Chemical Engineering Thermodynamics-

II
Lecture-8
(Ideal Binary Phase Diagrams)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
 Outline of presentation
• Review of previous lecture
• Gibbs phase rule
• Ideal Binary Phase diagrams(VLE diagrams)
• Txy, Pxy and xy
• Applications and preparation of Txy, Pxy and xy dia.
• Common types of VLE Calculations
• Bubble point and Dew point, examples
• P,T Flash calculations
• Examples based on Flash calculations
 Review of previous lecture

Property changes of mixing process-Ideal

solution
Ideal gas versus Ideal solution
Understanding of VLE system and its
Purpose
Derivation of Ideal VLE model - Raoult’s law
Raoult’s law - Applicability and limitations
 Objectives
 To estimate distributions of different species in vapor and
liquid phase that are in equilibrium
 Each species should have a finite volatility and solubility to
re-distribute itself between the two phases.
 Species redistribution brings about separation of the
species; e.g. distillation.
 Needs a knowledge of pressure, temperature and
composition in each phase of the system.
 Distribution of components in two phases is governed by
 Vapor liquid equilibrium relationship.
 VLE data enables us to relate the composition of liquid to
vapor phase.
 Equilibrium relations depend on the ideality or no-ideality of
each phase.
 Objectives
 Our emphasis will be mainly on binary mixtures.
 Equilibrium data may be obtained by experiment, by
thermodynamic calculation, or in published sources.
 It is typically represented either in tabular form or as in
equilibrium diagram. Diagrams may take several forms:
 Txy , Pxy diagrams
 Xy diagrams
Statement of Raoult's law
 Gibbs phase rule

 Gibbs phase rule is used to define number of intensive

properties that must be specified to fix the state of
equilibrium unambiguously
 In the absence of chemical reactions, this rule says that:

“No. of intensive properties to be fixed (F)= No. of

components (N) – No. of Phases (P) + 2”
 Gibbs phase rule(Continued)

 Ex.: For two component and two phase system, F = 2

 Intensive variables: T, P, x1, x2, y1, y2
 D.o.f F=2-2+2 = 2
 x1+x2=1
 y1+y2=1
  vapor pressure of pure i @ T

 Any two of these must be specified to define
equilibrium and then the remaining variables can be
found
 Gibbs phase rule(Contd.)

 Ex.: For three component and two phase system, F = 3

 Intensive variables: T, P, x1, x2,x3, y1, y2,y3
 D.o.f F=3-2+2 = 3
 x1+x2+x3=1
 y1+y2+y3=1
  vapor pressure of pure i @
T


 Any three of these must be specified to define
equilibrium and then the remaining variables can be
found
Application of Raoult’s law
 Applicability of Raoult’s law

 The pressure is low and all intermolecular forces

are approximately small
 Both liquid and vapor mixtures should be ideal.
 Ideal liquid mixture has
 Liquid compositions that are miscible in all
proportions to give a single liquid
 Zero volume change on mixing and zero enthalpy
of mixing
 Solutions comprised of molecules not too
different in size and of the same chemical nature.
 Limitations of Raoult’s law

 Only for ideal vapor

 Only to ideal liquid solutions
 Only for solutes that do not change their nature
when they dissolve(i.e., they do not ionize or
associate).
Binary Phase Diagrams
of VLE System
Equilibrium composition of an ideal binary
mixture a and b that follows Raoult’s law
Constant Temperature Binary Equilibrium Diagram
 The Lever Rule or Reverse arm Rule

 If, at the given pressure and temperature, the overall

composition of the system (z ) is found within the
A
values (x  < z  < y  in the Txy diagram or y  < z  < x  in the
A A A A A A
Pxy diagram), the system will be in a two-phase
condition and the vapor fraction (α ) and liquid fraction
G

(α ) can be determined by the lever rule:

L

 Note that αL and αG are not independent of each other,

since α  + α  = 1.
L G

 it is also known as the “reverse arm rule,” because for

the calculation of α  (liquid) you use the “arm” within
L
the (y -x ) segment closest to the vapor, and for the
A A
vapor calculation (α ) you use the “arm” closest to
G
the liquid.
The Lever Rule or Reverse arm Rule on Pxy diagram
Binary Phase diagrams
 Binary Phase diagrams

 Phase diagram are useful for identifying

thermodynamic state of a binary mixture, i.e.,
 these diagrams tell us what phase or phases are
present; and in the two-phase region, composition
of the liquid and vapor phases as well as their
relative amounts.
 From figure, we can see
 a sub-cooled liquid phase
 superheated vapor phase
 a combination of two phases i.e., a liquid phase in
equilibrium with vapor phase
 Binary Phase diagrams(Contd.)

