KMM3531 Chemical Engineering Thermodynamics II

Vapor/Liquid Equilibrium

Prof. Dr. Hasan SADIKOĞLU

Yıldız Technical University
Department of Chemical Engineering
• Understand that equilibrium implies absence of driving forces for net changes in the
macroscopic state of a system
• State and apply the phase rule and Duhem’s theorem for non-reacting systems
• Understand the relationship between excess Gibbs energy and activity coefficients
• Explain and interpret each of the following five types of VLE calculations:
-Bubble point pressure (BUBL P) calculations
-Dew point pressure (DEW P) calculations
-Bubble point temperature (BUBL T ) calculations
-Dew point temperature (DEW T ) calculations
-P, T-flash calculations
• Carry out each of the five types of VLE calculations using each of the following VLE
formulations:
-Raoult’s law
-Modified Raoult’s law, with activity coefficients
-State and apply Henry’s law
-K-value Correlations
The chemical composition and therefore the chemical equilibrium
depends on the pressure and temperature of the reacting system.
Therefore, when developing a general criterion for chemical
equilibrium, we consider a reacting system at a fixed temperature and
pressure.
A system and its surroundings form an
adiabatic system, and for such systems

The previous equation reduces to dSsys = 0.

That is, a chemical reaction in an adiabatic
chamber proceeds in the direction of increasing
entropy.

When the entropy reaches a maximum, the

reaction stops (Fig. 16–2).

Therefore, entropy is a very useful property in

the analysis of reacting adiabatic systems.
When a reacting system involves heat transfer, the increase of entropy
principle relation

becomes impractical to use, however, since it requires a knowledge of

heat transfer between the system and its surroundings. A more practical
approach would be to develop a relation for the equilibrium criterion in
terms of the properties of the reacting system only. Such a relation is
developed below.
Consider a reacting (or non-reacting) simple
compressible system of fixed mass with only
quasi-equilibrium work modes at a specified
temperature T and pressure P (Fig. 16–3).
Combining the first- and the second-law
relations for this system gives
The differential of the Gibbs function (G = H - TS) at constant
temperature and pressure is
Therefore, a chemical reaction at a specified
temperature and pressure proceeds in the direction of
a decreasing Gibbs function. The reaction stops and
chemical equilibrium is established when the Gibbs
function attains a minimum value (Fig. 16–4).
Therefore, the criterion for chemical equilibrium can
be expressed as
 Equilibrium criteria for open systems:

• If α and β are two phases, the following conditions hold at equilibrium:

Thermal equilibrium
Mechanical equilibrium
Chemical equilibrium

μ is called chemical potential. It is a measure of tendency of a substance to change.

In general, the chemical potential (μ) is defined as the partial molar Gibbs free
energy. Thus in equilibrium;
Phase stability
Why does water exist as a liquid when 0 < T < 100◦C under atmospheric conditions at sea level?
Why does CO2 exist as a gas under room conditions?

To answer such questions one should realize that any spontaneous process taking place at constant
temperature and pressure leads to a decrease in the Gibbs energy of a system.
The Gibbs energy reaches its minimum value when the system is at equilibrium. In
other words, at a given temperature and pressure, a pure substance is stable in a
phase in which it has the minimum Gibbs energy
Vapor- Liquid Equilibrium

• When a gas and a liquid phase which are not thermodynamically in equilibrium
are brought into close contact, transfer of one or more components may occur
from the gas phase to the liquid or, vice versa, by the mechanism of molecular
diffusion.

• Processes such as distillation, absorption, and extraction bring phases of

different composition into contact, and when the phases are not in equilibrium,
mass transfer between the phases changes their compositions.

• For quantitative treatment of mass transfer, the equilibrium T, P, and phase

compositions must be known.
Phase Rule
F: number of degrees of freedom (means the number of intensive properties such
as temperature or pressure, which are independent of other intensive variables)
Π : Number of phases
N: Number of components
F=#(independent variables)-#(independent equations)
Variables: T, P, composition
F=2+(N-1)x Π -(Π -1)xN
F=2- Π +N
If F=k, it means k variables must be specified thus equations involving these
variables at equilibrium can be used for determining the remaining unknown
variables.

