Solutions Thermo Coefficients Sample

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The document discusses various models for predicting activity coefficients in non-ideal solutions, including the Lewis/Randall rule, Henry's law, Wilson, NRTL, UNIQUAC and UNIFAC models.

Henry's law is derived from the Gibbs-Duhem equation and relates the fugacity of a species at infinite dilution to its mole fraction, consistent with the Lewis/Randall rule.

The Wilson model is based on interaction parameters, the NRTL model includes an additional entropy-related parameter, and UNIQUAC divides the excess Gibbs energy into combinatorial and residual parts based on molecular sizes and shapes.

CHE 305: SOLUTION THERMODYNAMICS

6.0 Applications of Solution Thermodynamics


Henry’s Law and Lewis/Randall Rule, Activity Coefficient Correlations & Local Composition Models
Related Readings: Chapter 13 (Sec. 13.4 & 13.5), Appendix G (Smith et al., 8th edition)

Instructor:
Engr. Michael Allan G. Ramos
Chemical Engineering Department
Technological Institute of the Philippines

1
Modified Raoult’s Law

Gamma/Phi Formulation for VLE: Φ! 𝑦! 𝑃 = 𝛾! 𝑥! 𝑃!"#$

• Raoult’s Law: Φ! = 1.0 (ideal gas) 𝛾! = 1.0 (ideal solution)

𝑦! 𝑃 = 𝑥! 𝑃!"#$

• Modified Raoult’s Law: Φ! = 1.0 (ideal gas)


𝑓'!
𝑦! 𝑃 = 𝛾! 𝑥! 𝑃!"#$ Where: 𝛾! = !"
𝑓'!

2
Henry’s Law & Lewis/Randall Rule

𝑓'!
𝛾! = !"
𝑓'!

• Lewis/Randall Rule: Ideal solution 𝑓'!!" = 𝑥! 𝑓!


• Fugacity of species is proportional to its mole fraction;
• This is given by the product of mole fraction of species in the
solution and the fugacity of pure species at the same physical state
and temperature and pressure as the solution.

• Henry’s Law: Dilute solution 𝑓'! = 𝑥! 𝐻!

Activity coefficient of a species in solution is the ratio of its


actual fugacity to the value given by the Lewis/Randall rule.

3
Henry’s Law & Lewis/Randall Rule (cont.)

Henry’s Law is related to the Lewis/Randall rule through the Gibbs/Duhem equation.

𝜕𝑀 𝜕𝑀
Gibbs/Duhem Equation: 𝑑𝑃 + .% = 0
𝑑𝑇 − , 𝑥% 𝑑 𝑀
𝜕𝑃 !,# 𝜕𝑇 $,#
%
𝜕𝐺 𝜕𝐺
Taking M as Gibbs energy: 𝑑𝑃 + 𝑑𝑇 − , 𝑥% 𝑑 𝐺̅% = 0
𝜕𝑃 !,# 𝜕𝑇 $,#
%

At constant T and P: , 𝑥% 𝑑 𝐺̅% = 0


%

But 𝐺̅% = 𝜇% : , 𝑥% 𝑑𝜇% = 0


%

For binary liquid solution: 𝑥& 𝑑𝜇&' + 𝑥( 𝑑𝜇(' = 0

4
Henry’s Law & Lewis/Randall Rule (cont.)

Henry’s Law is related to the Lewis/Randall rule through the Gibbs/Duhem equation.

