Chemical Engineering Thermodynamics

Vapor-Liquid Equilibrium (VLE)

Li Xi
[email protected]

McMaster University

Chemical Engineering 3D04

Copyright c 2020 by Li Xi.

Reproduction or distribution is prohibited without the prior written permission of the author.

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 1 / 24

 Equilibrium Criteria and One-Component VLE

Section 1

Equilibrium Criteria and One-Component VLE

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 2 / 24

Corresponding text in S&VN-8:

Equilibrium Criteria for Closed Systems section 12.4, pages 435–436.

1-component VLE section 6.5.
 Equilibrium Criteria and One-Component VLE Equilibrium Criteria

Thermodynamic equilibrium according to the 2nd law

General Criterion
t
dSuniv = dS t + dSsurr
t
≥0
dU t + PdV t − TdS t ≤ 0
(S&VN-8 12.2).
2nd law determines the
direction of spontaneous
processes: i.e., direction of the for non-equilibrium changes
equilibrium. within a closed system with
At equilibrium, dSunivt = 0 and uniform T and P.
t t
Suniv = (Suniv )max . at equilibrium:
dU t =

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 3 / 24

 Equilibrium Criteria and One-Component VLE Equilibrium Criteria

Equilibrium criteria
Equilibrium Criteria for Isolated Systems
Spontaneous Process: dS t ≥ 0
Equilibrium: S t = Smax
t

Equilibrium Criteria for Closed Systems

Constraints Spontaneous Process Equilibrium
T , P, n
T , V t, n
S t , P, n dH t ≤ 0 H t = Hmin
t

S t, V t, n dU t ≤ 0 U t = Umin
t

Requirements:
closed systems (constant n).
T and P are uniform within the system.

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 4 / 24

 Equilibrium Criteria and One-Component VLE Equilibrium Criteria

Example: Application in VLE of pure fluids

Consider a closed system where T and P are controlled. For a pure

substance, at any given T , one can adjust P to P sat where VLE occurs.
How should the molar Gibbs energies of the two phases – G l and G v –
compare at the phase equilibrium (T , P sat )?

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 5 / 24

 Equilibrium Criteria and One-Component VLE One-Component VLE

Phase equilibrium and Clapeyron equation

Two-Phase Equilibrium
– Pure fluids, constant T and P.

Question Clapeyron Equation

– How many variables can
be independently specified dP sat ∆H α→β
(how many degrees of = (S&VN-8 6.85)
dT T ∆V α→β
freedom)? where, ∆H α→β = H β − H α is the latent heat.

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 6 / 24

 Equilibrium Criteria and One-Component VLE One-Component VLE

VLE: Temperature dependence of vapor pressure

Clapeyron Equation Applied to VLE

d ln P sat ∆H l→v
=− (S&VN-8 6.88)
d (1/T ) R∆Z l→v

Further Simplifications
Add these assumptions:
Note: ∆H l→v ≡ ∆H vap vapor phase is ideal gas;
V l  V v.
How about add: ∆H l→v = const.?

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 7 / 24

 Equilibrium Criteria and One-Component VLE One-Component VLE

VLE: Temperature dependence of vapor pressure (cont’d)

Clausius-Clapeyron Equation
I.G. and V l  V v : Experimentally, ln P sat vs.
d ln P sat ∆H l→v 1/T does often give a
=−
d (1/T ) R straight line, but not for
the Clausius-Clapeyron
I.G., V l  V v and ∆H l→v = const.:
relation (why?).
P sat ∆H l→v 1 1
ln sat = − −
P0 R T T0

Antoine Equation (Empirical)

B
ln P sat = A −
T +C
(S&VN-8 6.90; A, B & C found in Table B.2 – note
the temperature unit.)
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 8 / 24
 Raoult’s Law and Multicomponent VLE Calculations

Section 2

Raoult’s Law and Multicomponent VLE Calculations

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 9 / 24

Corresponding text in S&VN-8:

Raoult’s Law section 13.3, pages 454–455.