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.
VLE diagrams

VLE is the state of coexistence of liquid and vapor phases. VLE data can be
presented in different forms:

Pressure-composition diagram (P-xy) (at a constant T)

Temperature-composition diagrams (T-xy) (at a constant P)
x-y diagrams (may be at constant T&variable P or at a constant P& variable T)
F=3 F=2 Bubble point curve: Saturated liquid
curve, where the first bubble of vapor is
formed
Dew point curve: Saturated vapor curve,
where the first drop of liquid is formed.
When liquid and vapor phases are in
equilibrium, their temperatures and
pressures must be equal to each other.
Thus, any horizontal line in the region
between dew point and bubble point
curves joins the vapor and liquid phases
that are in equilibrium. Such a line is
called the tie line.
The diagram is plotted according to more
volatile component, thus component 1 is
more volatile and P1sat> P2sat
P-xy diagrams: F=3

F=2

Bubble point curve: Saturated liquid curve, where the first bubble of vapor is formed
Dew point curve: Saturated vapor curve, where the first drop of liquid is formed.
When liquid and vapor phases are in equilibrium, their temperatures and pressures must be equal
to each other. Thus, any horizontal line in the region between dew point and bubble point curves
joins the vapor and liquid phases that are in equilibrium. Such a line is called the tie line.
The diagram is plotted according to more volatile component, thus component 1 is more volatile and
P1sat> P2sat
 P-xy diagram

-Suppose that a liq. mix of x1=0.5 at 15 kPa (at point A) -Suppose that a vapor mix of y1=0.7 at 2 kPa (at point A)
Let us decrease the P Let us increase the P
-At point B:first bubble occurs, the liq. start to boil at -At point B: first liq. droplet occurs, the vapor starts to
bubble point P condense at dew point P
-At point E: last liquid droplet -At point E: last vapor bubble
-Further decrease in P leads superheated -Further increase in P leads compressed
vapor with composition 0.5 liquid with composition 0.7
Remarks

At a given T, pure liquid boils at a single pressure, i.e. when its vapor pressure equals the ambient
pressure. On the other hand, for a multicomponent liquid at a specified temperature and initial
composition, boiling takes place over a range of pressure (10–3.1 kPa in the above example,
between B-E points) due to the varying composition of the liquid phase.

At a given T, pure vapor condenses at a single pressure. On the other hand, for a multicomponent
vapor at a specified temperature and initial composition, condensation takes place over a range of
pressure (5–13.3 kPa in the above example, between B-E points) due to the varying composition of
the vapor phase.
T-xy diagrams:

▪xi versus T and yi versus T, curves are called bubble point and dew point curves respectively.
▪The region between the bubble point and dew point curves represents the two phase region. The
horizontal line within the two-phase region joining the vapor and liquid phases that are in
equilibrium is called the tie line.
▪The region below the bubble point curve represents the subcooled (compressed)liquid. The region
above the dew point curve represents the superheated vapor.
▪T1 sat and T2 sat are boiling temperatures of pure components. Component 1 is more volatile
(T2 sat > T1 sat)
 T-xy diagrams

Suppose a liq. mix of x1=0.4 is at 280 K at point A. Suppose a vapor mix of y1=0.62 is at 330 K at
Let us increase the T point A.
Let us decrease the T
At point B, the first vapor bubble occurs, the liq
starts to boil, at its bubble point T. At point B, the first liq. droplet occurs, the
At point E, the last liq droplet. Further increase vapor starts to condense, at its dew-point T.
in T leads to superheated vapor at y1=0.4 At point E, the last bubble. Further decrease
in T leads to compressed liq. at x1=0.62
x-y Diagrams
• Vapor composition, y, is plotted versus x.
• Usually x=y (45°C line) is included on the diagram for reference.
• These diagrams are typically made at constant P and so each point represent a different T.

x-y diagram for a binary mixture of

1-propanol (1) and 1-butanol (2)
 Pxy diagrams at constant T .
(a) Tetrahydrofuran(1 )/carbon tetrachloride(2)
at 303.15 K (30°C);
(b) chloroform(l)/tetrahydrofuran(2)
at 303.15 K (30°C)
(c) furan(l)/carbon tetrachloride(2)
at 303.15 K (30°C);
(d) ethanol(l)/toluene(2) at 338.15 K (65°C).