For binary liquid solution: 𝑥& 𝑑𝜇&' + 𝑥( 𝑑𝜇(' = 0 Recall: 𝜇% ≡ 𝐺̅% = Γ% 𝑇 + 𝑅𝑇 ln 𝑓:%

𝑑𝜇% ≡ 𝑑 𝐺̅% = 𝑅𝑇 𝑑 ln 𝑓:%


𝑥& 𝑅𝑇 𝑑 ln 𝑓:&' + 𝑥( 𝑅𝑇 𝑑 ln 𝑓:(' = 0

𝑥& 𝑑 ln 𝑓:&' + 𝑥( 𝑑 ln 𝑓:(' = 0

𝑑 ln 𝑓:&' 𝑑 ln 𝑓:(' 𝑑 ln 𝑓:&' 𝑑 ln 𝑓:('


Division by dx1: 𝑥& + 𝑥( =0 𝑥& = − 𝑥(
𝑑𝑥& 𝑑𝑥& 𝑑𝑥& 𝑑𝑥&

𝑑 𝑓:&' 𝑑 𝑓:('
𝑑 ln 𝑓:&' 𝑑 ln 𝑓:(' 𝑑𝑥& 𝑑𝑥(
Since dx1 = -dx2: 𝑥& = 𝑥( = '
𝑑𝑥& 𝑑𝑥( :
𝑓& '
𝑓:(
𝑥& 𝑥(
5
Henry’s Law & Lewis/Randall Rule (cont.)
𝑑 𝑓:&' 𝑑 𝑓:('
𝑑𝑥& 𝑑𝑥(
= '
:
𝑓& '
𝑓:(
𝑥& 𝑥(

𝑑 𝑓:&' 𝑑 𝑓:('
𝑑𝑥& 𝑑𝑥(
In the limit as 𝑥& → 1 and 𝑥( → 0: lim = lim
#! →& 𝑓:&' #" *+ 𝑓:('
𝑥& 𝑥(

1
𝑑 𝑓:(' ≡ 𝐻𝑒𝑛𝑟𝑦 ! 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
1 𝑑 𝑓:&' 𝑑𝑥(
#" *+
But 𝑓:&' = 𝑓&' when 𝑥& = 1: =
𝑓&' 𝑑𝑥& 𝑓:('
#! *& lim ≡ 𝐻𝑒𝑛𝑟𝑦 ! 𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
#" *+ 𝑥(

6
Henry’s Law & Lewis/Randall Rule (cont.)

1 𝑑 𝑓:&'
=1
𝑓&' 𝑑𝑥& #! *&

𝑑 𝑓:&' This equation is the exact expression of the


= 𝑓&'
𝑑𝑥& #! *&
Lewis/Randall Rule as applied to real solutions.

Henry’s Law applies to a species as it approaches infinite dilution in a


binary solution, and the Gibbs/Duhem equation insures validity of
Lewis/Randall rule for the species as it approaches purity

7
Relating Activity Coefficients to Excess Gibbs Energy

𝑓:% Implies a direct relationship between


Recall: 𝜇% ≡ 𝐺̅% = 𝑅𝑇 ln %- = 𝑅𝑇 ln 𝛾%
, ,
partial molar excess Gibbs energy of a
𝑓:% species and its activity coefficient in
solution
Summability Relation: .%
𝑀 = , 𝑥% 𝑀
%

Taking M as 𝐺 , : 𝐺 , = , 𝑥% 𝐺̅%,
𝑛𝐺 ,
% 𝜕
𝑅𝑇
ln 𝛾% =
𝐺 , = 𝑥& 𝐺&̅ , + 𝑥( 𝐺̅(, 𝜕𝑛% $,!, .#

𝐺 , = 𝑥& 𝑅𝑇 ln 𝛾& + 𝑥( 𝑅𝑇 ln 𝛾( • We need only one model or


analytical expression for the excess
𝐺,
= 𝑥& ln 𝛾& + 𝑥( ln 𝛾( Gibbs energy, GE to obtain activity
𝑅𝑇 coefficient for every species.

