Nonideal Behavior: ITK-234 Termodinamika Teknik Kimia II

Nonideal Behavior
Dicky Dermawan
ITK-234 Termodinamika Teknik Kimia II
Nonideal Behavior, Outline
Introduction: Effect of Nonideality
Partial Molar Properties
Residual Properties
Fugacity & Fugacity Coefficient
Excess Properties
Activity & Activity Coefficient

Intorduction: Effect of Nonideality:
Tetrahydrofuran(1)/Carbon-tetrachloride(2)
t-x-y diagram P-x-y diagram
30
o
C 1 atm
P - xy Diagram
Acet onit ril( 1) / Nit romet ana( 2) @
75
o
C
40
45
50
55
60
65
70
75
80
85
0 0.2 0.4 0.6 0.8 1
x1, y1
P
txy diagram
Acetonitril(1)/Nitromethane(2)
65
70
75
80
85
90
0 0.2 0.4 0.6 0.8 1
x1, y1
t
,

o
C
@ P= 70 kPa
Effect of Nonideality:
Chloroform(1)/Tetrahydrofuran(2)
30
o
C 1 atm
P - xy Diagram
75
o
C
40
45
50
55
60
65
70
75
80
85
0 0.2 0.4 0.6 0.8 1
x1, y1
P
txy diagram
65
70
75
80
85
90
0 0.2 0.4 0.6 0.8 1
x1, y1
t
,

o
C
@P= 70 kPa
Furan(1)/Carbontetrachloride(2)
30
o
C 1 atm
P - xy Diagram
75
o
C
40
45
50
55
60
65
70
75
80
85
0 0.2 0.4 0.6 0.8 1
x1, y1
P
txy diagram
65
70
75
80
85
90
0 0.2 0.4 0.6 0.8 1
x1, y1
t
,

o
C
@ P= 70 kPa
Ethanol(1)/Toluene(2)
65
o
C
1 atm
P - xy Diagram
75
o
C
40
45
50
55
60
65
70
75
80
85
0 0.2 0.4 0.6 0.8 1
x1, y1
P
txy diagram
65
70
75
80
85
90
0 0.2 0.4 0.6 0.8 1
x1, y1
t
,

o
C
@ P= 70 kPa
x y Diagram at Constant P = 1 atm
a. Tetrahydrofuran(1)/Carbon-tetrachloride(2)
b Chloroform(1)/Tetrahydrofuran(2)
c. Furan(1)/Carbontetrachloride(2)
d. Ethanol(1)/Toluene(2)
Partial Molar Properties
. etc , G or , V , S , H , U M
i i i i i i
=
=
i i
M x M
Solution Properties:
.are properties of component i in the state of mixtures,
which, in general different from that in the state of pure
species
Partial Properties:
Pure-species Properties: . etc , G or , V , S , H , U M
i i i i i i
=
NOT:
=
i i
M x M
What physical interpretation can be given for, viz.
partial molar volume ?
Methanol Water Mixture, An Example
For pure species at 25
o
C:
Methanol (1) : V
1
= 40.727 cm
3
/mol
Water (2) : V
2
= 18.068 cm
3
/mol
What is the volume of 10 moles of methanol/water solution containing
30% mol of methanol?
Most people would think, logically:
Mol of methanol : 0.3 x 10 moles = 3 moles
Mol of water : (1-0.3) x 10 moles = 7 moles
Volume of methanol : 3 moles x 40.727 = 122.181 cm
3

Volume of water : 7 moles x 18.068 = 126.476 cm
3

Thus, the total volume : 122.181 + 126.476= 248.657 cm
3

Wrong answer! The correct answer is 240.251 cm
3
Thus there is 240.251 248.657 = -8.406 cm
3
deviation from expected value
=
i i
M x M
More on Partial Molar Properties
( )
j
n , P , T
i
i
n
nM
M
(
c
c
( )
( ) ( ) ( )
. dn
n
nM
dP
P
nM
dT
T
nM
nM d
i
n , P , T
i
n , T n , P
j
c
c
+
(
c
c
+
(
c
c
=

.) ,......... n , n , n , P , T ( M nM
3 2 1
=
( )
( ) ( )
( ) ( )
..... dn
n
nM
dn
n
nM

dP
P
nM
dT
T
nM
nM d
2
,... n , n , P , T
2
1
,... n , n , P , T
1
n , T n , P
3 1 3 2
+
(
c
c
+
(
c
c
+
c
c
+
(
c
c
=
=
i i
M x M
NOT:
=
i i
M x M
Chemical Potential as Partial Molar Property
Criteria for Vapor - Liquid Equilibria

i
P P
T T
i
g
i
g
g
=
=
=
j
n , P , T
i
i
n
) nG (
(
c
c

The chemical potential of i-th
component is defined as:
Chemical Potential as Partial Molar Property
( )
j
n , P , T
i
i
n
nG
G
(
c
c
i i
G =
( )
( ) ( ) ( )
. dn
n
nG
dP
P
nG
dT
T
nG
nG d
i
n , P , T
i
n , T n , P
j
c
c
+
(
c
c
+
(
c
c
=