An azeotrope mixture have the same composition

in liquid and vapor phase and boil at a constant
temperature!!.
In a xy diagram, the point at which
a curve crosses the diagonal line of
the diagram represents an azeotrope,
for such a point y1=x1
Simple Models for VLE
The goal is to find by calculation T, P and compositions in equilibrium.

▪ Raoult’s law
▪ Henry’s law
▪ Modified Raoult’s law
▪ K value correlations
▪ Flash calculations
Rault’s Law

In VL equilibrium

fi : fugacity of pure ccomponent i. Fugacity is ‘escaping tendency’

Fugacity of component i in a solution or mixture

All spontaneous physical/chemical processes take place in the direction of decreasing

fugacity and molar Gibbs energy. For example, the driving force for mass transfer is the
difference in fugacity
Rault’s Law

• The two major assumptions required to reduce VLE calculations to Raoult’s law
are:
• The vapor phase is an ideal gas

• The liquid phase is an ideal solution

Pisat=vapor pressure of pure component i at the temperature of the system

yiP=partial pressure of component i
yi, xi : mole fractions of i in vapor and liquid phases, respectively
 Dew point and Bubble Point Calculations with Raoult’s law
Chemical Engineering interest focuses on dew point and bubble point
calculations, which can be given in four classes:

Bubble P: Given xi and T; Calculate yi and P

Dew P: Given yi and T; Calculate xi and P
Bubble T: Given xi and P, Calculate yi and T
Dew T: Given yi and P, Calculate xi and T

Raoult’s law:

Dew point calculations: Bubble point calculations:

xi is unknown ∑xi=1 and yi is unknown: ∑yi=1 and
Dew point and Bubble Point Calculations with Raoult’s law

Antoine equation
∑yi=1 The use of these equations gives the bubble pressure as:
∑xi=1
 Henry’s law
Application of Raoult's law to species i requires a value for Pisat at the
temperature of application, and thus is not appropriate for a component whose
critical temperature is less than the temperature of application. (The critical
temperature of a substance is the temperature at and above which vapor of the
substance cannot be liquefied, no matter how much pressure is applied.)
If a system of air in contact with liquid water is presumed at equilibrium, then
the air is saturated with water. The mole fraction of water vapor in the air is
usually found from Raoult's law applied to the water with the assumption that no
air dissolves in the liquid phase. Thus, the liquid water is regarded as pure and
Raoult's law for the water (species 2) becomes y2 P = P2sat.
If one wishes to calculate the mole fraction of air dissolved in the water, then
Raoult's law cannot be applied, because the critical temperature of air is much
lower than 298.15 K (25°C). This problem can be solved by Henry's law, applied
here for pressures low enough that the vapor phase may be assumed an ideal gas.
 Henry’s law
• For a component present as a 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 its liquid-phase mole fraction. Thus,
Example
Assuming that carbonated water contains only CO2 (1) and H 2 O(2), determine
the compositions of the vapor and liquid phases in a sealed can of “soda” at 25°C
if the pressure inside the can is 5 bar.

Solution
Expecting that the liquid phase will be nearly pure water and the vapor phase
will be nearly pure CO2 , we apply Henry’s law for CO2 (species 1) and Raoult’s
law for water (species 2):

With the vapor phase nearly pure CO2, we obtain the liquid-phase CO2 mole
fraction as
Similarly, with the liquid phase nearly pure water, we have

From the steam tables, the vapor pressure of water at 25°C is 3.166 kPa, or
0.0317 bar. Thus, y2 = 0.0317/5 = 0.0063. Consistent with our expectations, the
liquid is 99.7% water and the vapor is 99.4% CO2.
Example
Assuming that carbonated water contains only CO2 (1) and H2O (2), determine
the compositions of the vapor and liquid phases in a sealed can of “soda” and the
pressure exerted on the can at 10°C (283.15 K).Henry’s constant for CO 2 in water
at 10°C (283.15 K) is about 990 bar.