8
Estimating Activity Coefficients from Experimental VLE
𝑛𝐺 #
𝜕 𝑅𝑇
ln 𝛾" =
𝜕𝑛" $,&, '!

Limited Fitting / Modeling Analytical expression for GE Partial differentiation


Experimental as a function of
Results composition
(i.e. P-x-y data) • Margules Equation
• Van Laar Equation
• Wilson Equation
• NRTL Equation Activity coefficients
• UNIQUAC/UNIFAC Method of species
over the whole
composition range

Prediction of VLE

9
Activity Coefficient Models

𝐺6
Generally: = 𝑔(𝑇, 𝑃, 𝑥7, 𝑥8, … , 𝑥9 )
𝑅𝑇

For liquid at low to moderate pressure at constant T: 𝐺6


• Weak dependence on P (effect of P is neglected)
= 𝑔(𝑥7, 𝑥8, … , 𝑥9 )
𝑅𝑇
• Sole function of composition

For binary system, this is often represented as


𝐺6
= 𝑥7𝑥8(𝑎 + 𝑏𝑥7 + 𝑐𝑥78 + ⋯ )
a power series: 𝑅𝑇

An equivalent power series is given by 𝐺6 8


Redlich/Kister expansion:
= 𝐴 + 𝐵 𝑥7 − 𝑥8 + 𝐶 𝑥7 − 𝑥8 +⋯
𝑥7𝑥8𝑅𝑇
𝐺6
For an ideal solution: A=B=C=…=0 =0
𝑅𝑇
10
The Two-suffix Margules Equation (A≠0, B=C=…=0)
𝐺6 𝐺6
The simplest non-ideal model for GE : =𝐴 = 𝐴𝑥7𝑥8
𝑥7𝑥8𝑅𝑇 𝑅𝑇
• Where the parameter A is fit for experimental data for a given binary mixture.
• A strong function of temperature but may be a weak function of pressure (low to moderate pressure).
• Independent of composition of the system.

𝑛𝐺 ,
𝜕
ln 𝛾& =
𝑅𝑇 𝐺&̅ , = 𝑅𝑇 ln 𝛾& = 𝐴𝑥((
𝜕𝑛&
𝑛𝐺 , $,!, ."
ln 𝛾& = 𝐴𝑥((
𝜕
𝑅𝑇
ln 𝛾% =
𝜕𝑛% $,!, .# 𝑛𝐺 ,
𝜕 𝑅𝑇
ln 𝛾( = 𝐺̅(, = 𝑅𝑇 ln 𝛾( = 𝐴𝑥&(
𝜕𝑛( $,!, .!
ln 𝛾( = 𝐴𝑥&(

11
The Three-suffix Margules Equation (A≠0, B ≠ 0, C=…=0)

𝐺6 𝐺6
= 𝐴 + 𝐵(𝑥7 − 𝑥8) = 𝐴87𝑥7 + 𝐴78𝑥8 𝑥7𝑥8
𝑥7𝑥8𝑅𝑇 𝑅𝑇
Where: 𝐴78 = 𝐴 − 𝐵 (single molecule of 1 surrounded by 2)
𝐴87 = 𝐴 + 𝐵 (single molecule of 2 surrounded by 1)

𝑛𝐺 ,
𝜕
𝑅𝑇 ln 𝛾& = 𝑥(( 𝐴&( + 2 𝐴(& − 𝐴&( 𝑥&
ln 𝛾& =
𝜕𝑛&
𝑛𝐺 , $,!, ."
𝜕
𝑅𝑇
ln 𝛾% =
𝜕𝑛% $,!, .# 𝑛𝐺 ,
𝜕
𝑅𝑇 ln 𝛾( = 𝑥&( 𝐴(& + 2 𝐴&( − 𝐴(& 𝑥(
ln 𝛾( =
𝜕𝑛( $,!, .!

12
The Three-suffix Margules Equation (A≠0, B ≠ 0, C=…=0)

13
The Three-suffix Margules Equation (A≠0, B ≠ 0, C=…=0)

14
The Three-suffix Margules Equation (A≠0, B ≠ 0, C=…=0)

15
Determination of 𝜸𝒊 from Experimental VLE

1. Carry out an experiment to


collect the necessary VLE data
(columns 1, 2, 3)

2. Calculate the activity


coefficients 𝛾! & 𝛾" using the
Modified Raoult’s Law
(columns 6 & 7).