If we set M = G:

Thus:

j
n , P , T
i
i
n
) nG (
(
c
c

The definition of chemical potential:

Evaluation of Partial Molar Properties
Methanol Water Mixture Example
Methanol
mol fraction
Molar volume,
mL/mol
0 18.1
0.114 20.3
0.197 21.9
0.249 23.0
0.495 28.3
0.692 32.9
0.785 35.2
0.892 37.9
1 40.7
16
20
24
28
32
36
40
0 0.2 0.4 0.6 0.8 1
x
1
M
i
x
t
u
r
e

P
r
o
p
e
r
t
y

M
M
2
M
1
M
1
2 1
x
M
x M M
c
c
+ =
1
1 2
x
M
x M M
c
c
=
=
i i
M x M
Exercise
A group of students came across an unsuspected supply of laboratory
alcohol, containing 96 mass-percent ethanol and 4 mass-percent water.
As an experiment they decided to convert 2 L of this material into vodka,
having a composition of 56 mass-percent ethanol and 44 mass-percent
water. Wishing to perform the experiment carefully, they search the
literature and found the following partial-specific volume data for
ethanol water mixtures at 25
o
C and 101.3 kPa.
The specific volume of water at 25
o
C is 1.003 L/kg. How many L of water
should be added to the 2 L of laboratory alcohol, and how many L of
vodka result?
1.243 1.273 L/kg , V
0.953 0.816 L/kg , V
In vodka ethanol 96% In
OH Et
O H
2
Fugacity, f
( ) P ln d T R dG
ig
=
( ) f ln d T R dG
( ) | ln d T R dG
R
Ideal gas :
Real gas :
P
f
= |
ig R
G G G =
Residual Gibbs energy :
Fugacity coefficient :
| =
ln
T R
G
R
At constant T
Residual Property
ig R
V V V =
P
RT
) 1 Z ( V
R
=
dP V dT S dG + =
Evaluation of Pure Component
Fugacity, f
i

dP V dG
R
i
R
i
=
} }
=
P
0
R
i
R
i
dP
RT
V
RT
dG
P f
i i
| =
Real gas :
Pure Component Fugacity Coefficient:
The fugacity :
i
R
i
ln
T R
G
| =
At constant T:
}
=
P
0
i
R
i
P
dP
) 1 Z (
RT
G
}
= |
P
0
i i
P
dP
) 1 Z ( ln
P
RT
) 1 Z ( V
i
R
i
=
Fugacity, f
i

From the following compressibility data for hydrogen at 0
o
C,
determine the fugacity of hydrogen at 950 atm
P, atm Z P, atm Z
100 1.069 600 1.431
200 1.138 700 1.504
300 1.209 800 1.577
400 1.283 900 1.649
500 1.356 1000 1.720
Fugacity, f
i

From the following compressibility data for isobutane,
determine the fugacity of butane at various temperature and pressure
P/bar 340 K 350 K 360 K 370 K 380 K
Fugacity, f
i
from Equation of State
RT
P B
1 Z
RT
PV
i
i
i
+ = =
RT
P B
ln
i
i
= |
1 0
c
c
B B
T R
P B
e + =
Virial :
6 . 1
r
0
T
422 . 0
083 . 0 B =
2 . 4
r
1
T
172 . 0
139 . 0 B =
c
r
T
T
T =
( )
1 0
r
r
i
B B
T
P
ln e + = |
c
r
P
P
P =
Critical Constants & Accentric Factors:
Paraffins
T
c
/K P
c
/bar V
c
/10
-6
m
3.
mol
-1
Z
c
e
Olefin & Miscellaneous Organics
T
c
/K P
c
/bar V
c
/10
-6
m
3.
mol
-1
Z
c
e
Miscellaneous Organic Compounds
T
c
/K P
c
/bar V
c
/10
-6
m
3.
mol
-1
Z
c
e
Elementary Gases
T
c
/K P
c
/bar V
c
/10
-6
m
3.
mol
-1
Z
c
e
Miscellaneous Inorganic Compounds
T
c
/K P
c
/bar V
c
/10
-6
m
3.
mol
-1
Z
c
e
Evaluation of Pure Component Fugacity, f
i
from Virial Equation of State, Example
Using virial equation of state,
calculate the fugacity and fugacity coefficient of:
1. Pure methyl-ethyl-ketone
2. Pure toluene
at 50
o
C and 25 kPa.