Solution
Take species 1 as the CO2 and species 2 as H2O. Henry’s law species 1 and
Raoult’s law for species 2 are written:

These equations are added to give:

With H1=990 bar P2sat=0.01277 bar (from the steam tables at 10 10°C ),

Whence y1=1-y2=1-0.0012=0.9988, and the vapor phase nearly pure CO2, as one
might expect.
 Modified Raoult’s law
• If the liquid phase can not be assumed as ideal while vapor phase is assumed as
ideal, modified Raoult’s law can be applied:

Ɣi= Activity coefficient

Dew point calculations: Bubble point calculations:

Example
For the system methanol(1)/methyl acetate(2), the following equations provide a
reasonable correlation for the activity coefficients:

In addition, the following Antoine equations provide vapor pressures:

where T is in kelvins and the vapor pressures are in kPa. Assuming the validity of
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 the azeotropic composition for T = 318.15 K.
 Solution
In the dew point and bubble point calculations of parts (a) through (d), the key is the
dependence of the activity coefficients on T and x1. In (a), both values are given, and
solution is direct. In (b) only T is given, and solution is by trial with x1 varied to reproduce
the given value of y1. In (c) only x1 is given, and T is varied to reproduce the given value of
P. In (d) neither T nor x1 is given, and both are varied alternately, T to yield P and x1 to
yield y1 In parts (b) through (d), the trial and error calculations are readily automated
using Microsoft Excel’s Goal Seek function.

(a) A BUBL P calculation. For T = 318.15 K, the Antoine equations yield P1sat= 44.51 and
P2sat= 65.64 kPa. The activity-coefficient correlation provides
A = 1.107, γ1 = 1.864, and γ2 = 1.072.
(b) A DEW P calculation. With T unchanged from part (a), P1sat= 44.51 and P2sat= 65.64
kPa, and A are also unchanged. However, the liquid-phase composition is here unknown ,
but is required in the calculation of activity coefficient. An iterative procedure is
indicated; initial values are provided by Raoult’s law, for which γ1=γ2=1. The required
steps, with current values γ1 and γ2, are:

G(1)=1;P=0;y(1)=0.6;y(2)=1-y(1);
G(2)=1;PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(1)));
while abs(PN-P)>0.001
P=PN;
x(1)=y(1)*P/(G(1)*PS(1));x(2)=1-x(1);
G(1)=exp(A*x(2)^2);
G(2)=exp(A*x(1)^2);
PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(2)));
end
'Results of Part b_______________________'
P,x,G,PS
Evaluate activity coefficient;
return the first step

P = 62.59 kPa x1 = 0.8169 γ1 = 1.0378 γ2 = 2.0935

(c) A BUBL T calculation. Solution by trial here varies T until the given value of P is
reproduced. A reasonable starting value for T is found from the saturation temperatures
of the pure species at the known pressure. The Antoine equation, solved for T, becomes:

A mol-fraction-weighted average of these values then provides an initial T:

For the current values of A, γ1,γ2 and From the given equations
 x(1)=0.85;x(2)=1-x(1);P=101.325;
G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
PS(1)=P;PS(2)=P;
TS(1)=b1/(a1-log(101.325))-c1;
TS(2)=b2/(a2-log(PS(2)))+c2;T=0;
TN=x(1)*TS(1)+x(2)*TS(2);
Find a new value for T from the TS,P;
Antoine Equation written for while abs(TN-T)>0.0001
species 1: T=TN;A=2.771-0.00523*T;
G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
PS(1)=exp(a1-(b1/(T+c1)));PS(2)=exp(a2-(b2/(T-c2)))
;
alfa=PS(1)/PS(2);
PS(1)=P/(x(1)*G(1)+x(2)*G(2)/alfa);
TN=b1/(a1-log(PS(1)))-c1;
Return to the initial step. end
'Results of Part C_________________________'
y(1)=(x(1)*G(1)*PS(1))/P;
y(2)=(x(2)*G(2)*PS(2))/P;
T,y,PS,G
The known value of P = 101.33 kPa is reproduced when:
T = 331.20 P1sat = 77.99kPa, P2sat = 105.35 kPa, A = 1.0388, γ1 = 1.0236, γ2 = 2.1182
The vapor-phase mole fractions are given by:

(d) A DEW T calculation. Because P = 101.33 kPa, the saturation temperatures are the
same as those of part (c), and an average value again serves as an initial value for T.

Because the liquid-phase composition is not known, the activity coefficients are
initialized as γ1 = γ2 = 1. Trial calculations alternately vary T to reproduce the given
value of P and then x1 to reproduce the known value of γ1.
• Evaluate A, P1sat, P2sat and at the current value of T from the Antoine equations

• Calculate x1

• Calculate values γ1 and γ2 of from the correlating equations,

• Find a new values for P1sat

• Find a new values for T from the Antoine equation written for species 1:
The process yields the following final values:
T = 326.70 K , P1sat = 64.63 kPa, P2sat = 89.94 kPa, A = 1.0624 γ1 = 1.362 γ2 = 1.252
x1 = 0.4602 , x2 = 0.5398
 We don’t know γ, so we make
an assumption of γ1= γ2=1

Use new
calculated γi Calculate P
P=1/∑yi γiPisat

Calculate xi
xi=Pyi /γiPisat

γi is not close to Calculate new γi

initial value with calculated xi
γi close to
initial value
Compare γi with the End of iteration
initial value of γi
%Smith and van Ness "Introduction to Chemical Engineering Thermodynamics Example 10.3
%by Prof. Dr. Hasan SADIKOGLU
%clc; Clear all;
T=318.15;x(1)=0.25;x(2)=1-x(1);a1=16.59158;b1=3643.31;c1=-33.424;
a2=14.25356;b2=2665.54;c2=53.424;
PS(1)=exp(a1-(b1/(T+c1)));PS(2)=exp(a2-(b2/(T-c2)));
A=2.771-0.00523*T;G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
%Part a_____________________________________
P=x(1)*PS(1)*G(1)+x(2)*PS(2)*G(2);
for i=1:2
y(i)=x(i)*G(i)*PS(i)/P;
end
'Results of Part a_________________________'
P,y,G
%Part b_________________________________________
G(1)=1;P=0;y(1)=0.6;y(2)=1-y(1);
G(2)=1;PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(1)));
while abs(PN-P)>0.001
P=PN;
x(1)=y(1)*P/(G(1)*PS(1));x(2)=1-x(1);
G(1)=exp(A*x(2)^2);
G(2)=exp(A*x(1)^2);
PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(2)));
end
'Results of Part b_________________________'
P,x,G,PS
%PART c________________________'
x(1)=0.85;x(2)=1-x(1);P=101.325;G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
PS(1)=P;PS(2)=P;
TS(1)=b1/(a1-log(101.325))-c1;TS(2)=b2/(a2-log(PS(2)))+c2;T=0;
TN=x(1)*TS(1)+x(2)*TS(2);
TS,P;
while abs(TN-T)>0.0001
T=TN;
A=2.771-0.00523*T;
G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
PS(1)=exp(a1-(b1/(T+c1)));PS(2)=exp(a2-(b2/(T-c2)));