𝒚𝒊 𝑷 = 𝜸𝒊 𝒙𝒊 𝑷𝒔𝒂𝒕
𝒊
D! E
𝛾! = F E"#$
! !

16
Determination of 𝜸𝒊 from Experimental VLE (cont.)

17
Determination of 𝜸𝒊 from Experimental VLE (cont.)

3. Calculate the the values for


𝐺 # /𝑅𝑇 and 𝐺 # /𝑥! 𝑥" 𝑅𝑇
(columns 6 & 7).

𝐺,
= 𝑥& ln 𝛾& + 𝑥( ln 𝛾(
𝑅𝑇

4. Plot ln 𝛾! , ln 𝛾" , 𝐺 # /𝑅𝑇,


𝐺 # /𝑥! 𝑥" 𝑅𝑇 vs 𝑥!

18
Determination of 𝜸𝒊 from Experimental VLE (cont.)

19
Determination of 𝜸𝒊 from Experimental VLE (cont.)

5. Develop a correlation of 𝛾$ from the data.

Using the Three-suffix Margules Equation as the model:

𝐺6 𝐺6 Provides a
= 𝐴87𝑥7 + 𝐴78𝑥8 𝑥7𝑥8 = 𝐴87𝑥7 + 𝐴78𝑥8 linear relation
𝑅𝑇 𝑥7𝑥8𝑅𝑇
𝐺6
= 𝐴87𝑥7 + 𝐴78(1 − 𝑥7)
𝑥7𝑥8𝑅𝑇

𝐺6
= 𝐴87 − 𝐴78 𝑥7 + 𝐴78 𝑦 − 𝑖𝑛𝑡𝑒𝑟𝑐𝑒𝑝𝑡 = 𝐴78
𝑥7𝑥8𝑅𝑇
𝑠𝑙𝑜𝑝𝑒 = 𝐴87 − 𝐴78
𝒚 = 𝒎 𝒙 + 𝒃

20
Determination of 𝜸𝒊 from Experimental VLE (cont.)

5. Develop a correlation of 𝛾$ from the data.

Using the Three-suffix Margules Equation as the model:

𝐺6 𝐺6 Provides a
= 𝐴87𝑥7 + 𝐴78𝑥8 𝑥7𝑥8 = 𝐴87𝑥7 + 𝐴78𝑥8 linear relation
𝑅𝑇 𝑥7𝑥8𝑅𝑇

𝐺6
• When 𝑥! = 1, 𝑥" = 0: = 𝐴87 1 + 𝐴78 0 = 0.198
𝑥7𝑥8𝑅𝑇
∴ 𝑨𝟐𝟏 = 𝟎. 𝟏𝟗𝟖
𝐺6
• When 𝑥! = 0, 𝑥" = 1: = 𝐴87 0 + 𝐴78 1 = 0.372
𝑥7𝑥8𝑅𝑇
∴ 𝑨𝟏𝟐 = 𝟎. 𝟑𝟕𝟐
21
Determination of 𝜸𝒊 from Experimental VLE (cont.)

22
Determination of 𝜸𝒊 from Experimental VLE (cont.)

6. Recalculate ln 𝛾! , ln 𝛾" , 𝐺 # /𝑅𝑇 using the obtained correlation.

𝐺6 𝐺6
= 𝐴87𝑥7 + 𝐴78𝑥8 = 0.198𝑥7 + 0.372𝑥8 𝑥7𝑥8
𝑥7𝑥8𝑅𝑇 𝑅𝑇

ln 𝛾7 = 𝑥88 𝐴78 + 2 𝐴87 − 𝐴78 𝑥7 ln 𝛾7 = 𝑥88 0.372 + 2 0.198 − 0.372 𝑥7

ln 𝛾8 = 𝑥78 𝐴87 + 2 𝐴78 − 𝐴87 𝑥8 ln 𝛾8 = 𝑥78 0.198 + 2 0.372 − 0.198 𝑥8

23
Determination of 𝜸𝒊 from Experimental VLE (cont.)

24
Determination of 𝜸𝒊 from Experimental VLE (cont.)
7. Plot again the liquid properties (calculated from correlation) vs 𝑥! .