The required data:

ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
Fugacity, f
i
T R Z
P b
h
i

=
ci
5 . 2
ci
2
i
P
T R 42748 . 0
a

=
h 1
h
T R b
a
h 1
1
Z
5 . 1
i
i
+
=
Redlich-Kwong:
| |
|
|
.
|
\
|

= |
5 . 1
T R b
a
Z ) h 1 ( ln 1 Z ln
ci
ci
i
P
T R 08664 . 0
b

=
}to be solved simultaneously
i
from Redlich-Kwong Equation of State
Using Redlich - Kwong equation of state,
2. Pure toluene
at 50
o
C and 25 kPa.

The required data:

ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
i
:
Pitzers Generalized Correlation
( ) T , P f
r r
0
i
= |
( ) ( )
e
| | = |

1
i
0
i i

( ) T , P f
r r
1
i
= |
c
r
P
P
P =
c
r
T
T
T =
Evaluation of
Pure
Component
Fugacity, f
i
:

Pitzers
Generalized
Correlation
c
r
P
P
P =
c
r
T
T
T =
0
i
|
Evaluation of
Pure
Component
Fugacity, f
i
:

Pitzers
Generalized
Correlation
c
r
T
T
T =
0
i
|
c
r
P
P
P =
Evaluation of
Pure
Component
Fugacity, f
i
:

Pitzers
Generalized
Correlation
c
r
P
P
P =
c
r
T
T
T =
1
i
|
Evaluation of
Pure
Component
Fugacity, f
i
:

Pitzers
Generalized
Correlation
c
r
P
P
P =
c
r
T
T
T =
1
i
|
Evaluation of Pure Component Fugacity,
f
i
: Pitzer Correlation
Using Pitzer Correlation,
2. Pure toluene
at 50
o
C and 25 kPa.

The required data:

ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
Evaluation of Liquid
Pure Component Fugacity, f
i

dP V
T R
1

f
f
ln
P
P
i
sat
i
i
sat
i
}

Poynting factor
Fugasity of saturated vapor,
calculated exactly as calculating gas phase fugacity
( )

T R
P P V
exp P f
sat
i i
sat
i
sat
i i
(
(

| =

Since V
l
is a weak function of P at temperatures well below T
c
:
Estimation of Liquid Density

Rackett Equation:
c
r
P
P
P =
c
r
T
T
T =
V
V
c
r
=
2857 . 0
r
) T 1 (
c c
sat
Z V V

=
Examples of
Evaluation of Liquid Pure Component Fugacity, f
i

11.5
Estimate the fugacity of liquid acetone at 110
o
C and 275 bar.
At 110
o
C the vapor pressure of acetone is 4.36 bar and the
molar volume of saturated-liquid acetone is 73 cm
3.
mol
-1
11.6
Estimate the fugacity of liquid n-butane at 120
o
C and 34 bar.
At 120
o
C the vapor pressure of n-butane is 22.38 bar and the
molar volume of saturated-liquid n-butane is 137 cm
3.
mol
-1
Examples of
Evaluation of Liquid Pure Component Fugacity, f
i

11.10
The normal boiling point of n-butane is 0.5
o
C.
Estimate the fugacity of liquid n-butane at this
temperature and 200 bar.

11.11
The normal boiling point of 1-pentene is 30.0
o
C.
Estimate the fugacity of liquid 1-pentene at this

11.12
The normal boiling point of isobutane is -11.8
o
C.
Estimate the fugacity of liquid isobutane at this

Examples of
Evaluation of Gas & Liquid Pure Component
Fugacity, f
i

2 5 3
P 10 41 . 11 P 10 86 . 9 1 Z =

11.13
Prepare plots of f vs P and | vs P for isopropanol at 200
o
C for the
pressure range from 0 to 50 bar. For the vapor phase, values of
Z are given by:

Where P is in bars. The vapor pressures of isopropanol at 200
o
C
is 31.92 bar, and the liquid-phase isothermal compressibility k
at 200
o
C is 0.3.10
-3
bar
-1
, independent of P.