alfa=PS(1)/PS(2);
PS(1)=P/(x(1)*G(1)+x(2)*G(2)/alfa);
TN=b1/(a1-log(PS(1)))-c1;
end
'Results of Part C_________________________'
y(1)=(x(1)*G(1)*PS(1))/P;y(2)=(x(2)*G(2)*PS(2))/P;
T,y,PS,G
%End of Part C_________________________'
%PART d________________________'
y(1)=0.4;y(2)=1-y(1);P=101.325;TS(1)=b1/(a1-log(101.325))-c1;
TS(2)=b2/(a2-log(101.325))+c2;TN=y(1)*TS(1)+y(2)*TS(2);G(1)=1;G(2)=1;T=0;
while abs(TN-T)>0.001
T=TN;A=2.771-0.00523*T;
PS(1)=exp(a1-(b1/(T+c1)));PS(2)=exp(a2-(b2/(T-c2)));alfa=PS(1)/PS(2);
x(1)=y(1)*P/(G(1)*PS(1));x(2)=1-x(1);
G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
PS(1)=P*(y(1)/G(1)+(y(2)/G(2))*alfa);
TN=b1/(a1-log(PS(1)))-c1;
end
'RESULTS of d________________________'
T,PS,A,G,x
%PART e________________________'
T=318.15;
PS(1)=exp(a1-(b1/(T+c1)));PS(2)=exp(a2-(b2/(T-c2)));
A=2.771-0.00523*T;G(1)=exp(A*x(2)^2);G(2)=exp(A*x(1)^2);
a120=PS(1)*exp(A)/PS(2);a121=PS(1)/(exp(A)*PS(2));
RGAZ=PS(2)/PS(1);xaz(1)=(1-log(RGAZ)/A)/2
xaz(2)=1-xaz(1);GAZ2=exp(A*xaz(1)^2);GAZ1=exp(A*xaz(2)^2);
'RESULTS of e________________________'
PAZ=GAZ1*PS(1)
xaz(1)
VLE From K-Value Correlations
K-value: A convenient measure of the tendency of a given chemical
species to partition itself preferentially between liquid and vapor
phases equilibrium ratio.
The relative volatility is a ratio of the K value for one component to that of
another. This is useful because it will often be only a weak function of
temperature, and thus depends almost exclusively on pressure.
Substituting in Raoult

Substituting in modified Raoult

Dew calculations:
Bubble calculations:
 Example
Determine (a) the dew-point pressure and bubble point pressure. For a mixture of 10
mol-% methane, 20 mol-%ethane and 70 mol-% prophane at 283.15 K (10 °C) determine
system methanol(1)/methyl acetate(2), the following equations provide a reasonable
correlation for the activity coefficients:
(a) When the system is at its dew point, only an insignificant amount of liquid is present,
and the give mole fractions are values of yi. For the given temperature, the K values
depend on the choice of P, and by trial we find the value for which is
satisfied. Results for several values of P are given as follows:
700 kPa 1034 kPa 870 kPa
Species yi Ki yi/Ki Ki yi/Ki Ki yi/Ki

Methane 0.1 20.0 0.005 13.2 0.008 16.0 0.006

Ethane 0.2 3.25 0.062 2.25 0.089 2.55 0.075
Propane 0.7 0.92 0.761 0.65 1.077 0.762 0.919

0.828 1.174 1
 The results given in the last two columns shows that is satisfied
when P=8.7 bar. This is the dew point pressure, and the composition of the dew is
given by the values of listed in the last column of the table.

(a) When the system is almost completely condensed, it is at its bubble point and the
given mole fractions becomes values xi. In this case we find by trial the value of P for
which the K values satisfy . Results for several values of P are given in
the following table:

2654 kPa 2696 kPa 2689 kPa

Species xi Ki xiKi Ki xiKi Ki xiKi

Methane 0.1 5.60 0.56 5.25 0.525 5.49 0.549

Ethane 0.2 1.11 0.222 1.07 0.214 1.10 0.220
Propane 0.7 0.335 0.235 0.32 0.224 0.33 0.231

1.017 0.963 1
Equation is satisfied when P=2689 kPa. This is the bubble point pressure.
The composition of the bubble of the vapor is given by , as shown in the last
column.
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 its bubble-point pressure "flashes" or partially evaporates when
the pressure is reduced to a pressure between dew point and bubble point
pressures, producing a two-phase system of vapor and liquid in equilibrium.

A flash vaporization unit.

Extremum values of pressure and temperature to ensure a two-phase mixture within the flash drum.

