VAPOR/LIQUID

EQUILIBRIUM
Chapter 4
Lecture 7

Learning Outcomes of Chapter 4

Able to understand the 2-phase system that is
in equilibrium
Able to describe the P-T-x-y diagram for
vapour-liquid equilibrium (VLE)
Able to plot phase diagrams such as Pxy, Txy
and obtain the relevant equilibrium data
Able to solve the VLE problems (calculating T,
P and composition) by applying models such
as Raoults Law, Henrys Law, modified
Raoults Law and K-value correlations

SUMMARY OF CHAPTER 4
VAPOUR-LIQUID EQUILIBRIUM

VLE Models

Phase Diagrams

3-D diagram
P-T-x,y

2-D diagrams
P-x,y, T-x,y, y-x, P-T

Raoult
s Law

Henry
s Law

K-value

Modified
Raoults Law

VLE Calculations:
Bubble point (BP, BT)
Dew point (DP, DT)
Flash

NATURE OF EQUILIBRIUM
Equilibrium: a static condition in which
no changes occur in the macroscopic
properties of a system with time.

When T, P,
and x
reaches
final values
which will
remain
fixed:

Vapour Liqud Equilibrium (VLE)

VLE equilibrium between liquid phase and vapour phase.

VLE problem determination of T, P or composition (xi or yi).
Phase composition:
Liquid composition xi
Vapour composition yi
Requirement for equilibrium:
Both phases L and V @ the same T and P.
Gibbs energy for each phase is similar.
VAPOUR
y 1, y 2
LIQUID
x1 , x2

@ T,
P

VLE Diagrams
3-D
diagram
(PTxy)
2-D
diagrams
P-x1,y1 @ Tconst
or
T-x1,y1 @ Pconst

P-T

y1-x1 @ Tconst
or
y1-x1 @ Pconst

NATURE OF EQUILIBRIUM

Mass (mole) fraction

or
mi or ni = mass or moles of species
m or n = total mass or moles

Molar concentration [unit mol per volume]

or

xi = mole fraction of a particular species

V = molar volume of the mixture or solution
q = volumetric flow rate

Phase Rule & Duhems Theory

Equilibrium state compositions are
determined by

Phase Rule and,

Duhems Theory

Gibbs Phase Rule

Number of variables that may be
independently fixed in a system at
equilibrium
=
Difference between total number of
variables that characterize the intensive
state of the system and number of
independent equation

F=2+N
Where : F degree of freedom

Duhems Theory
For any closed system
formed initially from given
masses of prescribed
chemical species, the
equilibrium state is
completely determined when
any two independent
variables are fixed

E: QUALITATIVE BEHAVIOR

VLE: QUALITATIVE BEHAVIOR

VL = Tie line

Upper surface: saturated

Liquid state (P-T-x1), x is
liquid phase mole-fraction

Bubble Point: For a

liquid at point F, at
constant
Temperature,
pressure is reduced &
composition moves
along FG, boiling
starts
at point
Dew
Point:
As L.
pressure is lowered,
more & more Liquid
vaporizes until
vaporization completes
at W; point where
Lowerdisappears
surface:
liquid
saturated Vapor state
(P-T-y1),
y is vapor phase molefraction

(dew
____line)
bubble line; -----

Pxy @ Tconstant and Txy @ Pconstant

PBsat

TAsat
TBsat

PAsat

WHAT ARE THE DIFFERENCES AND

SIMILARITIES ???

SIMPLE MODELS for VLE

To determine:
T, P and phase compositions in equilibrium (x1, y1).

Involve 3 types of calculations:

Bubblepoint Calculations
Dewpoint Calculations
Flash Calculations

Models used:
Raoults Law Modified Raoults Law
Henrys Law
K-value from De Priester Chart
VAPOUR
y1, y2 (yi=1)
LIQUID
x1 , x2 (xi=1)

@ T,
P

Raoults Law

Assumptions:
Vapourphaseasanidealgas(used@lowtomoderateP).
Liquid phase as an ideal solution (the species comprise in
thesystemarechemicallysimilar).
Molecular species not too different in size and of the same
chemicalnature.
Eg: isomers of orth-, meta- and para-xylene; n-benzene/ nheptane,ethanol/propanol,benzene/toluene.

