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CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013

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SOLUTION THERMODYNAMICS:
APPLICATION
Fundamental equations of solution thermodynamics are given in the
preceding chapter.
In this chapter, experimental vapor/liquid equilibrium (VLE) data are
considered, from which the activity coefficient correlations are derived.
2
LIQUID PHASE PROPERTIES FROM VLE DATA
MODELS FOR THE EXCESS GIBBS ENERGY

3











4
The figure shows coexistence of a vapor mixture and liquid solution in
vapor/liquid equilibrium. T and P are uniform throughout the vessel and
can be measured with appropriate instruments. Vapor and liquid samples
may be withdrawn for analysis and this provides experimental values for
mole fractions in the vapor {y
i
} and mole fractions in the liquid {x
i
}.
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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For species i in the vapor mixture, eq. (11.52) is written as


The criterion of vapor/liquid equilibrium, as given by eq. (11.48), is that
. Therefore,


VLE measurements are made at low pressure (P s 1 bar) that the vapor
phase may be assumed an ideal gas. In this case . Therefore,


The fugacity of species i (in both the liquid and vapor phase) is equal to
the partial pressure of species i in the vapor phase.

5

l v
i i i
f y P | =
l v
i i i
f f y P = =

v v
i i i
f y P | =

l v
i i
f f =

1
v
i
| =

i
i
i
f
y P
|
(11.52)
Fugacity increases from zero at infinite dilution (x
i
= y
i
0) to P
i
sat
for
pure species i. This is illustrated by the data of Table 12.1 for methyl ethyl
ketone(1)/toluene(2) at 50
o
C (323.15K). The first three columns list a set
of experimental P-x
1
-y
1
data and columns 4 and 5 show
6
1 1 2 2

and f y P f y P = =
i
i sat
i i
y P
x P
=
Eqn. (12.1)
The fugacities are plotted in Fig. 12.2
as solid lines. The straight dashed
lines represent the Lewis/Randall
rule expressing the composition
dependence of the constituent
fugacities in an ideal solution,

This figure illustrates the general
nature of relationships
for a binary liquid solution at
constant T.


id
i i i f x f =
7
id
i i i
f x f =
1 2 1

and vs. f f x
7
The equilibrium pressure P varies
with compositions but has negligible
influence on the liquid phase values
of
Therefore, a plot at constant T and P
is as shown in Fig. 12.3 for species i
(i = 1, 2) in a binary solution at
constant T and P.

8
1 2

and . f f
8
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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The lower dashed line in Fig. 12.3 represent the Lewis/Randall rule, which
characterize ideal solution behavior.
Activity coefficient as defined by eq. (11.90) provide the actual behavior
(non-ideal) from the idealize one:



The activity coefficient of a species in solution is the ratio of its actual
fugacity to the value given by Lewis/Randall rule at the same T, P and
composition. To obtain experimental values, both are defined as
follow:



This is restatement of eq. (10.5), modified Raoults law, and allow
calculation of activity coefficient from VLE data as shown in the last two
columns of Table 12.1.


i i
i id
i i i
f f
x f f
=
9
1 2
i i
i sat
i i i i
y P y P
(i , , ....N)
x f x P
= = =

and
id
i i
f f
(12.1)
9
The solid lines in Fig. 12.2 and 12.3, representing experimental values of ,
become tangent to the Lewis/Randall rule lines at x
i
= 1.
In the other limit, becomes zero. The ratio is indeterminate
in this limit, and application of lHopital rule yields



Eq. (12.2) defines Henrys constant, H
i
as the limiting slope of the
curve at x
i
= 0.
As shown by Fig. 12.3, this is the slope of a line drawn tangent to the curve
at x
i
= 0. The equation of this tangent line expresses Henrys law:


Henrys law as given by eq. (10.4) follows immediately from this equation
when i.e. when has its ideal gas value.
10

i
f

0,
i i
x f

i i
f x
0
0

lim
i
i
i i
i
x
i i
x
f df
x dx

=
| |
= H |
\ .
(12.2)

vs
i i
f x

i i i
f x = H (12.3)

,
i i
f y P =

i
f
( ) 10.4
i i i
y P x H =
Henrys law is related to the Lewis/Randal rule through the Gibbs/Duhem
equation.
Writing eq. (11.14) for a binary solution and replacing


Differentiate eq. (11.46) at constant T and P yields:



Therefore,

Divide by dx
1
becomes


This is the special form of the Gibbs/Duhem equation.