▪ At a specified feed composition (z1) and flash drum temperature (T), the drum pressure
(P) should lie between the bubble point and dew point pressures in order to have a
two-phase mixture within the drum.

▪ On the other hand, at a specified feed composition (z1) and flash drum pressure (P), the
drum temperature (T) should lie between the bubble point and dew point temperatures
in order to have a two-phase mixture within the drum.
• Consider a system containing 1 mole of non-reacting chemical species 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:
Material balance Component balance

Combining above equations to eliminate L

Substituting xi = yi / Ki , and solving for yi yields

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

Solution
First, do a BUBL P calculation with {zi} = {xi} to determine Pbubble:

Next, do a DEW P calculation with {zi} = {yi} to find Pdew:

Because the given pressure lies between Pbubble and Pdew the system is in the two phase
region, and a flash calculation is possible.

From Raoult’s law from which: K1 = 1.7795; K2 = 0.8895; K3 = 0.4575

Substituting known values into

This non-linear equation can be solved by MATLAB unknowns yields:

V= 0.7364 mol L=1-V= 0.2636 mol function Z=flash(V)

Z1=0.45*1.7795./(1+0.7795*V);
Z2=0.35*0.8895./(1-0.1105*V);
Z3=0.20*0.4575./(1-0.5425*V);
Z=Z1+Z2+Z3-1;
fzero(@flash,.1)=0.7364 end
Reassuringly,
clc;clear %Part b
x(1)=0.65;x(2)=1-x(1); z=0.65;x(1)=0.75;x(2)=1-x(1);
G(1)=exp(0.67*x(2)^2); G(1)=exp(0.67*x(2)^2);
G(2)=exp(0.67*x(1)^2); G(2)=exp(0.67*x(1)^2);
PS(1)=32.27;PS(2)=73.14; PS(1)=32.27;PS(2)=73.14;
%Buble Point %Buble Point
Pbubl=x(1)*PS(1)*G(1)+x(2)*PS(2)*G(2) Pbubl2=x(1)*PS(1)*G(1)+x(2)*PS
%Dew Point (2)*G(2)
G(1)=1;P=0;y(1)=0.65;y(2)=1-y(1); y(1)=x(1)*G(1)*PS(1)./Pbubl2;
G(2)=1;PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G V=(z-x(1))./(y(1)-x(1))
(2)*PS(1))); %Part c
while abs(PN-P)>0.001 a120=PS(1)*exp(0.67)/PS(2)
P=PN; a121=PS(1)/(exp(0.67)*PS(2))
x(1)=y(1)*P/(G(1)*PS(1));x(2)=1-x(1);
G(1)=exp(0.67*x(2)^2);
G(2)=exp(0.67*x(1)^2);
PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(
2)))
end
PN
clc;clear
%Part c
x(1)=0.05;x(2)=1-x(1);
a120=PS(1)*exp(0.95)/PS(2)
G(1)=exp(0.95*x(2)^2);
a121=PS(1)/(exp(0.95)*PS(2))
G(2)=exp(0.95*x(1)^2);
xaz=(1-log(PS(2)./PS(1))./0.95)./2
PS(1)=79.80;PS(2)=40.50;
G1AZ=exp(0.95*(1-xaz).^2);
%Buble Point
Paz=G1AZ*PS(1)
Pbubl=x(1)*PS(1)*G(1)+x(2)*PS(2)*G(2)
y(1)=G(1)*x(1)*PS(1)./Pbubl
%Partb Dew Point
G(1)=1;P=0;y(1)=0.05;y(2)=1-y(1);
G(2)=1;PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(1)));
while abs(PN-P)>0.001
P=PN;
x(1)=y(1)*P/(G(1)*PS(1));x(2)=1-x(1);
G(1)=exp(0.95*x(2)^2);
G(2)=exp(0.95*x(1)^2);
PN=1/(y(1)/(G(1)*PS(1))+y(2)/(G(2)*PS(2)))
end
'Dew Point',PN,x(1)=y(1)*PN/(G(1)*PS(1))
%End of Part b