Limitations:
appliedifPisatisknown
appliedifoperatingTlowerthanTc(T<Tc)
Strength:
Valid for any species present at a mole fraction
approachingunitywithconditionthatitsvapourisideal.

Raoults Law

(i = 1, 2,)

(10.1)

where
xi

: Liquid phase mole-fraction

yi

: Vapor phase mole-fraction

: Vapor pressure of pure species i

: total pressure

yi P xi Pi
Partial
Pressure

Pi yi P

sat

P y P P y P
i

Daltons Law: Sum of Pi =

Dewpoint & Bubblepoint Calculations

with Raoults Law
FIND
GIVEN
BUBL P: Calculate {yi} and P, given {xi} and T
DEW P: Calculate {xi} and P, given {yi} and T
BUBL T: Calculate {yi} and T, given {xi} and P
DEW T: Calculate {xi} and T, given {yi} and P

Antoine
equations
used to solve VLE
problem that relate
vapour pressure as a
function of T for
species of a system
Table B.2, App. B).

B
ln P / kPa A
t K C
sat

RAOULTs
LAW

yi P xi Pi
BUBBLEPOINT
CALCULATION
(xi given)
iyi=1

x P

sat

sat

DEWPOINT
CALCULATION
(yi given)
ixi=1
(10.2)

i i

(10.3)

sat
y
P
i i
i

binary system (x2=1-x1):

P = P2sat + (P1sat P2sat)x1
Plot of P vs. x1 @ Tconst is a straight line that
connects P sat @ x =0 and P sat @ x =1

Guidelines on VLE calculations through

Raoults Law
ln P1sat A1
ln P2sat A2

B1
T1 C1
B2
T2 C2

{I
}

Binary system with its Antoine equations, relate the vapour

pressure with T

(A) BUBL P (Given x1 and T, compute y1 and P)

Rare in normal practice, but calculations the easiest.
BUBL P required to determine P:
to prevent liquid from boiling, or
to lower the boiling point in vacuum distillation.

BUBL P CALCULATION
(Given x1 and T, find y1 and P)

With T, find P1sat and P2sat from

Antoine {I}
Determine:
( a) P= xi Pisat, and
( b) yi=(xi Pisat)/P
ANSWERS: P and yi

(B) DEW P (Given y1 and T, compute x1 and P)

For DEW P, T does not change, hence P1sat and P2sat also do
not change.
Also, the liquid composition is not known.

DEW P CALCULATIONS
(Given y1 and T, find x1 and P)
With given T and y1, determine:
(a) P1sat and P2sat from Antoine {I}
1
(b) P
, and
sat
yi Pi
i

(c) x1=(y1P)/( P1sat) and x2=1-x1

y
i

1
i

ANSWERS:
Pi sat

and x1=(y1P)/( P1sat)

(C) BUBL T (Given x1 and P, compute y1 and T)

Iterative procedure required to solve BUBL T.

In BUBL T calculation, T is not known initial guess for
unknown T can be made from saturated T for pure species at
given P from Antoine equations {I}.

ln P

Ti

sat

sat

B
A
T C

Bi

Ci
Ai ln P

Tguess xiTi sat x1T1sat x2T2sat

BUBL T CALCULATION
(Given x1 and P, find y1 and T)
With given P, find T1sat and T2sat from {I}:
Ti sat

Bi
Ci
Ai ln P

Determine Tguess:
Tguess=xiTisat= x1T1sat + x2T2sat
With x1 and Tguess, determine:
(a) P1sat, P2sat from Antoine {I}; and (b) = P1sat/P2sat
Find the new value for: sat
P1

P
x1 x2

Calculate new T from

Antoine {I}:
B1
Tcalc

A1 ln P1sat

C1

And compare Tguess with Tcalc.

ARE THEY SIMILAR?
YES
ANSWERS:
T and y1=(x1 P1sat)/P

TcalcTguess
???
NO

(D) DEW T (Given y1 and P, compute x1 and T)

AsinBUBL Tcalculation,TalsoisunknowninDEW
T initial guess for T from saturated T of pure
speciesatgivenPfromAntoineequations({I}):
ln P

Ti sat

sat

B
T C

Bi

Ci
Ai ln P

Tguess yiTi sat y1T1sat y2T2sat

Liquid composition also not known Iterative

procedureisrequiredtosolveDEW T.