T
P
V
V
1
|
.
|
\
|
c
c
k
Hint:

Examples of
Evaluation of Gas & Liquid Pure Component
Fugacity, f
i

11.14
Prepare plots of f vs P and | vs P for 1,3-butadiene at 40
o
C for
the pressure range from 0 to 10 bar. At 40
o
C The vapor
pressures of 1,3-butadiene is 4.287 bar.
Assume virial model to be valid for the vapor phase.
The molar volume of saturated liquid 1,3-butadiene at 40
o
C is
90.45 cm3.mol-1
Fugacity of Steam and Water,
Using Steam Table
) S S (
T
H H
R
1

* P
f
ln
*
i i
*
i i i
(
(
= |
.
|
\
|
P* : lowest value of P in steam table
At P >= P
i
sat
, i.e. liquid phase water:
( )

T R
P P V
exp P f
sat
i i
sat
i
sat
i i
(
(

| =

Up to P
i
sat
, i.e. gas phase water (steam):

Example of Steam and Water Fugacity
Calculation Using Steam Table
11.7
From data in the steam tables, determine a good estimate for f/f
sat

of liquid water at 100
o
C and 100 bar, where fsat is the fugacity
of saturated liquid at 100
o
C.
11.8
Steam at 13000 kPa and 380
o
C undergoes an isothermal change of
state to a pressure of 275 kPa. Determine the ratio of the
fugacity in the final state to that in the initial state
11.9
Steam at 1850 psia and 700
o
F undergoes an isothermal change of
state to a pressure of 40 psia. Determine the ratio of the fugacity
in the final state to that in the initial state
Fugacity of Mixtures
B y B y y 2 B y B
22
2
2 12 2 1 11
2
1
+ + =
| |
1
ij
0
cij
cij
ji ij
B B
P
T R
B B e +
= =
=
i
ij
j
j i
B y y B
Are formulated exactly as calculation for pure component,
but we use Mixing Rules to obtain the parameters
Virial :
For binary mixtures, i = 1,2 and j = 1,2
i component pure of B B B
i ii
= =
2
j i
ij
e + e
= e
( ) ) k 1 ( T T T
ij cj ci cij
2
1
=
cij
cij cij
cij
V
T R Z
P

=
2
Z Z
Z
cj ci
cij
+
=
3
cj ci
cij
2
V V
V
3
1
3
1
|
|
|
|
.
|
\
|
+
=
RT
P B
ln
i
i
= |
Example of Calculation for
Fugacity of Mixtures Using Virial Equation
Estimate the fugacity and fugacity coefficient of an equimolar mixture
of methyl-ethyl-ketone (1) and toluene (2) at 50
o
C and 25 kPa
The required data are as follows:
ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
Fugacity of Components in Mixture

P y
f
i
i
i
|
( )

n
ln n

ln
j
n P, T,
i
i (
c
| c
= |
i
R
i

ln
T R
G
| =
Thus:
i
R
i
ln
T R
G
| =
is partial molar property of )
ln(
i
|
) ln(
i
|
Virial, binary mixtures:
) y B (
RT
P
ln
) y B (
RT
P
ln
12
2
1 22 2
12
2
2 11 1
o + = |
o + = |
12 11 12 12
B B B 2 = o
Fugacity of Components in Binary Mixtures,
Example using Virial Eqn.
Estimate the fugacity and fugacity coefficient of methyl-ethyl-ketone
(1) and toluene (2) for an equimolar mixture at 50
o
C and 25 kPa.
Set all k
ij
= 0
The required data are as follows:
ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
11.18
Estimate the fugacity and fugacity coefficient of ethylene (1) and
propylene (2) for a binary mixture of 25% ethylene as a gas at 200
o
C
and 20 bar.
Set all k
ij
= 0
More on Virial Eqn:
Fugacity of Ternary and Multicomponent Mixtures
(
(
o o +
= |

i
i ik i kk k
) 2 ( y y
2
1
B
T R
P
ln

| |
1
ij
0
cij
cij
ji ij
B B
P
T R
B B e +
= =
=
i
ij
j
j i
B y y B
Mixing Rules :
For ternary mixtures, i = 1,2,3 and j = 1,2,3
i component pure of B B B
i ii
= =

B B B 2
B B B 2
ii i i
kk ii ik ik
o
o
ik ki
kk
ii
0
0
o = o
= o
= o
More on Virial: Fugacity of
Ternary & Multicomponent Mixtures Example
11.19
Estimate the fugacity and fugacity coefficient of each component in a
ternary mixture of methane (1) / ethane (2) / propane (3) at 40
o
C
and 20 bar with the composition of 17% methane and 35% ethane
Set all k
ij
= 0
Evaluation of Mixture Fugacity, f
,
T R Z
P b
h

=
=
i j
ij j i
a y y a
h 1
h
T R b
a
h 1
1
Z
5 . 1
+
=
Redlich-Kwong:
| |
|
|
.
|
\
|