11
( )
1 2
1 2
1 1

ln ln
0 const T,P
d f d f
x x
dx dx
+ = (12.4)
11
by
i i i
M G =
0
i i
i
x d M

=
(11.14)
( )
1 1 2 2
0 const , x d x d T P + =
( )

ln
i i i
T RT f I + (11.46)

ln
i i
d RTd f =
( )
1 1 2 2

ln ln 0 const , x d f x d f T P + =
Substitute dx
1
by dx
2
in the second term produces


In the limit as x
1
1 and x
2
0,


Because when x
1
= 1, this may be rewritten as



According to eq. (12.2), the numerator and denominator on the right side
of this equation are equal.


12
1 1 2 2 1 2
1 2
1 2 1 1 2 2

ln ln
or

d f dx d f dx d f d f
x x
dx dx f x f x
= =
1 2
1 1 2 2
1 0
1 1 2 2

lim lim
x x
d f dx d f dx
f x f x

=
1 1

f f =
( )
( )
2
1
2
2 2
0 1
1 1 2 2 1
0

lim
x
x
x
d f dx
df
f dx f x
=
=

| |
= |
\ .
0
0

lim
i
i
i i
x
i i
x
f df
x dx

=
| |
= |
\ .
(12.2)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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Therefore the exact expression of Lewis/Randall rule applied to real
solutions is:


It also implies that eq. (11.83) provides approximately correct values of
when x
i
~ 1:

13
Henrys law applies to a species as it approaches infinite
dilution in a binary solution, and the Gibbs/Duhem equation
insures validity of the Lewis/Randall rule for the other species
as it approaches purity.
1
1
1
1
1

x
df
f
dx
=
| |
= |
\ .
(12.5)

i
f

id
i i i i
f f x f ~ =
14
When the second species is
methanol, acetone exhibits positive
deviations from ideality and with
chloroform it exhibits negative
deviations.
The fugacity of pure acetone, f
acetone

is the same regardless of the identity
of the second species.
Henrys constants are represented
by the slopes of the two dotted
lines.
For a binary system,


15
1 1 2 2
ln ln
E
G
x x
RT
= +
(12.6)
Properties
of liquid
phase
i
i sat
i i
y P
x P
=
Experimen
tal data
16
Activity coefficient of a species in solution becomes unity as the species becomes pure,
each ln
i
(i=1,2) tends to zero as x
i
1.
As x
i
0, species i becomes infinitely dilute, ln
i
approaches a finite limit, namely ln
i

.
For
i
> 1 and ln
i
> 0
P-x
1
data points all lie
above dash line (Raoults
law) positive deviation.
Raoults law
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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The most important step in determining composition of species in
solution (that is in equilibrium with vapor) is to calculate the species
activity coefficients. There are a number of models that can be used to
determine the activity coefficients depending on the type of species.
Excess Gibbs free energy model e.g. Margules and Van Laar
Local composition model e.g. Wilson, NRTL and UNIQUAC
17

18
Model Equations
Margules
Van Laar




Wilson


NRTL











( )
2
1 2 12 21 12 1 ln 2 x A A A x = + (

( )
2
2 1 21 12 21 2 ln 2 x A A A x = + (

(12.10a)
(12.10b)
21 1 12 2
1 2
E
G
A x A x
x x RT
= +
(12.9a)
' '
12 21
' '
1 2 12 1 21 2
E
G A A
x x RT A x A x
=
+
(12.16)
2
'
' 12 1
1 12 '
21 2
ln 1
A x
A
A x


| |
= + |
\ .
2
'
' 21 2
2 21 '
12 1
ln 1
A x
A
A x


| |
= + |
\ .
(12.17a)
(12.17b)
( )
12 21
1 1 2 12 2
1 2 12 2 1 21
ln ln x x x
x x x x

| | A A
= + A + |
+ A + A \ . ( ) ( ) 1 1 2 12 2 2 1 21 ln ln
E
G
x x x x x x
RT
= + A + A
( )
12 21
2 2 1 21 1
1 2 12 2 1 21
ln ln x x x
x x x x

| | A A
= + A |
+ A + A \ .
21 21 12 12
1 2 1 2 21 2 1 12
E
G G G
x x RT x x G x x G
t t
= +
+ + ( )
2
2 21 12 12
1 2 21 2
1 2 21 2 1 12
ln
G G
x
x x G x x G
t
t
(
| |
= + ( |
+ + ( \ .

