineering Themodynamics

Vapour b;

Feed Fz, Separator

Heater

Flash vaporizer
Liquid

Fig. 10.15 Demonstration of flash distillation.

Material balance for the componcnts gives

F, =Lx, + by, (10.96)
where
z, = Mole fraction of component i in feed stream
x, = Mole fraction of component i in liquid phase
V =Mole fraction of component in vapour phasc.
We knowv from the basic concept of the vapour-liquid equilibrium that y, - K, Substituting
V, = Kx, to replace y, from Eq. (10.96), we get
Fz, = Lx, + VKx, = x,(L + VK,)
Fz; F
(10.97)
(L+ VK;)

Asx, = 1, we have
F
= ] (10.98)

Again, if x, is replaced by substituting x, = K, from Eq. (10.96). we get

Fz, = Lx, + Vy, = L (10.99)

K,
Fz; F
Y, = (10.100)
V L
VK,