Pxy and Txy Behaviors section 12.3, pages 432-435.
Dew- and Bubble-Point Calculations section 13.3, pages 455–456.
Flash Calculation section 13.8, pages 503–506. Notes:
Eq. 13.113 and contents below involve concepts to be
covered later.
 Raoult’s Law and Multicomponent VLE Calculations Raoult’s Law

Raoult’s law

(S&VN-8 13.16)

Convention for notation:

Assumptions xi –liquid mole fraction;
vapor:
yi –vapor mole fraction.
good for:
low or moderate pressure.
Phase Diagram
liquid: ∗
For a two component mixture following
good for:
the Raoult’s law:
chemically similar
components; Sketch the P − x1 plot at given
or: T.
any species i when xi → 1. How about the P − y1 curve?
∗
Not the same as I.G. (more to come.)
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 10 / 24
 Raoult’s Law and Multicomponent VLE Calculations Raoult’s Law

Pxy and Txy diagrams of the Raoult’s law

Pxy (const. T ) Txy (const. P)

Note
convention: 1–lighter component; 2–heavier component.
Pisat = Fn(T ); Tisat = Fn−1 (P).

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 11 / 24

 Raoult’s Law and Multicomponent VLE Calculations Dew-Point and Bubble-Point Calculations

VLE calculations: the equation setup

DoF Analysis
Equation System (Raoult’s Law)
– For an N-component
VLE problem, how many
independent variables need y1 P =x1 P1sat (T )
to be specified? y2 P =x2 P2sat (T )
..
Book-keeping .
yi P =xi Pisat (T )
Equations N
..
T &P 2 .
{xi } N−1 N−1
! !
X X
{yi } 1− yi P = 1 − xi PNsat (T )
Tot. Var. 1 1

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 12 / 24

 Raoult’s Law and Multicomponent VLE Calculations Dew-Point and Bubble-Point Calculations

Typical dew- and bubble-point calculations

2-Component/Raoult’s Law
Types of Calculations
Type T P {xi } {yi } y1 P = x1 P1sat (T )
Bubl-P K U K U (1 − y1 ) P = (1 − x1 ) P2sat (T )
Dew-P K U U K
Bubl-T U K K U
Dew-T U K U K If T is known (Bubl-P, Dew-P):
solve analytically.
K–known; U–unknown.
If P is known (Bubl-T, Dew-T):
iteration is usually needed.

∗
source: wikipedia.org
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 13 / 24
 Raoult’s Law and Multicomponent VLE Calculations Dew-Point and Bubble-Point Calculations

Example: dew- and bubble-point calculations

For the benzene (1)/toluene (2) system, parameters

Species A B C t range (◦ C)
1 Benzene 13.7819 2726.81 217.572 6 − 104
2 Toluene 13.9320 3056.96 217.625 13 − 136
of the Antoine equation
 sat 
P B
ln =A− t
kPa ◦C + C

are given. Calculate the following.

1 (Bubble-P) P and {yi }, for t = 100 ◦C and x1 = 0.4.
2 (Dew-P) P and {xi }, for t = 100 ◦C and y1 = 0.6.
3 (Bubble-T ) T and {yi }, for P = 101.325 kPa and x1 = 0.4.
4 (Dew-T ) T and {xi }, for P = 101.325 kPa and y1 = 0.6.

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 14 / 24

 Raoult’s Law and Multicomponent VLE Calculations Flash Calculation and Separation Using VLE

Separation in a “flash”

Feed: liquid mixture of two

components with different boiling
points.
Sudden increase in T or/and
decrease in P to trigger phase
separation.

Class Exercise
– Sketch the flash process shown on
this graph on a Txy diagram.
∗

∗
source: Themis Matsoukas

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 15 / 24

 Raoult’s Law and Multicomponent VLE Calculations Flash Calculation and Separation Using VLE

Separation in a “flash” (cont’d)

Notation:
L & V: mole fractions of the two
phases from the inlet stream.
zi : mole fraction of component i
in the inlet stream.
Class Exercise
– Identify L & V on the diagram.

Lever Rule

∗
source: Themis Matsoukas

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 16 / 24

 Raoult’s Law and Multicomponent VLE Calculations Flash Calculation and Separation Using VLE

Flash calculation: equation setup

Take the 2-component system for example:

– Book-keeping
variables:
y1 P = x1 P1sat (T ) (from VLE);
(1 − y1 ) P = (1 − x1 ) P2sat (T ) (from mass balance).
z1 = x1 (1 − V) + y1 V need to specify variables to
solve the problem.

