AdvanceThermodynamics Materi 6

ACTIVITY MODELS
Modified Raoult's Law and Excess Gibbs

Free Energy
Equilibrium criteria: fVi = fiL
For vapor phase: fV = y
P
i
For liquid phase, we may use an activity coefficient
f iL= xi i f iL
Poynting method is used to calculate the pure
component liquid phase fugacities: f = P exp
Combining:
V L PP sat
(i), giving:
L
i
sat
y i i P=x i i sat
P
i
i exp
sat
i
RT
sat
i
V iL PPsat
i
RT
K-ratio ==> Ki=yi/xi
P
Ki= i i
P
L
sat
V PPi /RT
sat
i exp i
i
L
sat
At low pressure: Poynting Correction and ratio of isat / i
for the component approach unity ==> MODIFIED

RAOULT'S LAW
i P i
Ki=
P
L
sat
atau
yi P= xi i Psat
i
Excess Gibbs free energy: GE=G-Gis

E
G
=RT xi ln i
dst diperoleh:
i
Activity Coefficient and excess Gibbs free energy
are coupled.
Excess Gibbs energy is zero for an ideal solution
Activity Coefficients as derivatives:

GE
ni
=RT ln i
T , P , n ji
Comparison with Equation of State

Methods
Determination of G from
Experimental Data
yi P
Modified Raoult's Law:

x i P sat
i
Excess Gibbs energy from activity coefficient (for
i =
binary system):
G
=x 1 ln1 x 2 ln2
RT
plot GE/RT vs x1
Example (1): system of 2-propanol (1) + water (2)
from citation data: T=30 oC, P1sat = 60.7 mmHg, P2sat = 32.1
mmHg, y1 = 0.6462, when x1 = 0.6369 at P=66.9 mmHg

==> determine activity coefficient and relate to excess Gibbs
energyy P
y 2 P 0.353866.9
0.646266.9
1
=
=
=1.118
=
=
=2.031
1
2
sat
sat
0.363132.1
x 1 P 1 0.636960.7
x 2 P2
E
G
6
=x 1 ln1 x 2 ln2 =0.6369 ln1.1180.3631 ln 2.031=0.328
RT
plot to G /RT vs x1
One-Parameter MARGULES
Equation
the simplest expression for Gibbs excess energy
function
G
= A x1 x2
RT
Parameter A is a constant which is not associated with
the other uses of the variable (equation of state

parameters, Helmholtz energy, Antoine coefficients).
Example: derive the expression for the activity
coefficients for the one-parameter Margules equation
n1
G
= A n2
RT
n
==> 1 G E
RT ni
=An 2
T , P , n ji
[ ] [ ]
n1
n2
1 n1
2 =A
1
=Ax 2 1 x1
n n
n
n
8
==>
ln 1= Ax 2
2
Dengan cara yg sama ==>
ln 2=Ax 1
2
Example (2): continued from example (1), at 30 oC
show x1=0.1168 and y1=0.5316 at P=60.3 mmHg.

What are the pressure and vapor phase compositions
predicted by the one-parameter Margules Equation.
at x1=0.6369, we found GE/RT = 0.328.
Fitting the Margules equation:
G
= A x 1 x 2 A=0.328 /[0.63690.3631]=1.42
RT
at the new composition:
x 1=0.1168, we find : ln 1= Ax 22=1.420.88322=1.107, 1 =3.03

ln 2=Ax 21=1.42 0.1168 =0.0194, 2=1.02
2
Substituting into Modified Raoult's Law:
y 1 P=x 1 1 P1 =0.11683.0360.7=21.48 mmHg

sat
y 2 P=x 1 2 P 2 =0.88321.0232.1=28.92 mmHg
sat
P= y1 P y 2 P=50.4 mmHg
y 1= y 1 P /P=21.48/50.4=0.426
10
Two-Parameters MARGULES
Equation
GE
GE
= A21 x 1 A12 x 2 alternatively
= A21 x1 A12 x2 x 1 x 2
x1 x 2 RT
RT
requires differentiation of nGE/RT with respect to a
mole number
the equation is multiplied by n (mole numbers)
where x1=n1/(n1+n2), and x2=n2/(n1+n2):
E
n1n2
nG
= A21 n 1 A12 n 2
RT
n1n2 2
differentiation with respect to n1:
ln 1=n2 A 21 n 1A12 n2
nG / RT
n1
E
=ln1
T , P , n2
2n 1
n1 A21
1
n1n2 2 n1 n 23 n 1n 22
Reconversion of ni to xi:
ln 1= x 2 [ A21 x1 A12 x 2 12x 1 A21 x 1 ]
11
note: x2=1-x1, so:
ln 1= x 22 [ A122 A21 A12 x 1 ]
ln 2=x 1 [ A212 A12 A21 x 2 ]
Margules Equation
For the limiting conditions of infinite dilution:
ln 1 = A12 x 1=0
andd
ln 2 = A21 x 2=0
12
Example of Margules Equation

