VLE Calculations

Purpose of this lecture:
To demonstrate how Raoult’s 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.
Raoult’s 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

1

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

2

for the single component system. specifying either T or P fixes all intensive variables. + N F = 2.Phase Rule in VLE: Single Component Systems For a two phase (=2) system of a single component (N=1): F = 2. VLE for Pure Components Pressure: kPa 800 600 400 200 0 270 CHEE 311 320 370 Temperature: K Acetonitrile Lecture 2 Nitromethane 420 3 .2 + 1 = 1 Therefore.

64 / kPa  14. or the vapour pressure of component i. SVNA 7th ed.2724  2945.2043  T / C  209 These functions are the only component properties needed to characterize ideal VLE behaviour CHEE 311 Lecture 2 4 .2. is commonly represented by Antoine Equation (Appendix B.47 T / C  224 For nitromethane (Component 2): ln P2sat 2972. Table B.): ln Pisat B A TC For acetonitrile (Component 1): ln P1sat / kPa  14.Correlation of Vapour Pressure Data Pisat.

CHEE 311 Lecture 2 5 .2 + 2 = 2 Therefore. for the binary case. two intensive variables must be specified to fix the state of the system.Phase Rule in VLE: Ideal Binary Mixtures (General Case) For a two phase (=2). binary system (N=2): F = 2.

y1 0. kPa 80 70 60 50 40 0.0 6 .0 CHEE 311 0.6 y1 x1 Lecture 2 0.Nitromethane(2) @ 75C 90 Pressure.4 x1.8 1.2 0.Phase Rule in VLE: Binary Systems (Pxy diagrams) Example: Acetonitrile (1) / Nitromethane (2) system Acetonitrile(1) .

80 1.0 Acetonitrile(1) Nitromethane(2) @ 70kPa Temp.20 0.00 x1 7 .0 70.0 80. 90.Phase Rule in VLE: Binary Systems (Txy diagrams) Alternatively.0 75.00 0.y1 y1 CHEE 311 Lecture 2 0.0 0.0 65. deg C 85. we can specify a system pressure and examine the VLE behaviour as a function of temperature and composition.60 0.40 x1.

Pisat. T. we can apply Raoult’s law to the solution of 5 types of problems:  Dew Point: Pressure or Temperature  Bubble Point: Pressure or Temperature  P.VLE Calculations using Raoult’s Law Raoult’s Law for ideal phase behaviour relates the composition of liquid and vapour phases at equilibrium through the component vapour pressure.T Flash: calculation of equilibrium composition (P. zi given) CHEE 311 Lecture 2 8 . y i Pisat  xi P Given the appropriate information.

y1. yn CHEE 311 Lecture 2 9 .. x1. x2. .. y1. xn Dew Point Temperature: Given a vapour composition at a specified pressure.... x2. y2.. find the composition of the liquid in equilibrium Given T. x2... find the composition of the vapour in equilibrium Given T. xn find P. y1. xn Bubble Point Pressure: Given a liquid composition at a specified temperature.. x1.. y2. find the composition of the liquid in equilibrium Given P... . x1. . yn find P. yn find T. find the composition of the liquid in equilibrium Given P. yn Bubble Point Temperature: Given a vapour composition at a specified pressure. x2. y2.Dew and Bubble Point Calculations Dew Point Pressure: Given a vapour composition at a specified temperature. y2...... y1.. xn find T. x1. ...

VLE Calculations . 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) Raoult’s law for ideal phase behaviour: Pi  y i * P  x i * Pisat (1) 2) Antoine’s Equation Bi ln( P )  A i  T  Ci sat i CHEE 311 Lecture 2 (2) 10 .Introduction • For now.

Substitute y1 and y2 in Eqn (3) by using Raoult’s law: x1 * P1sat x 2 * P2sat x1 * P1sat ( 1  x1 )* P2sat    1 P P P P (4) . x1 known) P1sat sat 2 from Antoine’s Equation P .Calculate and .For the vapour-phase composition (bubble) we can write: y1+y2=1 (3) . y2 = 1-y1 CHEE 311 Lecture 2 11 . (4) for P .Re-arrange and solve Eqn.Now you can obtain y1 from Eqn (1) .BUBL P Calculation (T.Finally.

x2 = 1-x1 CHEE 311 Lecture 2 12 .DEW P Calculation (T.Substitute x1 and x2 in Eqn (5) by using Raoult’s law: y1 * P y 2 * P y1 * P ( 1  y1 )* P  sat  sat  1 sat sat P1 P2 P1 P2 (6) . y1 known) P1sat P2sat .Re-arrange and solve Eqn.Now you can obtain x1 from Eqn (1) . (6) for P .Finally.For the liquid-phase composition (dew) we can write: x1+x2=1 (5) .Calculate and from Antoine’s Equation .

