05.

Liquid phase properties from VLE data

Prof. Ángel Darío González-Delgado
 5. Liquid phase properties from VLE data
• If TL=TV, system is in thermal equilibrium V
• If PL=PV, system is in mechanical equilibrium
• If FL=FV, the same amount of moles that are moving
from liquid to vapor phase, return from vapor to
liquid phase.
Also, chemical potentials are equal in both phases, if
not, molecules will move to the phase with lower
chemical potential
L
5. Liquid phase properties from VLE data

fˆiV  fˆi L For all components, i = 1, 2, …k

How do we model fugacities in real systems?

ˆf V  y ˆV P
i i i

You can calculate fugacity coefficients using:

P
ln ˆi    Zi  1
dP
0
P
 5. Liquid phase properties from VLE data
However, for low pressures (less than 1 bar), vapor phases usually can be
approximated to ideal gases, for which fugacity coefficient is 1, then:
ˆf V  y P
i i

What about the liquid phase?

fˆiV  fˆi L  yi P
Table 5.1. VLE Data for Methyl Ethyl Ketone(1)/Toluene(2) at 50°C
Table 5.1. VLE Data for Methyl Ethyl Ketone(1)/Toluene(2) at 50°C
5. Liquid phase properties from VLE data
How about the liquid phase?

First approximation:

fˆi L  fˆi id  xi f i Lewis/Randall rule

Figure 5.1. Fugacities for methyl ethyl ketone (1)/toluene (2) (from data at constant T)
5. Liquid phase properties from VLE data
Remember activity coefficient (comparison of ideal with real solution):

fˆi fˆi
i   id
xi fi fˆi
For calculation of experimental values, fugacities are eliminated in favor
of measurable quantities:

f i  Pi sat This equation is

known as
modified
yi P Raoult’s law
sat
 i
xi Pi
 5. Liquid phase properties from VLE data
The activity coefficients are related to GE
By the additivity rule for a binary mixture:

GE
 x1 ln  1  x2 ln  2
RT

So, if gi are obtained experimentally, is GE

 These four thermodynamic functions
are properties of the liquid phase

Table 5.1. VLE Data for Methyl Ethyl Ketone(1)/Toluene(2) at 50°C

Becomes
indeterminate
in both limits
(0/0)

Calculated from yi P  xi Pi sat  i From additivity

rule
 If 2 becomes pure, Ln
ϒ1 trends to a finite Indeterminate in both
value, namely limits
If 1 becomes
Liquid phase pure, Ln ϒ2
presents positive trends to a
deviations from finite value,
Raoult’s law namely

Ln ϒ1 trends to
zero if 1
becomes pure
GE
 x1 ln  1  x2 ln  2  (0) ln  1  (1)(0)
RT

GE
Ln ϒ2 trends to zero if
 x1 ln  1  x2 ln  2  (1)(0)  (0) ln  2
2 becomes pure RT
Figure 5.1. The Methyl Ethyl Ketone(1)/Toluene(2) system at 50°C. (a) Pxy data and their
correlation (b) Liquid-phase properties and their correlation
 5. Liquid phase properties from VLE data
Lim x10 of GE/x1x2RT
GE G E / RT dG E / RT
lim x1 0  lim x1 0  lim x1 0 L’Hopital’s rule
x1 x2 RT x1.1 dx1

But:
GE
 x1 ln  1  x2 ln  2 d(1-x1)/dx1=-1
RT

dG E
/ RT d ln  1 d ln  2
Then:  x1  ln  1  x2  ln  2
dx1 dx1 dx1
 5. Liquid phase properties from VLE data
From the Gibbs-Duhem equation:
d ln  1 d ln  2
x1  x2 0
dx1 dx1
Remember the
figure

Then, Lim x10 of GE/x1x2RT:

GE d ln  1 d ln  2 1
lim x1 0  x1  ln  1  x2  ln  2  lim x1 0 ln  ?
x1 x2 RT dx1 dx1 2
5. Liquid phase properties from VLE data

Similarly, Lim x11 of GE/x1x2RT

GE
lim x1 1  ln  2
x1 x2 RT
 5. Liquid phase properties from VLE data
Data Reduction
• We measure VLE experimentally and we want to
obtain analytical expressions to calculate VLE at other
conditions

• For example, we see that GE/x1x2RT

follows a straight line

How can be defined a mathematical expression

For this lineal relation?
 5. Liquid phase properties from VLE data
We can get GE/RT as a function of composition
GE
 A21 x1  A12 x2
x1 x2 RT

Where A21 and A12 are constants in any particular application.

In an alternate form:
GE
 ( A21 x1  A12 x2 ) x1 x2
RT
 5. Liquid phase properties from VLE data
nG E n1n2
Multiplying by n:  ( A21n1  A12 n2 )
 n1  n2 
2
RT

From this equation we can calculate 𝑙𝑛 𝛾1 and 𝑙𝑛 𝛾2 as functions of

composition and compare with the experimental values.
 5. Liquid phase properties from VLE data

To do:
Find 𝑙𝑛 𝛾1 and 𝑙𝑛 𝛾2 as functions of composition using the following
expression