Following is set of VLE data for the system
methanol(1)/water(2) at 333.15 K:
13
calculate i ==> modified Raoult's law
i =
calculate ln i
yi P
x i P sat
i
plot ln i vs xi
A12 and A21 are values of the intercepts at x1=0 and x1=1 of
the straight line drawn to represent the GE/x1x2RT:
ln 1 = A12 x 1=0
andd
ln 2 = A21 x 2=0
we get: A12=0.372 and A21=0.198

calculate GE/RT and GE/x1x2RT
E
G
We have equation:
=x 1 ln 1x 2 ln 2
RT
E
G
or ==>
=0.198 x10.372 x 2 x 1 x2
RT
14
15
16
Use 1 and 2 to calculate VLE predictions:

yi P
sat
sat
i =
P=x
P
x
P
1 1 1
2 2 2
x i P sat
i
sat
x1 1 P1
y 1=
sat
x1 1 P sat
1 x2 2 P 2
Another method:
by fitting ln i vs xi for the following Margules equation:

ln 1= x 22 [ A122 A21 A12 x 1 ]
or
ln 2=x 1 [ A212 A12 A21 x 2 ]

2
to obtain A12 and A21
17
van Laar Equation for Activity

Coefficient Model
ln 1=
A12
A x
1 12 1
A21 x 2
ln 2=
van Laar Equation
A21
A x
1 21 1
A12 x 2
by infinite solutions method:

ln 1 = A12 x 1=0 andd
or rearranging to:
x 2 ln 2
A12=ln 1 1
x 1 ln 1
ln 2 = A21 x 2=0
x1 ln 1
A21=ln 2 1
x2 ln 2
18
Example of van Laar Equation

Consider benzene(1) + ethanol(2) system which exhibits an
azeotrope at 760 mmHg and 68.24 oC containing 44.8 mole

% ethanol. Calculate the composition of the vapor in
equilibrum with an equimolar liquid solution at 760 mmHg
given the Antoine constants:
log P1sat=6.87987-1196.76/(T+219.161)
log P2sat=8.1122-1592.86/(T+226.18)
Solution:
at T=68.24 oC, P1sat=519.7 mmHg; P2sat=503.5 mmHg
at azeotrope: x1=y1 ==> 1=P/P1sat; =P/P2sat
1=760/519.7=1.4624; =760/503.5=1.5094
where x1=0.552; x2=0.448
19
calculate A12 and A21:
A12=ln 1 1
x 2 ln 2
x 1 ln 1
x ln 1
A21=ln 2 1 1
x2 ln 2
A12=1.3421; A21=1.8810
now consider x1=x2=0.5 ==> van Laar:
1=1.579; =1.386
Problem ==> bubble temperature?

Guess T=60oC ==> P1sat=391.6 mmHg; P2sat=351.8 mmHg
yi=xi Pisat/P ==>y1=0.407; y2=0.321; yi=0.728 ==> T is too low
at T=68.24oC, P1sat=519.7 mmHg; P2sat=503.5 mmHg
yi=xi Pisat/P ==>y1=0.540; y2=0.459; yi=0.999 ==> T is ok
(Tazeotrope)
20
Wilson's Equation for Activity

Coefficient
Wilson's Equation
GE
=x 1 ln x1 x 2 12 x 2 ln x 2 x1 21
RT
ln 1=ln x 1x 2 12 x 2
ln 2=ln x 1 21x 2 x1
V2
A12
12=
exp
V1
RT
and.
12
21
x 1 x2 12 x1 21x 2
21
12
x1 x 2 12 x1 21 x2
V1
A21
21 = exp
V2
RT
Vi, Vj : molar volume of pure liquid i, j, at temperature T

21
NRTL Equation for Activity

Coefficient (3 parameters)
E
G 21 21
G 12 12
G
=
x1 x 2 RT x1 x 2 G 21 x 2 x1 G 12
[
[
NRTL Equation
]
]
ln 1= x 2 21
G 21
G 12 12
2
x 1 x2 G 21
x 2x 1 G 12
ln 2=x 1 12
G 12
G 21 21
2
x 2 x1 G 12
x 1x 2 G 21
G 12=exp 12
G 21=exp 21
b12
b21
21=
12=
RT
RT
, b12, and b21 are parameters specific to a particular pair of
species, and are independent of composition and temperature

NRTL: Non Random Two Liquid
22
For the infinite-dilution values of the activity coefficient:
ln 1 = 2112 exp 12
ln 2 =12 21 exp 21
23
UNIQUAC Equation for Activity