25
Determination of 𝜸𝒊 from Experimental VLE (cont.)

26
Determination of 𝜸𝒊 from Experimental VLE (cont.)

For limiting conditions (infinite dilutions):

ln 𝛾7 = 𝑥88 𝐴78 + 2 𝐴87 − 𝐴78 𝑥7


ln 𝛾7< = 𝐴78 (𝑥7 → 0)

ln 𝛾8 = 𝑥78 𝐴87 + 2 𝐴78 − 𝐴87 𝑥8


ln 𝛾8< = 𝐴87 (𝑥8 → 0 𝑜𝑟 𝑥7 → 1)

27
Determination of 𝜸𝒊 from Experimental VLE (cont.)
8. Predict the VLE using Modified Raoult’s Law and the calculated activity coefficients from
the correlation .

𝑃 = 𝑥7𝛾7𝑃7=>? + 𝑥8𝛾8𝑃8=>?

@! A! B!"#$ @! A! B!"#$
𝑦7 = B
= @! A! B!"#$ C@% A% B%"#$

28
Determination of 𝜸𝒊 from Experimental VLE (cont.)

29
Determination of 𝜸𝒊 from Experimental VLE (cont.)

30
Thermodynamic Consistency Test
If the experimental data are inconsistent with the Gibbs/Duhem equation,
then the data are incorrect due to systematic error in the data.

𝐺,
= 𝑥& ln 𝛾&∗ + 𝑥( ln 𝛾(∗ Where: (*) denotes experimental values
𝑅𝑇

𝐺,
𝑑 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾 ∗
𝑅𝑇 (
= 𝑥& + ln 𝛾&∗ + 𝑥( − ln 𝛾(∗
𝑑𝑥& 𝑑𝑥& 𝑑𝑥&

𝐺, 𝐺,
𝑑 𝛾&∗ 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾(∗ 𝑑
𝑅𝑇 𝑅𝑇 𝛾& 𝑑 ln 𝛾& 𝑑 ln 𝛾(
= ln ∗ + 𝑥& + 𝑥( = ln + 𝑥& + 𝑥(
𝑑𝑥& 𝛾( 𝑑𝑥& 𝑑𝑥& 𝑑𝑥& 𝛾( 𝑑𝑥& 𝑑𝑥&
(Based on experimental property values) (Based on derived property values from correlations)

31
Thermodynamic Consistency Test (cont.)
𝐺,
𝑑 𝛾& 𝑑 ln 𝛾& 𝑑 ln 𝛾(
𝑅𝑇
= ln + 𝑥& + 𝑥(
𝑑𝑥& 𝛾( 𝑑𝑥& 𝑑𝑥&

𝑑 ln 𝛾& 𝑑 ln 𝛾( (Gibbs/Duhem Equation at for binary system


Recall: 𝑥& + 𝑥( =0
𝑑𝑥& 𝑑𝑥& at constant T & P)

𝐺,
𝑑 𝛾&
𝑅𝑇 (Based on derived property values from correlations)
= ln
𝑑𝑥& 𝛾(

Subtracting the experimental equation & derived equation:



𝐺, 𝐺,
𝑑 𝑅𝑇 𝑑 𝑅𝑇 𝛾& 𝛾&∗ 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾(∗
− = ln − ln ∗ + 𝑥& + 𝑥(
𝑑𝑥& 𝑑𝑥& 𝛾( 𝛾( 𝑑𝑥& 𝑑𝑥&

