VLE Calculations

Purpose of this lecture:

To demonstrate how Raoults law can be used in the prediction of the
VLE behaviour of ideal mixtures
Highlights
Phase rules gives the number of variables we need in order to
determine the intensive state of a system at equilibrium
Saturation pressures can be calculated by means of the Antoine Eqn.
Raoults law can be used for constructing Pxy, Txy diagrams and
performing dew point and bubble point calculations
Reading assignment: Section 10.4, pp. 347-357 (7th edition), or
Section 10.4, pp. 338-348 (6th edition)

CHEE 311

Lecture 2

Phase Rule for Intensive Variables

SVNA-

10.2

For a system of phases and N species, the degree of freedom is:

F=2-+N
# variables that must be specified to fix the intensive state of the
system at equilibrium
Phase Rule Variables:
The system is characterized by T, P and (N-1) mole fractions for each
phase
Requires knowledge of 2 + (N-1) variables
Phase Rule Equations:
At equilibrium i = i = i for all N species
These relations provide (-1)N equations
The difference is
= 2- +N
CHEE 311

F = 2 + (N-1) - (-1)N

Lecture 2

Phase Rule in VLE: Single Component Systems

For a two phase (=2) system of a single component (N=1):
F = 2- + N
F = 2- 2 + 1 = 1
Therefore, for the single component system, specifying either T or
P fixes all intensive variables.
VLE for Pure Components

Pressure: kPa

800
600
400
200
0
270
CHEE 311

320
370
Temperature: K
Acetonitrile
Lecture 2 Nitromethane

420
3

Correlation of Vapour Pressure Data

Pisat, or the vapour pressure of component i, is commonly represented
by Antoine Equation (Appendix B, Table B.2, SVNA 7th ed.):

ln Pisat

B
A
TC

For acetonitrile (Component 1):

ln P1sat / kPa 14.2724

2945.47
T / C 224

For nitromethane (Component 2):

ln P2sat

2972.64
/ kPa 14.2043
T / C 209

These functions are the only component properties needed to

characterize ideal VLE behaviour
CHEE 311

Lecture 2

Phase Rule in VLE: Ideal Binary Mixtures

(General Case)
For a two phase (=2), binary system (N=2):
F = 2- 2 + 2 = 2
Therefore, for the binary case, two intensive variables must be
specified to fix the state of the system.

CHEE 311

Lecture 2

Phase Rule in VLE: Binary Systems (Pxy diagrams)

Example: Acetonitrile (1) / Nitromethane (2) system

Acetonitrile(1) - Nitromethane(2) @ 75C

90

Pressure, kPa

80
70
60
50
40
0.0

CHEE 311

0.2

0.4

x1,y1

0.6

y1

x1

Lecture 2

0.8

1.0

Phase Rule in VLE: Binary Systems (Txy diagrams)

Alternatively, we can specify a system pressure and examine the
VLE behaviour as a function of temperature and composition.

90.0

Acetonitrile(1) Nitromethane(2) @ 70kPa

Temp, deg C

85.0
80.0
75.0
70.0
65.0
0.00

0.20

0.40

x1,y1
y1

CHEE 311

Lecture 2

0.60

0.80

1.00

x1
7

VLE Calculations using Raoults Law

Raoults Law for ideal phase behaviour relates the composition of liquid
and vapour phases at equilibrium through the component vapour
pressure, Pisat.

y i Pisat

xi
P
Given the appropriate information, we can apply Raoults law to the
solution of 5 types of problems:
Dew Point:
Pressure or Temperature
Bubble Point: Pressure or Temperature
P,T Flash: calculation of equilibrium composition (P, T, zi given)

CHEE 311

Lecture 2

Dew and Bubble Point Calculations

Dew Point Pressure:
Given a vapour composition at a specified temperature, find the
composition of the liquid in equilibrium
Given T, y1, y2,... yn find P, x1, x2, ... xn
Dew Point Temperature:
Given a vapour composition at a specified pressure, find the
composition of the liquid in equilibrium
Given P, y1, y2,... yn find T, x1, x2, ... xn
Bubble Point Pressure:
Given a liquid composition at a specified temperature, find the
composition of the vapour in equilibrium
Given T, x1, x2, ... xn find P, y1, y2,... yn
Bubble Point Temperature:
Given a vapour composition at a specified pressure, find the
composition of the liquid in equilibrium
Given P, x1, x2, ... xn find T, y1, y2,... yn
CHEE 311

Lecture 2

VLE Calculations - Introduction

For now, we are going to employ these calculations only for
identifying the state and composition of binary and ideal mixtures
As we are going to see later in the course, the aforementioned
VLE calculations are also applicable to non-ideal or/and
multi-component mixtures
The calculations revolve around the use of 2 key equations:
1) Raoults law for ideal phase behaviour:

Pi y i * P x i * Pisat

(1)

2) Antoines Equation

Bi
ln( P ) A i
T Ci
sat
i

CHEE 311

Lecture 2

(2)
10

BUBL P Calculation (T, x1 known)

P1sat

sat
2 from Antoines Equation

- Calculate
and
- For the vapour-phase composition (bubble) we can write:
y1+y2=1

(3)