( )
2
2 12 21 21
2 1 12 2
2 1 12 1 2 21
ln
G G
x
x x G x x G
t
t
(
| |
= + ( |
+ + ( \ .

exp (i j)
j ij
ij
i
V a
V RT

A = =
12 12 21 21
12 21
12 21
exp( ) exp( )

G G
b b
RT RT
ot ot
t t
= =
= =
(12.18)
(12.24)
(12.19a)
(12.19b)
(12.20)
(12.21a)
(12.21b)
19
Set of points in Fig. 12.5(b) provide linear
relation for G
E
/x
1
x
2
RT


where A
21
and A
12
are constant.
Alternatively,


From eqn. (12.10a) & (12.10b), the limiting
conditions of infinite dilution (at x
i
= 0)




( )
21 1 12 2 1 2
E
G
A x A x x x
RT
= +
20
21 1 12 2
1 2
E
G
A x A x
x x RT
= + (12.9a)
(12.9b)
20
( ) ( ) 1 12 1 2 21 2
ln at 0 and ln at 0 A x A x

= = = =
Fig. 12.5(b)
A
12
= 0.372
A
21
= 0.198
From Fig. 12.5(b), the intercepts at
x
1
= 0 and x
1
=1 of the straight line
G
E
/x
1
x
2
RT gives the parameters A
12

and A
21
.
( )
2
1 2 12 21 12 1
ln 2 x A A A x = + (

( )
2
2 1 21 12 21 2
ln 2 x A A A x = + (

(12.10a)
(12.10b)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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Linear relation for G
E
/x
1
x
2
RT



where A
21
and A
12
are constant.
Alternatively,


From eqn. (12.17a) & (12.17b), the limiting conditions of infinite dilution
(at x
i
= 0)




Values of A
12
and A
21
are obtained from the intercept of plot G
E
/x
1
x
2
RT vs. x
1
at
x
1
= 0 and x
1
=1. Or from plot of x
1
x
2
RT/G
E
vs. x
1
, intercept at x
1
=0 is 1/A
12

and at x
1
=1 is 1/A
21
.


21
' '
12 21
' '
1 2 12 1 21 2
E
G A A
x x RT A x A x
=
+
(12.16)
' '
1 2 12 1 21 2 1 2
' ' ' '
12 21 21 12
E
x x RT A x A x x x
G A A A A
+
= = +
2
'
' 12 1
1 12 '
21 2
ln 1
A x
A
A x


| |
= +
|
\ .
2
'
' 21 2
2 21 '
12 1
ln 1
A x
A
A x


| |
= +
|
\ .
(12.17a) (12.17b)
( ) ( ) 1 12 1 2 21 2
ln ' at 0 and ln ' at 0 A x A x

= = = =
22
( )
12 21
1 1 2 12 2
1 2 12 2 1 21
ln ln x x x
x x x x

| | A A
= + A +
|
+ A + A
\ .
( ) ( )
1 1 2 12 2 2 1 21
ln ln
E
G
x x x x x x
RT
= + A + A
( )
12 21
2 2 1 21 1
1 2 12 2 1 21
ln ln x x x
x x x x

| | A A
= + A
|
+ A + A
\ .
exp (i j)
j ij
ij
i
V a
V RT

A = =
(12.18)
(12.24)
(12.19a)
(12.19b)
The limiting conditions of infinite dilution (at x
i
= 0),
( ) ( ) 1 12 21 1 2 21 12 2
ln ln 1 at 0 and ln ln 1 at 0 x x

= A + A = = A + A =
23
21 21 12 12
1 2 1 2 21 2 1 12
E
G G G
x x RT x x G x x G
t t
= +
+ +
( )
2
2 21 12 12
1 2 21 2
1 2 21 2 1 12
ln
G G
x
x x G x x G
t
t
(
| |
= + (
|
+ + ( \ .

( )
2
2 12 21 21
2 1 12 2
2 1 12 1 2 21
ln
G G
x
x x G x x G
t
t
(
| |
= + (
|
+ + ( \ .

12 12 21 21
12 21
12 21
exp( ) exp( )

G G
b b
RT RT
ot ot
t t
= =
= =
(12.20)
(12.21a)
(12.21b)
1 21 12 12 2 12 21 21
ln exp( ) and ln exp( ) t t ot t t ot

= + = +
The limiting conditions of infinite dilution (at x
i
= 0),
All models provide eqns. for ln
1
and ln
2
. This allow construction of a
correlation of the original P-x
1
-y
1
data set (experimental values). Eq. (12.1) is
rearranged to give

Addition gives


From eqn. (12.1), therefore





Values of
1
and
2
from all models with their parameters are combined
with experimental values of P
1
sat
and P
2
sat
to calculate P and y
1
by
eqs. (12.11) and (12.12) at various x
1
.
Then, P-x
1
-y
1
diagram can be plotted to compare the experimental data and
calculated values.