32
Thermodynamic Consistency Test (cont.)

𝐺, 𝐺,
𝑑 𝑑 𝛾& 𝛾&∗ 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾(∗
𝑅𝑇 𝑅𝑇
− = ln − ln ∗ + 𝑥& + 𝑥(
𝑑𝑥& 𝑑𝑥& 𝛾( 𝛾( 𝑑𝑥& 𝑑𝑥&
0
𝐺,
𝑑 𝛿 𝑅𝑇 𝛾& 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾(∗
= 𝛿 ln − 𝑥& + 𝑥( Where: (𝛿) denotes residual (derived - actual).
𝑑𝑥& 𝛾( 𝑑𝑥& 𝑑𝑥&

𝛾& 𝑑 ln 𝛾&∗ 𝑑 ln 𝛾(∗


𝛿 ln = 𝑥& + 𝑥( Should be equal to zero if it is to obey Gibbs/Duhem Equation
𝛾( 𝑑𝑥& 𝑑𝑥&

Provides a measure of deviation from Gibbs/Duhem Equation


Average values of the residuals:
< 0.030 (high degree of consistency) < 0.10 (Acceptable) > 0.10 (Data contain significant errors)

33
Thermodynamic Consistency Test (cont.)

34
Thermodynamic Consistency Test (cont.)

35
Thermodynamic Consistency Test (cont.)

36
Barker’s Method
• With the aid of a computer, values for the Margules parameters A12 and A21 are
searched to yield pressure values as close as possible to the measured values.

Step 1: Get the difference between 𝑷𝒄𝒂𝒍𝒄𝒖𝒍𝒂𝒕𝒆𝒅 & 𝑷𝒆𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍. 𝑃R>SR − 𝑃T@U?

"
Step 2: Calculate the sum of squared errors (SSE). Σ 𝑃%&'% − 𝑃()*+

Step 3: Using Excel Solver, set the objective to minimize the SSE by changing variable
cells A12 and A21.

Result: ∴ 𝑨𝟐𝟏 = 𝟎. 𝟏𝟗𝟑 ∴ 𝑨𝟏𝟐 = 𝟎. 𝟑𝟓𝟏


(0.198 using GE/RT method) (0.372 using GE/RT method)

37
The van Laar Equation

• Another two-parameter excess Gibbs energy model;


• Developed from an expansion of (𝑅𝑇𝑥7𝑥8)/𝐺 6 instead of 𝐺 6 /(𝑅𝑇𝑥7𝑥8).
0
𝑥& 𝑥( 𝑅𝑇 𝑥& 𝑥( 𝐴&( 𝑥& + 𝐴0(& 𝑥(
= 0 + 0 = 0 𝐴0
𝐺, 𝐴(& 𝐴&( 𝐴&( (&

0
𝐺, 𝐴&( 𝐴0(&
= 0
𝑥& 𝑥( 𝑅𝑇 𝐴&( 𝑥& + 𝐴0(& 𝑥(

0 1( 1(
0 𝐴&( 𝑥& 𝐴0(& 𝑥(
ln 𝛾& = 𝐴&( 1+ 0 ln 𝛾( = 𝐴0(& 1+ 0
𝐴(& 𝑥( 𝐴&( 𝑥&

ln 𝛾&2 = 𝐴&(
0 (when 𝑥( = 0) ln 𝛾(2 = 𝐴0(& (when 𝑥) = 0)

38
The van Laar Equation (cont.)

0
𝑥& 𝑥( 𝑅𝑇 𝑥& 𝑥( 𝐴&( 𝑥& + 𝐴0(& 𝑥(
= 0 + 0 = 0
𝐺 , 𝐴(& 𝐴&( 𝐴&( 𝐴0(&

𝑥& 𝑥( 𝑅𝑇 1 1 1
= − 𝑥& +
𝐺, 𝐴0(& 𝐴&(
0 0
𝐴&(

𝒚 = 𝒎 𝒙 + 𝒃

0 1 1
𝐴&( = 𝐴0(& =
𝑏 𝑚+𝑏

𝑨X𝟏𝟐 = 𝟎. 𝟒𝟏𝟎𝟗 𝑨X𝟐𝟏 = 𝟎. 𝟐𝟏𝟒𝟗

39
The van Laar Equation (cont.)

40
Features of Margules and van Laar Equations

• Applicable to binary mixtures only

• Empirical (fitting experimental VLE data)

• No theoretical foundations

• Constrained to constant temperature and independency of activity coefficient on pressure.