 (nG E / RT ) 
ln  1   
 n 1  P ,T ,n2
 5. Liquid phase properties from VLE data
Results:

ln  1  x22 [ A12  2( A21  A12 ) x1 ]

ln  2  x [ A21  2( A12  A21 ) x2 ]
2 2-parameters Margules
1 equations

Margules equations represents a commonly used empirical model of

solution behavior.
Max Margules
Max Margules was a mathematician, physicist, and chemist. During his
doctoral studies he was a Privatdozent: an unpaid position, but one
which allowed him to lecture students. Students' fees gave him some
income. Later, administration offered this teaching job to someone else
after he refused to convert from Judaism to acquire the position.
In 1919 the Austrian Society for Meteorology awarded him the silver
Hann Medal of Acknowledgement. Margules accepted the medal, but
rejected the money. He rejected all attempts to make the last year of
his life bearable. His small pension and the devaluation of the currency
due to WWI led to a life in poverty. He contented himself with food
coupons in the post WWI period. He developed hunger edema, which
he refused to remedy and on the October 4, 1920 he died from
starvation.
 5. Liquid phase properties from VLE data
For this figure that was obtained from experimental
data:
GE
 ( A21 x1  A12 x2 ) x1 x2
RT

How to obtain A21 and A12?

 5. Liquid phase properties from VLE data
For this figure that was obtained from experimental
data:
𝐺𝐸
= (0.198𝑥1 + 0.372𝑥2 )𝑥1 𝑥2
𝑅𝑇

A set of VLE data has been REDUCED to a simple

mathematical equation for the dimensionless
excess Gibbs energy.
 5. Liquid phase properties from VLE data
A set of VLE data has been REDUCED to a simple
mathematical equation for the dimensionless
excess Gibbs energy.

What are the activity coefficients at infinite

dilution for this model?
 5. Liquid phase properties from VLE data
A set of VLE data has been REDUCED to a simple
mathematical equation for the dimensionless
excess Gibbs energy.

What are the activity coefficients at infinite

dilution for this model?

The Margules parameters

 Data reduction can be
made for other systems

Table 5.2. VLE Data for Chloroform(1)/1,4-Dioxane(2) at 50°C

Figure 5.2. The Chloroform(1)/1,4-Dioxane(2) system at 50°C (a) Pxy
data and their correlation. (b) Liquid-phase properties and their
correlation
 5.1.Thermodynamic consistency
• Experimental values of activity coefficients, and the following equation
give values of excess Gibbs energy.
GE
 x1 ln  1  x2 ln  2
RT
• This addition process is independent of Gibbs-Duhem equation
• On the other hand, Gibbs-Duhem equation is implicit in equation
 (nG E / RT ) 
ln  1   
 n 1  P ,T ,n2
And activity coefficients derived from this equation necessarily obey the
Gibbs-Duhem equation
 5.1.Thermodynamic consistency
• The Gibbs-Duhem equation imposes a constraint on activity coefficients that
may not be satisfied by a set of experimental values.

• These derived activity coefficients cannot possibly be consistent with

experimental values unless these experimental values also satisfy the Gibbs-
Duhem equation.

• If the experimental data are inconsistent with the Gibbs-Duhem equation,

they are necessarily incorrect as the result of systematic error in the data.

• We need to check that the experimentally obtained activity coefficients satisfy

the Gibbs-Duhem equation.
 5.1.Thermodynamic consistency
• Consistency test
*
G E The * denotes
   x1 ln  1
*
 x2 ln  2
*
experimental values
 RT 
d (G E / RT )* d ln  1* d ln  *
By differentiation gives:  x1  ln  1*  x2 2
 ln  2*
dx1 dx1 dx1

d (G E / RT )* d ln  1* 1 * d ln  2*
Or:  x1  ln  x2
dx1 dx1 2 * dx1
 5.1.Thermodynamic consistency
• Equation for Derived property values (values given by a correlation as
Margules equations)
d (G E / RT ) 1
 ln
dx1 2

• Subtracting the equations:

d (G E / RT ) d (G E / RT )* 1  1 *  d ln  1* d ln  2* 
  ln  ln   x1  x2 
dx1 dx1 2 2 *  dx1 dx1 

• The differences between like terms are RESIDUALS, which can be represented
by sigma
d (G E / RT )  1  d ln  1* d ln  2* 
  ln   x1  x2 
dx1 2  dx1 dx1 
 5.1.Thermodynamic consistency
Consistency test

If data set is reduced so as to make the residuals in GE/RT scatter about

zero, then the derivative is effectively zero, reducing the equation to:

 1  d ln  1* d ln  2* 
 ln   x1  x2 
2  dx1 dx1  Right side is
Residual of the left
provides a direct measure Gibb/Duhem equation,
of deviation from requires to be zero for
Gibbs/Duhem equation consistent data
 5.1.Thermodynamic consistency
An alternative objective function: Barker’s method

• Fit the model GE/RT to make the calculated pressures the closest possible to
the experimental data.

• For example, obtain A12 and A21 for the Margules equation to minimize the
calculated pressures with respect to the experimental values (see dashed
lines in Figure 5.2)
 5.1.Thermodynamic consistency

ln  1  x22 [ A12  2( A21  A12 ) x1 ]

ln  2  x [ A21  2( A12  A21 ) x2 ]
2
1
Minimize the sum of squares of the following function:

[ P
i
i
exp
 x1 1 ( A12 , A21 , x1 , x2 ) P1  x2 2 ( A12 , A21 , x1 , x2 ) P2 ]
sat sat 2

Starting with A12=0.5, A21=1, get A12= 0.758, A21=0.435