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

10.2

SVNA-

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

CHEE 311

F = 2 + (N-1) - (-1)N = 2- +N
Lecture 2 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.
800 Pressure: kPa 600 400 200 0 270
CHEE 311

VLE for Pure Components

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 T+C

For acetonitrile (Component 1):

ln P1sat / kPa = 14.2724

For nitromethane (Component 2):
sat ln P2

2945.47 T / C + 224

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 4

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

90 80 Pressure, kPa 70 60 50 40 0.0

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

0.2

0.4

x1,y1 y1

0.6 x1

0.8

1.0

CHEE 311

Lecture 2

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.
Acetonitrile(1) Nitromethane(2) @ 70kPa

90.0 85.0 Temp, deg C 80.0 75.0 70.0 65.0 0.00

0.20

0.40

x1,y1 y1

0.60 x1

0.80

1.00

CHEE 311

Lecture 2

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, z i 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 = yi * P = x i * Pisat
2) Antoines Equation

(1)

Bi ln( P ) = A i T + Ci
sat i
Lecture 2 10

(2)

CHEE 311

BUBL P Calculation (T, x1 known)

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

P1sat

sat 2

(3)

(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)

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

P1sat

P2sat

(5)

(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): sat sat T < T ' < T - Select a temperature T so that 1 2 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
sat sat P P - Calculate 1 and 2 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

sat i.e., - Now you can obtain y1 fromxEqn * P(1),

y1 =

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:
A 1-chlorobutane (1) Chlorobenzene (2) 13.9600 13.9926 B 2826.26 3295.12 C 224.10 217.55

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 P 2sat to P1sat. The results can be tabulated as shown below:
P (kPa)

P P2sat x1 = sat P1 P2sat P2sat

0.0 1.0

x1 * P1sat y1 = P
0.0 1.0

P1sat

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
100.00 P (kPa) x1 80.00

VLE
60.00

y1

40.00

vapor
20.00

0.00 0.00 0.20 0.40 0.60 0.80 1.00

CHEE 311

Lecture 2

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:
T (oC)

P P2sat x1 = sat P1 P2sat

T2sat
0 1.0

x1 * P1sat y1 = P
0 1.0

T1sat

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

P T1sat T2sat T (degC) 74.65 80.00 85.00 90.00 95.00 100.00 105.00 110.00 115.00 120.00 125.00 129.57 90.00 74.65 129.57 kPa degC degC A1 B1 C1 13.96 2826.26 224.10 A2 B2 C2 13.99 3295.12 217.55

P1sat 90.00 106.29 123.53 142.88 164.52 188.61 215.33 244.86 277.39 313.10 352.18 391.01

P2sat 15.12 18.51 22.23 26.54 31.50 37.18 43.67 51.04 59.38 68.77 79.30 90.00

x1 1.00 0.81 0.67 0.55 0.44 0.35 0.27 0.20 0.14 0.09 0.04 0.00

x2 0.00 0.19 0.33 0.45 0.56 0.65 0.73 0.80 0.86 0.91 0.96 1.00

y1 1.00 0.96 0.92 0.87 0.80 0.73 0.65 0.55 0.43 0.30 0.15 0.00

CHEE 311

Lecture 2

21

Example (b) Construction of a Txy Plot

Txy diagram for 1-chlorobutane (1) and chlorobenzene (2) at P = 90 kPa (assuming validity of Raoult's law)
140.00 120.00 100.00 T (degC) 80.00 60.00 40.00 20.00 0.00 0.00

vapor VLE
x1 y1

liquid

0.20

0.40 x1,y1

0.60

0.80

1.00

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:
Specified/Known Variables Unknown Variables Calculation

T, x T, y P, x P, y P, T
CHEE 311

P, y P, x T, y T, x x, y
Lecture 2

BUBL P DEW P BUBL T DEW T P, T Flash

23