41
Local Composition Models

• Theoretical development in the molecular thermodynamics of liquid solution behavior are often
based on the concept of local composition (concentration around a molecule is different from the
bulk concentration).

• Local compositions presumed to account for the short-range order and non-random molecular
orientations that results from differences in molecular size and intermolecular forces

1. Wilson Equation (G.M. Wilson, 1964)


2. Non-Random Two Liquid (NRTL) Equation (H. Renon & J.M. Prausnitz, 1968)
3. Universal Quasi-Chemical (UNIQUAC) Equation (D.S. Abrams & J.M. Prausnitz, 1975)
4. UNIQUAC Functional-Group Activity Coefficient (UNIFAC) Method
(A.A. Fredenslund, R.L. Jones & J.M. Prausnitz, 1975)

42
The Wilson Equation
𝐺,
= −𝑥& ln 𝑥& + 𝑥( Λ&( − 𝑥( ln 𝑥( + 𝑥& Λ (&
𝑅𝑇

Λ&( Λ (&
ln 𝛾& = − ln 𝑥& + 𝑥( Λ&( + 𝑥( − ln 𝛾&2 = − ln Λ&( + 1 − Λ (&
𝑥& + 𝑥( Λ&( 𝑥( + 𝑥& Λ (&
Λ&( Λ (&
ln 𝛾( = − ln 𝑥( + 𝑥& Λ (& − 𝑥& − ln 𝛾(2 = − ln Λ (& + 1 − Λ&(
𝑥& + 𝑥( Λ&( 𝑥( + 𝑥& Λ (&

𝑉( 𝜆&(
Λ&( = exp −
𝑉& 𝑅𝑇 Wilson parameters must be restricted to positive numbers to
𝑉& 𝜆(& ensure validity of the above equations at infinite dilution.
Λ (& = exp −
𝑉( 𝑅𝑇

𝜆%3 is an energetic parameter (decribes how i-i interaction varies from i-j interaction)
𝑉3 /𝑉% is ratio of molar volumes (accounts for the relative sizes of molecules of i and j)

43
The Wilson Equation (cont.)
𝐺,
= −𝑥& ln 𝑥& + 𝑥( Λ&( − 𝑥( ln 𝑥( + 𝑥& Λ (&
𝑅𝑇

Λ&( Λ (&
ln 𝛾& = − ln 𝑥& + 𝑥( Λ&( + 𝑥( − ln 𝛾&2 = − ln Λ&( + 1 − Λ (&
𝑥& + 𝑥( Λ&( 𝑥( + 𝑥& Λ (&
Λ&( Λ (&
ln 𝛾( = − ln 𝑥( + 𝑥& Λ (& − 𝑥& − ln 𝛾(2 = − ln Λ (& + 1 − Λ&(
𝑥& + 𝑥( Λ&( 𝑥( + 𝑥& Λ (&

Applicability: • Mixtures of polar and non polar species (i.e. alcohols & alkanes)
• Hydrocarbon mixtures
Limitation: • Systems exhibiting partial miscibility