DEW T CALCULATION
(Given y1 and P, find x1 and T)
With given P, find T1sat and T2sat from Antoine {I}:
Bi
Ci
Ai ln P

Ti sat

Find Tguess=yiTisat= y1T1sat + y2T2sat

With Tguess, determine:
(a) P1sat and P2sat from Antoine {I}, and
(b) =P1sat/P2sat
Find:

P1satsat P y1 y2
P1 P y1 y2

Calculate new T Bfrom

Antoine {I}:
1
Tcalc

Tkira

C1
A1 B
1 ln satP1sat
C1

A1 ln P1

And compare Tguess with Tcalc.

ARE THEY SIMILAR?
YES
ANSWERS:
T and x1=(y1P)/( P1sat)

TcalcTguess
???
NO

Example 10.1 (page 352)

Binary

system acetonitrile(1)/nitromethane(2) conforms closely to

Raoults law. Vapor pressure for the pure species are given by the
following Antoine equations:

a) Prepare a graph showing P vs. x1 and P vs. y1 at temperature 750C

b) Prepare a graph showing T vs. x1 and T vs. y1 for a pressure of 70
kPa

Example 10.1 (a)

BUBL
P calculations are required, T and x is given

This is a binary system, therefore eq. 10.2 is used.

Saturated pressures is calculated from Antoine
equation, at given T = 348.15 K (75oC),

BUBL P CALCULATION
(Given x1 and T, find y1 and P)

83.21 kPa and 41.98 kPa

With
equation (10.2)

Let taken x1 = 0.6;

y1 can then be calculated from

equation (10.1)

With T, find P1sat

and P2sat from
Antoine {I}

Determine:
( a) P = xi Pisat, and
( b) yi =(xi Pi sat)/P

ANSWERS: P and yi

Example 10.1 (a)

At 75 C, the liquid 0.6 (by
mol)
acetonirile
is
in
equilibrium with vapor 0.75
(by mol) acetonitrile
By using different values for
x1, the table below can be
obtained and the graph can
be plotted
x1
y1
P (kPa)
o

0.0

0.0000

41.98

0.2

0.3313

50.23

0.4

0.5692

58.472

0.6

0.7483

66.72

0.8

0.8880

74.96

1.0

1.0000

83.21

85

85

Acetonitrile(1)/nitromethane(2) at 75 celsius (348.15K)

75

75

65

65

pressure, P/kPa

pressure, P/kPa
55

55

45

45

35

35
0

0.1

0.2

0.3

0.4

0.5
x1,y1

0.6

0.7

0.8

0.9

Example 10.1 (a)

Example 10.1 (a)

This

is DEW P, by eq. (10.3);

At 75 C and y1 = 0.6
o

DEW P CALCULATIONS
(Given y1 and T, find x1 and P)

kPa
With given T and y1, determine:

At point c, vapor composition, y1=0.6

Pressure and liquid composition at c can
be read from graph or calculated.
x1 is the liquid phase composition at point
c

(a) P1sat and P2sat from Antoine {I}

(b)

1
yi Pi sat , and
i

(c) x1=(y1P)/( P1sat) and x2=1-x1

ANSWERS:

1
yi Pi sat
i

and x1=(y1P)/( P1sat)

Example 10.1 (b)

b)

As P is fixed, temperature changes. So BUBL T is used.

and are calculated from Antoine equation as follows

Finding x1 from equation (10.2)

(A)
1.

Calculate boiling point for both liquids at the pressure given

2.

Selecting different temperatures between the two boiling points

3.

Calculate and for these temperatures

4.

Calculate x1 from

Example 10.1 (b)

At P = 70 kPa,
= 69.84oC, = 89.58oC.
Choosing different temperatures, for
example at 78oC,
= 91.76 kPa and = 46.84 kPa, so
= 0.5156
Then from equation (10.1)

Applying the same method at different

temperatures, the following table can
be obtained and the graph can be
plotted

x1

y1

T (oC)

0.0000
0.1424
0.3184
0.5156
0.7378
1.0000

0.0000
0.2401
0.4742
0.6759
0.8484
1.0000

89.58
86
82
78
74
69.84

Example 10.1 ( b)
BUBL T calculation to find T and :
For x1 = 0.6, and P = 70 kPa,

This procedure should be followed:

1.