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 17 / 24

 Raoult’s Law and Multicomponent VLE Calculations Flash Calculation and Separation Using VLE

Achieving better separation

A flash unit separates a

mixture into:
a vapor enriched with the
lighter component;
a liquid enriched with the
heavier component.
Can we achieve higher purity
of, e.g., the heavier
component, with VLE?

Serial flash units for the liquid stream ∗

∗
source: Themis Matsoukas
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 18 / 24
 Raoult’s Law and Multicomponent VLE Calculations Flash Calculation and Separation Using VLE

Application of VLE: distillation

(Left) concept behind distillation;

(right) schematic of a distillation
column. ∗
A typical distillation tower †
∗
source: Themis Matsoukas
†
source: www.scuolacascia.it
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 19 / 24
 VLE of General Mixtures: Pxy Behaviors and Models

Section 3

VLE of General Mixtures: Pxy Behaviors and Models

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 20 / 24

Corresponding text in S&VN-8:

Pxy Behaviors section 12.3, pages 423–426, 428–432.

Modified Raoult’s Law section 13.3, pages 456–459.
Henry’s Law section 13.3, pages 462–464.
Note: in this section, we focus on the application of these models and
their applicability conditions. Discussion related with their theoretical
foundations, including thermodynamic properties of mixtures, will be
covered later.
 VLE of General Mixtures: Pxy Behaviors and Models Qualitative Behaviors

Pxy behaviors of general mixtures

Positive/negative deviations from the
Roult’s law.
Azeotrope
no separation.
occurs when there is a
maximum/minimum in P-x1 or
P-y1 curves (why?).

S&VN-8 Fig 12.8

(a) tetrahydrofuran/carbon tetrachloride (30◦ C)
(b) chloroform/tetrahydrofuran (30◦ C)
(c) furan/carbon tetrachloride (30◦ C)
(d) ethanol/toluene (65◦ C)
(corresponding Txy diagrams: S&VN-8
Fig 12.9)

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 21 / 24

 VLE of General Mixtures: Pxy Behaviors and Models VLE Models

Modified Raoult’s law

Equation setup for VLE calculations

y1 P = x1 γ1 (T , {xi })P1sat (T )
(i = 1, 2, . . . , N)
y2 P = x2 γ2 (T , {xi })P2sat (T )
(S&VN-8 13.19)
..
.
yi P = xi γi (T , {xi })Pisat (T )
vapor – ideal gas; liquid –
..
general solution. .
activity coefficient: N−1
!
X
γi = γi (T , {xi }). 1− yi P =
1
how to obtain γi ?–will be
N−1
!
discussed later. X
1− xi γN (T , {xi })PNsat (T )
1

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 22 / 24

 VLE of General Mixtures: Pxy Behaviors and Models VLE Models

Henry’s law

(i = 1, 2, . . . , N)

applies to species i at the

xi → 0 limit: such as a gas
solute in a non-solvent.
assumes the gas/vapor phase
is an ideal gas.
H–Henry’s “constant”∗
(S&VN-8 Table 13.2).

∗
Not really a constant.
†
source: kidsaquariumsquotes.wordpress.com
c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 23 / 24
 VLE of General Mixtures: Pxy Behaviors and Models VLE Models

Summary: Simplified models for multicomponent VLE

Model Equilibrium Relation Vapor Liquid

Id. Sol.
Raoult’s Law yi P = xi Pisat (T ) I.G.
or xi → 1
Modified Raoult’s Law yi P = xi γi (T , {xi }) Pisat (T ) I.G. General
Henry’s Law yi P = xi Hi (T ) I.G. xi → 0

All of them are simplified from the general thermodynamic criterion for
VLE (to be discussed later).

Summation of mole fractions requires:

Equilibrium Ratio
X X yi
Ki xi = 1; =1
Ki
i i

c 2020 Li Xi (McMaster University) Vapor-Liquid Equilibrium (VLE) ChemE 3D04 24 / 24