𝚲𝟏𝟐 = 𝟎. 𝟒𝟒𝟔𝟐 𝚲𝟐𝟏 = 𝟏. 𝟒𝟎𝟐𝟎

44
The Wilson Equation (cont.)

45
The NRTL Equation
𝐺, 𝐺(& 𝜏(& 𝐺&( 𝜏&(
= +
𝑥& 𝑥( 𝑅𝑇 𝑥& + 𝑥( 𝐺(& 𝑥( + 𝑥& 𝐺&(
(
𝐺(& 𝐺&( 𝜏&(
ln 𝛾& = 𝑥(( 𝜏(& + ( ln 𝛾&2 = 𝜏(& + 𝜏&( exp −𝛼 𝜏&(
𝑥& + 𝑥( 𝐺(& 𝑥( + 𝑥& 𝐺&(
(
𝐺&( 𝐺(& 𝜏(&
ln 𝛾( = 𝑥&( 𝜏&( + (
ln 𝛾(2 = 𝜏&( + 𝜏(& exp −𝛼 𝜏(&
𝑥( + 𝑥& 𝐺&( 𝑥& + 𝑥( 𝐺(&

𝐺&( = exp −𝛼 𝜏&( 𝜏%3 is an energetic parameter


𝐺(& = exp −𝛼 𝜏(& (decribes how j-j interaction varies from i-j interaction)
𝑏&(
τ&( = 𝛼 is an entropic parameter
𝑅𝑇
(related to the non-randomness of the mixture
𝑏(&
τ(& = à short-range order & molecular orientation)
𝑅𝑇
46
The NRTL Equation (cont.)
𝐺, 𝐺(& 𝜏(& 𝐺&( 𝜏&(
= +
𝑥& 𝑥( 𝑅𝑇 𝑥& + 𝑥( 𝐺(& 𝑥( + 𝑥& 𝐺&(
(
𝐺(& 𝐺&( 𝜏&(
ln 𝛾& = 𝑥(( 𝜏(& + ( ln 𝛾&2 = 𝜏(& + 𝜏&( exp −𝛼 𝜏&(
𝑥& + 𝑥( 𝐺(& 𝑥( + 𝑥& 𝐺&(
(
𝐺&( 𝐺(& 𝜏(&
ln 𝛾( = 𝑥&( 𝜏&( + (
ln 𝛾(2 = 𝜏&( + 𝜏(& exp −𝛼 𝜏(&
𝑥( + 𝑥& 𝐺&( 𝑥& + 𝑥( 𝐺(&

Applicability: • Systems with large deviations from ideality


• Systems exhibiting partial miscibility
• Mixtures of organic species with water

Limitation: • Optimal fitting of parameters to experimental data is relatively


more complicated
47
Parameter values for the Wilson and NRTL Equations

47
The UNIQUAC Model
• A more sophisticated excess Gibbs energy model.
• Divides the excess Gibbs energy into two parts: combinatorial part & residual part.
𝐺 6
g6 ≡
𝑅𝑇
g6 = g6RYZ[!9>?Y\!>S + g6\T=!"]>S

Based on sizes and shapes of the molecules. Based on intermolecular forces


Requires only pure component data (crystallographic measurements):
1. Volume parameter, 𝑟% ; volume fraction, Φ%∗
2. Surface parameter, 𝑞% ; area fraction, 𝜃%

Applicability: • Large number of polar and non-polar species


• Systems exhibiting partially miscible liquids

49
The UNIQUAC Model (cont.)

50
The UNIFAC Model

• Modified UNIQUAC model.


• The molecular interactions are decomposed into the interactions between each of the
functional groups or subgroups that comprise the molecule.

i.e. Ethanol (C2H5OH) 3 subgroups: CH3 , CH2 , OH

• Termed as predictive activity coefficient model: if data are available for all the functional
groups or subgroups that comprise the molecules in a system, activity coefficients can be
calculated without data from the specific molecules in the mixture.

51
The UNIFAC Model (cont.)

52
The UNIFAC Model (cont.)

53
The UNIFAC Model (cont.)

54
END.

References:
• Smith et al. (2018). Introduction to Chemical Engineering Thermodynamics (8th ed.)
• Koretzky, M. (2013). Engineering and Chemical Thermodynamics (2nd ed.)
• Dugos, N. (De La Salle University). Solution Thermodynamics: Applications. PIChE-MMAC UPLIFT X. Seminar-
Workshop on Teaching Solutions Thermodynamics. October 17, 2020.

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