Using , Calculate from equation (B)

2.

Calculate T from Antoine equation for

component 2

3.

Find a new value for from equation (C)

4.

Return to 1, iterate to converge for final

value of T

Calculate T:
Equation (10.2) is rewritten as
;

(B)

Subtract Antoine equation for both

components
(C)
Initial value for is calculated from arbitrary
intermediate temperature

Following this procedure, T = 349.57 K (76.42oC)

From Antoine equation, = 87.17 kPa, then from
equation (10.1)

BUBL T CALCULATION
(Given x1 and P, find y1 and T)
With given P, find T1sat and T2sat from {I}:
Ti sat

Bi
Ci
Ai ln P

Determine Tguess:
Tguess=xiTisat= x1T1sat + x2T2sat
With x1 and Tguess, determine:
(a) P1sat, P2sat from Antoine {I}; and (b) = P1sat/P2sat
Find the new value for: sat
P1

P
x1 x2

Calculate new T from

Antoine {I}:
B1
Tcalc

A1 ln P1sat

C1

And compare Tguess with Tcalc.

ARE THEY SIMILAR?
YES
ANSWERS:
T and y1=(x1 P1sat)/P

TcalcTguess
???
NO

DEW T CALCULATION
(Given y1 and P, find x1 and T)

Dew T calculations can also be

used, but , similar procedure is
followed, then T = 352.73 K
(79.58oC).
So, temperature rises from
76.42oC to 79.58oC during
vaporization step.

With given P, find T1sat and T2sat from Antoine {I}:

Ti sat

Bi
Ci
Ai ln P

Find Tguess=yiTisat= y1T1sat + y2T2sat

With Tguess, determine:
(a) P1sat and P2sat from Antoine {I}, and
(b) =P1sat/P2sat

Find:

P1satsat P y1 y2
P1 P y1 y2

Calculate new TB1 from Antoine {I}:

Tcalc

Tkira

AB1 ln P1sat
1

A1 ln P1sat

C1

C1

And compare Tguess with Tcalc.

ARE THEY
SIMILAR?
YES

ANSWERS:
T and x1=(y1P)/( P1sat)

TcalcTguess
???
NO

Henrys Law
Main assumptions:
1. Pressure is low enough that the vapor can be
taken as an ideal gas
2. Gas is present as a very dilute solute in the
liquid phase

Henrys Law
The partial pressure of the species in the
vapor phase is directly proportional to its
liquid-phase mole fraction
ApplicationofRLtoaspeciesirequiresPisatatthe
Tapplicationnotsuitableforspeciesiofwhich
theoperatingTishigherthanitscriticalT(T>Tc).
Hence,HenrysLawisappliedfor:
Systematlowerandintermediate P sothatassumption
ofidealconditionforitsvapourisstillvalid,and
Speciespresentasadilutesoluteintheliquidphase.

 For a binary system that consists of a dilute

species 1 in the liquid phase and is at equilibrium
with its vapour:
Liquid phase obeys Henrys Law
Vapor phase obeys Raoults Law

VAPOUR
y1 , y2

Raoults
Law

LIQUID
x1 << x2

Henrys
Law

@ T, P

Henrys Law

(i = 1, 2, N)

where
Hi : Henrys constant
xi : Liquid phase mole-fraction
yi : Vapor phase mole-fraction
P : total pressure

Example 10.2 (page 358)

Assuming that carbonated water contains only
CO2(1) and H2O(2), determine the compositions of
the vapor & liquid phases in a sealed can of soda
& the Pressure exerted on the can at 10 oC. Henrys
constant for CO2 in water at 10oC is about 990 bar.

Example 10.2 (page 358)

Assume x1 = 0.01
Henrys law for species 1:
Raoults law for species 2:
Sum is
H1 = 990 bar and = 0.01227 bar (steam tables)
P = (0.01 990) + (0.99 0.01227) = 9.912 bar

Example 10.2 (page 358)

Then from Raoults law, equation (10.1),

So,
Vapor phase is nearly pure CO2