24
24
1 1 1 1 2 2 2 2
and
sat sat
y P x P y P x P = =
1 1 1 2 2 2
sat sat
P x P x P = +
(12.11)
1 1 1 1 1 1
1
1 1 1 2 2 2
sat sat
sat sat
x P x P
y
P x P x P


= =
+
(12.12)
i i
i sat
i i i i
y P y P
x f x P
= =
(12.1)
24
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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25
Comparison of
experimental and
calculated data by
Margules eqn. These
clearly provide an
adequate
correlation of the
experimental data
points.
experimental
calculated
Fig. 12.5(a)
The Gibbs Duhem eqn imposes a constraint on activity coefficients that may
not be satisfied by a set of experimental values derived from P-x
1
-y
1
data.


The Gibbs Duhem eqn is implicit in eq. (11.96), and activity coefficients
derived from this equation necessarily obey the Gibbs Duhem eqn.



These derived activity coefficients cannot possibly be consistent with the
experimental values unless the experimental values also satisfy the Gibbs
Duhem eqn.

26
( )
1 2
1 2
1 1
ln ln
0 const T,P
d d
x x
dx dx

+ =
(12.7)
( )
, ,
ln
j
E
i
i
P T n
nG RT
n

(
(
(

c
=
c
(11.96)
If the experimental data are inconsistent with the Gibbs Duhem eqn, they are
necessarily incorrect as the result of systematic error in the data.
Therefore simple test is develop for the consistency with respect to the
Gibbs Duhem eqn of a P-x
1
-y
1
data set.
Application of the test for consistency is represented by Eq. (12.13) which
requires calculation of the residuals



The right side of this equation is exactly the quantity that eq. (12.7), the
Gibbs/Duhem equation, requires to be zero for consistent data.


The residual on the left therefore provides a direct measure of deviation
from the Gibbs/Duhem equation.
The extent to which a data set departs from consistency is measured by the
degree to which these residuals fail to scatter about zero.



27
* *
1 1 2
1 2
2 1 1
ln ln
ln
d d
x x
dx dx

o

= + (12.13)
Asterisk * denote the experimental values
( )
1 2
1 2
1 1
ln ln
0 const T,P
d d
x x
dx dx

+ =
(12.7)
28
Experimental
values
calculated from
eqn. (12.1) &
(12.6)
1 2
i i
i sat
i i i i
y P y P
(i , , ....N)
x f x P
= = =
(12.1)
1 1 2 2
ln ln
E
G
x x
RT
= +
(12.6)
CPE553 CHEMICAL ENGINEERING THERMODYNAMICS 5/9/2013
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P-x
1
-y
1
data and experimental values,
ln
1
*
, ln
2
*

and (G
E
/x
1
x
2
RT )* are
shown as points on Figs. 12.7(a) and
12.7(b) .
The data points of Fig. 12.7(b) for
(G
E
/x
1
x
2
RT )* show scatter.The
straight line drawn is represented by



This is eq. (12.9a) with A
21
= 0.70
and A
12
= 1.35.
Values of ln
1
, ln
2
at the given
values of x
1
, derived from this eqn,
are calculated by eqs. (12.10) and
derived values of P and y
1
at the
same values of x
1
come from eqs.
(12.11) and (12.12).
This results are plotted as the solid
lines of Fig. 12.7(a) and 12.7(b). They
clearly do not represent a good
correlation of the data.
1 2
1 2
0.70 1.35
E
G
x x
x x RT
= +
( )
2
1 2 12 21 12 1
ln 2 x A A A x = + (

(12.10a)
( )
2
2 1 21 12 21 2
ln 2 x A A A x = + (

(12.10b)
1 1 1 2 2 2
sat sat
P x P x P = + (12.11)
1 1 1
1
1 1 1 2 2 2
sat
sat sat
x P
y
x P x P


=
+
(12.12)
experimental
calculated
Barkers method
30
Application of test for consistency
represented by Eq. 12.13 requires
calculation of the residuals

which plotted vs. x
1
in Fig. 12.8.

The residuals distribute
themselves about zero, as required by
the test, but the residual ,
do not, which show the data fail to
satisfy the Gibbs/Duhem eqn.
( ) ( ) 1 2
and ln
E
G RT o o
( )
E
G RT o
( ) 1 2
ln o
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to
Chemical Engineering Thermodynamics. Seventh Edition. Mc
Graw-Hill.

31
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303