 By convention, lighter component one that boils

more easily, we label it as species ‘a’
 At high pressure, sub-cooled liquid; and at low
pressure, superheated vapor exist
 In between these two region, we observe a two
phase region where mixture is in vapor-liquid
equilibrium
 In this case, composition and amount of each
phase can also be determined from phase
diagram
 Binary Phase diagrams(Contd.)
 Liquid mole fraction vs pressure line is often termed
as the bubble point curve
 Because if we start at high pressure and decrease
system pressure at constant temperature, this curve
marks the pressure at which first bubble of vapor forms
 Bubble composition can be found where the tie line
intersects 𝑃 − 𝑦a curve
 Similarly vapor mole fraction vs pressure curve is
known as ‘dew point’ curve
 Because this mark when the first drop of liquid forms
when a superheated vapor mixture is isothermally
compressed
Binary Phase diagrams
Constant Pressure Binary Equilibrium Diagram
Chemical Engineering Thermodynamics-
II
Lecture-9
(Construct Pxy & Txy Diagrams)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
Prepare Binary Phase diagrams(Pxy & Txy)
 These results mean that at 75oC a liquid mixture of 60 mole percent
acetonitrile and 40 mole percent nitromethane is in equilibrium with
a vapor containing 74.83 mole percent acetonitrile at a pressure of
66.72 kPa.
Binary system-Acetonitrile(1)/Nitromethane(2)

 The results of this and similar calculations for 75oC

are tabulated as follows:

 These same results are shown by the Pxy diagram

of Figure10.1
Constant Temperature Binary Equilibrium Diagram
Binary Phase diagrams-Txy
Binary system-Acetonitrile(1)/Nitromethane(2)

 The results of this and similar calculations for P=70

kPa are given in the following table:

 Figure 10.2 is the Txy diagram showing these

results.
Constant Pressure Binary Equilibrium Diagram
 Equilibrium curve(xy diagram), y vs x

Equilibrium compositions of two phases are often very different from one
another and this difference enables us to separate mixtures by distillation,
extraction, and other phase contacting operation.
 Common types of VLE calculations

 Dew Point Pressure:

 Given T, y1, y2,... yn find P, x1, x2, ... xn

 Dew Point Temperature:

 Given P, y1, y2,... yn find T, x1, x2, ... xn

 Bubble Point Pressure:

 Given T, x1, x2, ... xn find P, y1, y2,... yn

 Bubble Point Temperature:

 Given P, x1, x2, ... xn find T, y1, y2,... yn
VLE calculations-Bubble Pressure from Pxy diagrams

 Known:- T, x1, x2
 Find:- P, y1, y2
 VLE calculations-Dew Pressure from Pxy diagram

 The Known:- T, y1, y2

 Find:- P, x1, x2

 The two points C and C’ together represent the

equilibrium state at y1=0.6, P=59.74 kPa and
x1=0.4308 for t=75oC
 VLE calculations-Bubble Temperature from Txy diagram

 Known:- P, x1, x2
 Find:- T, y1, y2
VLE calculations-Dew Temperature from Txy diagram

 Known:- P, y1, y2
 Find:- T, x1, x2
 Questions-Ideal Binary Phase Diagrams
[Hint: Use Txy diagram
Binary system-Acetonitrile(1)/Nitromethane(2)]
1. At what temp. does pure acetonitrile boil?
2. At what temp pure nitromethane condense at 70 kPa?
3. What phase or phases are present if a mixture containing
20 mol% acetonitrile at 70 kPa is heated to 90 C, 80 C and
0 0

88 C?
0

4. If a mixture containing 50 mol% acetonitrile is heated to

boiling at 70 kPa, what is the composition of the first
vapor that comes off?
5. What are the equilibrium composition of any phases
present at 30 mol% acetonitrile and 87 C?
0

6. What are the equilibrium composition of any phases

present at 20 mol% acetonitrile and 87 C?
0

7. What are the equilibrium composition of any phases

present at 20 mol% acetonitrile and 84 C?
0

8. What is the dew point temp. & bubble point temp. of a

mixture containing 70 mol% acetonitrile at 70 Kpa?
Constant Pressure Binary Equilibrium Diagram
 Questions-Ideal Binary Phase Diagrams
[Hint: Use Pxy diagram
Binary system-Acetonitrile(1)/Nitromethane(2)]
9. What is the dew point pressure of a mixture containing 30
mol% acetonitrile at 75 C?
0

10. What is the bubble point pressure of a mixture containing

30 mol% acetonitrile at 75 C?
0

11. What are the compositions of the phases in equilibrium

for a 40 mol% acetonitrile mixture at 55 Kpa?(at 75 C )
0

12. What are the compositions of the phases in equilibrium

for 40 mol% acetonitrile mixture at 45 Kpa ?(at 75 C )
0

13. What are the composition of phases in equilibrium for a

80 mol% acetonitrile mixture at 72Kpa?
14. What are the composition of phases in equilibrium for a
80 mol% acetonitrile mixture at 80Kpa?
Constant Temperature Binary Equilibrium Diagram
Chemical Engineering Thermodynamics-II
Lecture-10
(VLE calculations for multicomponent
mixtures)

Prof.Hitesh N. Panchal
Department of Chemical Engineering
FOT, D. D. University
Nadiad-387001
 Common types of VLE calculations

 Dew Point Pressure:

 Given T, y1, y2,... yn find P, x1, x2, ... xn

 Dew Point Temperature:

 Given P, y1, y2,... yn find T, x1, x2, ... xn

 Bubble Point Pressure:

 Given T, x1, x2, ... xn find P, y1, y2,... yn

 Bubble Point Temperature:

 Given P, x1, x2, ... xn find T, y1, y2,... yn
 Ideal VLE Calculations
Multicomponent Mixtures
 The calculations has done by the use of following
equations:
 Raoult’s law for ideal behavior:

 Liquid phase mole fraction

 Vapor phase mole fraction
 Vapor pressure of pure species i at system
temperature B
sat
ln( Pi )  Ai  i

 Antoine’s Equation  T Ci

 For bubble point calculation 
 For Dew point calculation 
 VLE calculations-Bubble Pressure

 Given data:- T, x1, x2, ... xi

 Find:- P, y1, y2,... yi
 From the Raoult’s law, yiP = xiPisat i = 1,2,3, … , N
 For two component system:
 y1P = x1P1sat and y2P = x2P2sat
 Now as , for binary mixture; y1 + y2 = 1
sat sat
x1 * P1 x 2 * P2
 1
P P
 P = x1P1sat + x2P2sat
 For multicomponent system:
 P = xiPisat ----------[1]
 yi = xiPisat / P
----------[2]
 Calculation of saturation pressure is done by the use of
Antoine equations.
 VLE calculations-Dew Pressure

 Given data :- T, y1, y2,... yi

 Find:- P, x1, x2, ... xi
 From the Raoult’s law, yiP = xiPisat i = 1,2,3, … , N
 For two component system:
 y1P = x1P1sat and y2P = x2P2sat
 Now as , For binary mixture; x1 + x2 = 1
(y1P/ P1sat )+ (y2P/ P2sat ) = 1
 P = 1/( y1/ P1sat + y2/ P2sat)
 For multicomponent system:
 P = 1 / ( yi/ Pisat) ----------[3]
 xi = yiP/Pisat ----------[4]
 Calculation of saturation pressure is done by the use of
Antoine equations.
 VLE calculations-Bubble Temperature

 Given data :- P, x1, x2, ... xi

 Find:- T, y1, y2,... yi
 From the Raoult’s law, yiP = xiPisat i = 1,2,3, … , N
 For two component system:
 y1P = x1P1sat and y P = x P
2 2 2
sat

 Now consider P as the Pisat and calculate the temperature

which is called as the saturation temperature of the
substance at that pressure and then calculate the value of
the first value of temperature for the guess.
 tisat = {b[i] / (a[i] – ln[Pisat]) } – c[i]
 t0 =  xiTisat
 This value is the initial guess of the temperature for the
calculation.
 VLE calculations-Bubble Temperature(Contd.)

 Identify any species N

 After that we have to calculate the  values,
 [i][N] = exp{lnPisat - lnPNsat}  [i][N] = Pisat /PNsat
 Then PNsat = P/  xi[i][N]
 Now t = {b[N] / (a[N] – ln[PNsat]) } – c[N]
 This is the second guess for the further convergence
of the iteration for the actual value of the temperature.
 This calculation sequence is repeated until there is no
significant change from one iteration to the next.
 Final values of PNsat are found from the equations, and
final yi values come from Raoult's law.
 VLE calculations-Bubble Temperature(Contd.)

 y1+y2=1
 From Raoult’s law;
sat sat
x1 * P1 x 2 * P2
 1
P P

 Identify species 2,

 Then for multicomponent system

PNsat = P/  xi[i][N]
 VLE calculations-Dew Temperature

 Given data :- P, y1, y2,... yi

 Find:- T, x1, x2, ... xi
 From the Raoult’s law, yiP = xiPisat i = 1,2,3, … , N
 For two component system:
 y1P = x1P1sat and y P = x P
2 2 2
sat

 Now consider P as the Pisat and calculate the temperature

which is called as the saturation temperature of the
substance at that pressure and then calculate the value of
the first value of temperature for the guess.
 tisat = {b[i] / (a[i] – ln[Pisat]) } – c[i]
 t0 =  yiTisat
 This value is the initial guess of the temperature for the
calculation.
 VLE calculations-Dew Temperature(Contd.)

 Identify any species N

 After that we have to calculate the  values,
 [i][N] = exp{lnPisat - lnPNsat} [i][N] = Pisat /PNsat
 Then PNsat = P*(  yi [N][i])
 Now t = {b[N] / (a[N] – ln[PNsat]) } – c[N]
 This is the second guess for the further convergence
of the iteration for the actual value of the temperature.
 This calculation sequence is repeated until there is no
significant change from one iteration to the next.
 Final values of PNsat are found from the equations, and
final xi values come from Raoult's law.
 VLE calculations-Dew Temperature(Contd.)

 x1+x2=1
 From Raoult’s law;
y1 * P y2 * P
sat
 sat
1
P1 P2

 Identify species 2,

 Then for multicomponent system

PNsat = P*(  yi [N][i])
Example
Example-Dew Temperature
Solution
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Solution(Contd.)
Thank you