- Substitute y1 and y2 in Eqn (3) by using Raoults law:

x1 * P1sat x 2 * P2sat x1 * P1sat ( 1 x1 )* P2sat

1
P
P
P
P

(4)

- Re-arrange and solve Eqn. (4) for P

- Now you can obtain y1 from Eqn (1)
- Finally, y2 = 1-y1
CHEE 311

Lecture 2

11

DEW P Calculation (T, y1 known)

P1sat

P2sat

- Calculate
and
from Antoines Equation
- For the liquid-phase composition (dew) we can write:
x1+x2=1

(5)

- Substitute x1 and x2 in Eqn (5) by using Raoults law:

y1 * P y 2 * P y1 * P ( 1 y1 )* P
sat sat
1
sat
sat
P1
P2
P1
P2

(6)

- Re-arrange and solve Eqn. (6) for P

- Now you can obtain x1 from Eqn (1)
- Finally, x2 = 1-x1
CHEE 311

Lecture 2

12

BUBL T Calculation (P, x1 known)

Since T is an unknown, the saturation pressures for the
mixture components cannot be calculated directly. Therefore,
calculation of T, y1 requires an iterative approach, as follows:
- Re-arrange Antoines equation so that the saturation temperatures
of the components at pressure P can be calculated:
Tisat

Bi
Ci
A i ln( P )

(7)

sat
sat
T

T
'

T
- Select a temperature T so that 1
2
sat
sat

- Calculate P1 ( T' ) and P2 ( T' )

- Solve Eqn. (4) for pressure P
- If P P' , then P=P; If not, try another T-value
- Calculate y1 from Raoults law
CHEE 311

Lecture 2

13

DEW T Calculation (P, y1 known)

Same as before, calculation of T, x1 requires an iterative approach:
- Re-arrange Antoines equation so that the saturation temperatures
of the components at pressure P can be calculated from Eqn. (7):
- Select a temperature T so that T1sat T' T2sat
sat
sat
- Calculate P1 ( T' ) and P2 ( T' ) from Antoines Eqn.
- Solve Eqn. (6) for pressure P
- If P P' , then P=P; If not, try another T-value
- Calculate x1 from Raoults law

CHEE 311

Lecture 2

14

P, T Flash Calculation
- Calculate P1sat and P2sat from Antoines Equation
- Use Raoults law in the following form:

x1 * P1sat ( 1 x1 )* P2sat
1
yi P
P

(8)

- Re-arrange and solve Eqn. (8) for x1

- Now you can obtain y1 from Eqn (1),
sat i.e.,

x1 * P1
y1
P

CHEE 311

Lecture 2

15

Example
Assuming Raoults Law to be valid, prepare
(a) a Pxy diagram for T=90oC, and
(b) a Txy diagram for P=90 kPa
for a mixture of 1-chlorobutane (1) /chlorobenzene (2)
Antoine Coefficients:

1-chlorobutane (1)

13.9600

2826.26

224.10

Chlorobenzene (2)

13.9926

3295.12

217.55

CHEE 311

Lecture 2

16

Construction of Pxy diagrams

The construction of Pxy diagram requires multiple P, T Flash
calculations, where T is held constant and P is varied from P2sat to P1sat.
The results can be tabulated as shown below:
P P2sat
x1 sat
P1 P2sat

P (kPa)

x1 * P1sat
y1
P

P2sat

0.0

0.0

P1sat

1.0

1.0

This type of calculations can also be performed by keeping T constant

and varying x1 or y1 from 0.0 to 1.0
CHEE 311

Lecture 2

17

Example* (a) Generation of Pxy Data

CHEE 311

Lecture 2

18

Example (a) Construction of a Pxy Plot

160.00

140.00

120.00

liquid
P (kPa)

100.00
x1
80.00
y1

VLE
60.00

40.00

vapor
20.00

0.00
0.00

CHEE 311

0.20

0.40

0.60

Lecture 2

0.80

1.00

19

Construction of Txy diagrams

The construction of Txy, diagram requires multiple P, T, Flash
calculations, each one of which provides a set of equilibrium y1, x1
values for a given value of temperature (at fixed P)
The results can be tabulated as shown below:
P P2sat
x1 sat
P1 P2sat

T (oC)

x1 * P1sat
y1
P

T2sat

T1sat

1.0

1.0

This type of calculations can also be performed by keeping P constant

and varying x1 or y1 from 0.0 to 1.0
CHEE 311

Lecture 2

20

Example (b) Generation of Txy Data

CHEE 311

Lecture 2

21

Example (b) Construction of a Txy Plot

CHEE 311

Lecture 2

22

VLE Calculations - Summary

Why? To completely identify the thermodynamic state
of a mixture at equilibrium (single phase, 2 phases..?)
How? Through the calculation of its P, T, and composition
- The type of calculation that we need to perform is subject
to the variables we are looking to evaluate
- These calculations are classified as follows:

CHEE 311

Specified/Known
Variables

Unknown
Variables

Calculation

T, x

P, y

BUBL P

T, y

P, x

DEW P

P, x

T, y

BUBL T

P, y

T, x

DEW T

P, T

x, y

P, T Flash

Lecture 2

23