Coefficient
For multicomponent solution:
GE
= x j ln j / x j5 q j x j ln j / j q j x j ln
RT
j
j
j
ij
RES
ln k =ln COMB
ln
k
k
ln k
COMB
ln
RES
k
=ln k / x k 1 k / x k 5q k [ln k /k 1k /k ]
=q k 1ln
j kj
ik
ij
UNIQUAC equation requires two adjustable parameters
characterized from experimental data for each binary

system ==>
24
UNIQUAC for Binary Solution

==>
==>
1 1 5q 1 [ln 1 1 1 ]
x1
x1
1
1
1
12
q1 1ln 12 21
2
12 21
1 122
ln 1 =ln
2
2
2
2
ln 2=ln 1 5q 2 [ln 1 ]
x2
x2
2
2
1 21
2
q 2 1ln 1 122
12 21 1 122
where ==>
Q, R, v ???
xjrj
xi ri
i
j
k
r j = v Rk ;
k
x jqj
xi q i
i
q j = v k Q k
j
25
Rk parameter ==> group volume

Qk parameter ==> group surface area
Molecule size (rj) and molecule shape (qj) may be
calculated by multiplying the group parameters by the

number of times each group appears in the molecule,
and summing all the groups in the molecule
where vk(j) is the number of groups of the kth type in the jth
molecule.
26
27
Technique for Fitting Model to

Experimental data
Tools in Matlab: lsqcurvefit
%Assume you determined xdata and ydata experimentally
xdata = [0.9 1.5 13.8 19.8 24.1 28.2 35.2 60.3 74.6 81.3];
ydata = [455.2 428.6 124.1 67.3 43.2 28.1 13.1 -0.4 -1.3 -1.5];
x0 = [100; -1]
% Starting guess
[x,resnorm] = lsqcurvefit(@myfun,x0,xdata,ydata)
function F = myfun(x,xdata)
F = x(1)*exp(x(2)*xdata);
Result:
x =
498.8309 -0.1013
resnorm =
9.5049
or using GUI of Matlab: >>cftool
28

AdvanceThermodynamics Materi 6

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ACTIVITY MODELS

Modified Raoult's Law and Excess Gibbs

For liquid phase, we may use an activity coefficient

K-ratio ==> Ki=yi/xi

At low pressure: Poynting Correction and ratio of isat / i

for the component approach unity ==> MODIFIED

Excess Gibbs free energy: GE=G-Gis

Comparison with Equation of State

Modified Raoult's Law:

mmHg, y1 = 0.6462, when x1 = 0.6369 at P=66.9 mmHg

Parameter A is a constant which is not associated with

the other uses of the variable (equation of state

Dengan cara yg sama ==>

Example (2): continued from example (1), at 30 oC

show x1=0.1168 and y1=0.5316 at P=60.3 mmHg.

at the new composition:

x 1=0.1168, we find : ln 1= Ax 22=1.420.88322=1.107, 1 =3.03

Substituting into Modified Raoult's Law:

y 1 P=x 1 1 P1 =0.11683.0360.7=21.48 mmHg

requires differentiation of nGE/RT with respect to a

differentiation with respect to n1:

ln 1= x 2 [ A21 x1 A12 x 2 12x 1 A21 x 1 ]

note: x2=1-x1, so:

ln 1= x 22 [ A122 A21 A12 x 1 ]

ln 2=x 1 [ A212 A12 A21 x 2 ]

For the limiting conditions of infinite dilution:

Example of Margules Equation

calculate i ==> modified Raoult's law

the straight line drawn to represent the GE/x1x2RT:

we get: A12=0.372 and A21=0.198

Use 1 and 2 to calculate VLE predictions:

by fitting ln i vs xi for the following Margules equation:

ln 2=x 1 [ A212 A12 A21 x 2 ]

to obtain A12 and A21

van Laar Equation for Activity

van Laar Equation

by infinite solutions method:

Example of van Laar Equation

azeotrope at 760 mmHg and 68.24 oC containing 44.8 mole

calculate A12 and A21:

Problem ==> bubble temperature?

Wilson's Equation for Activity

Vi, Vj : molar volume of pure liquid i, j, at temperature T

NRTL Equation for Activity

, b12, and b21 are parameters specific to a particular pair of

species, and are independent of composition and temperature

For the infinite-dilution values of the activity coefficient:

UNIQUAC Equation for Activity

UNIQUAC equation requires two adjustable parameters

characterized from experimental data for each binary

UNIQUAC for Binary Solution

Rk parameter ==> group volume

calculated by multiplying the group parameters by the

Technique for Fitting Model to

or using GUI of Matlab: >>cftool

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