If not. (4) for pressure P’ . Therefore. as follows: .Re-arrange Antoine’s 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 . try another T’-value . calculation of T. the saturation pressures for the mixture components cannot be calculated directly. y1 requires an iterative approach.Calculate y1 from Raoult’s law CHEE 311 Lecture 2 13 .Calculate P1 ( T' ) and P2 ( T' ) . x1 known) Since T is an unknown.Select a temperature T’ so that 1 2 sat sat . then P’=P.Solve Eqn.If P  P'   .BUBL T Calculation (P.

(7): . try another T’-value . (6) for pressure P’ .Calculate P1 ( T' ) and P2 ( T' ) from Antoine’s Eqn. .Select a temperature T’ so that T1sat  T'  T2sat sat sat .Calculate x1 from Raoult’s law CHEE 311 Lecture 2 14 .Solve Eqn. then P’=P. If not.DEW T Calculation (P.Re-arrange Antoine’s equation so that the saturation temperatures of the components at pressure P can be calculated from Eqn.If P  P'   . x1 requires an iterative approach: . y1 known) Same as before. calculation of T.

Use Raoult’s law in the following form: x1 * P1sat ( 1  x1 )* P2sat 1  yi  P  P .Calculate P1sat and P2sat from Antoine’s Equation . x1 * P1 y1  P CHEE 311 Lecture 2 15 (8) .. sat i.P.e.Re-arrange and solve Eqn. (8) for x1 .Now you can obtain y1 from Eqn (1). T Flash Calculation .

9600 2826. and (b) a Txy diagram for P=90 kPa for a mixture of 1-chlorobutane (1) /chlorobenzene (2) Antoine Coefficients: A B C 1-chlorobutane (1) 13.Example Assuming Raoult’s Law to be valid.55 CHEE 311 Lecture 2 16 .26 224. prepare (a) a Pxy diagram for T=90oC.9926 3295.12 217.10 Chlorobenzene (2) 13.

0 1.0 … … … P1sat 1.0 CHEE 311 Lecture 2 17 . T Flash calculations.Construction of Pxy diagrams • The construction of Pxy diagram requires multiple P.0 This type of calculations can also be performed by keeping T constant and varying x1 or y1 from 0.0 0. • The results can be tabulated as shown below: P  P2sat x1  sat P1  P2sat P (kPa) x1 * P1sat y1  P P2sat 0.0 to 1. where T is held constant and P is varied from P2sat to P1sat.

Example* – (a) Generation of Pxy Data CHEE 311 Lecture 2 18 .

20 0.00 y1 VLE 60.00 CHEE 311 0.00 vapor 20.00 liquid P (kPa) 100.00 19 .00 140.00 40.00 120.80 1.00 0.00 x1 80.Example – (a) Construction of a Pxy Plot 160.00 0.40 Lecture 2 0.60 0.

0 This type of calculations can also be performed by keeping P constant and varying x1 or y1 from 0.0 CHEE 311 Lecture 2 20 . Flash calculations.0 to 1.0 1.Construction of Txy diagrams • The construction of Txy. diagram requires multiple P. 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 0 0 … … … T1sat 1. each one of which provides a set of equilibrium y1. T.

Example – (b) Generation of Txy Data CHEE 311 Lecture 2 21 .

Example – (b) Construction of a Txy Plot CHEE 311 Lecture 2 22 .

x DEW T P. y T. y P.These calculations are classified as follows: Specified/Known Variables Unknown Variables Calculation T. and composition .. x P. x T.Summary • Why? To completely identify the thermodynamic state of a mixture at equilibrium (single phase. y BUBL T P. T. 2 phases.VLE Calculations .?) • How? Through the calculation of its P. y BUBL P T. x DEW P P. y P.The type of calculation that we need to perform is subject to the variables we are looking to evaluate . T Flash CHEE 311 Lecture 2 23 . T x.