= |
5 . 1
T R b
a
Z ) h 1 ( ln 1 Z ln
=
i
i i
b y b
}to be solved simultaneously

, using
Redlich-Kwong Equation of State
calculate the fugacity and fugacity coefficient of an equimolar
mixture of methyl-ethyl-ketone (1) and toluene (2) at 50
o
C and
25 kPa

The required data:

ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
Evaluation of Component Fugacity in
Mixture Fugacity, f
,
| | ) h 1 ln(
a
a x 2
b
b
RT b
a
) h 1 ( Z ln ) 1 Z (
b
b
ln
k
k 1 k
1
5 . 1
1
1
+
|
|
|
|
.
|
\
|

+ = |

Redlich-Kwong:
| |
|
|
.
|
\
|

= |
5 . 1
T R b
a
Z ) h 1 ( ln 1 Z ln
| | ) h 1 ln(
a
a x 2
b
b
RT b
a
) h 1 ( Z ln ) 1 Z (
b
b
ln
k
k 2 k
2
5 . 1
2
2
+
|
|
|
|
.
|
\
|

+ = |


, using
Redlich-Kwong Equation of State
calculate the fugacity and fugacity coefficient of MEK and
toluene in equimolar mixture of methyl-ethyl-ketone (1) and
toluene (2) at 50
o
C and 25 kPa

The required data:

ij T
cij
/K P
cij
/bar
V
cij
/cm
3.
mol
-1
Z
cij
w
ij
11=MEK 535.6 41.5 267 0.249 0.329
12=Toluene 591.7 41.1 316 0.264 0.257
UTS 1
Excess Gibbs Energy
ig R
G G G =
. etc , G or , V , S , H , U M
i i i i i i
=
=
i i
M x M
Partial Properties:
i i i i i i
=
Residual Property
Excess Property
id E
G G G =
Partial Property of the Excess Property
id
i i
E
i
G G G =
ig
i i
R
i
G G G =
Excess Gibbs Energy
ig R
G G G =
. etc , G or , V , S , H , U M
i i i i i i
=
=
i i
M x M
Partial Properties:
i i i i i i
=
Residual Property
Excess Property
id E
G G G =
id
i i
E
i
G G G =
ig
i i
R
i
G G G =
Activity Coefficient
|
|
.
|
\
|
=
i
i
i i
f
f
ln T R G G
( ) f ln d T R dG
) x ln( T R G G
i i
id
i
=
Definition of fugacity:
Integration
|
|
.
|
\
|
=
i i
i
id
i i
f x
f
ln T R G G
|
|
.
|
\
|
i i
i
E
i
f x
f
ln
T R
G
The definition of activity coefficient
i
(Ideal solution)
( )
( )
i
n , P , T
i
E
ln
n
RT / G n
j
=
(
(
c
c
i i
E
ln x
T R
G
=

Models for Binary Mixtures Activity Coefficient:
Margules(1856 1920)
2 12 1 21
2 1
E
x A x A
RT x x
G
+ =

( )
( )
j
n , P , T
i
E
i
n
RT / G n
ln
(
(
c
c
=
| |
| |
2 21 12 21
2
1 2
1 12 21 12
2
2 1
x ) A A ( 2 A x ln
x ) A A ( 2 A x ln
+ =
+ =
van Laar
2
'
21 1
'
12
'
21
'
12
2 1
E
x A x A
A A
RT x x
G
+

=

( )
( )
j
n , P , T
i
E
i
n
RT / G n
ln
(
(
c
c
=
2
1
'
12
2
'
21 '
21 2
2
2
'
21
1
'
12 '
12 1
x A
x A
1 A ln
x A
x A
1 A ln
(
(
+ =
(
(
+ =
Models for Binary Mixtures Activity
Coefficient:
Wilson
|
.
|
\
|
= A
RT
a
exp
V
V
21
2
1
21
|
.
|
\
|
= A
RT
a
exp
V
V
12
1
2
12
i 21 12
2 1
x & T of t independen , ts tan cons a , a
2 & 1 liquid pure of me molar volu V , V
=
=
Renon: NonRandom Two-Liquid (NRTL)
Models for Multicomponent Mixtures
Activity Coefficient:
Wilson

A =
i j
ij j i
E
x ln x
RT
G

A
A
A =
j k
j
kj j
ki k
ij j i
x
x
x ln 1 ln
j) (i 1
j) (i
RT
a
exp
V
V
ij
ij
i
j
ij
= = A
=
|
|
.
|
\
|
= A
n compositio & T of t independen , ts tan cons a
i liquid pure of me molar volu V
ij
i
=
=
Models for
Multicomponent
Mixtures Activity
Coefficient:
UNIversal
QUAsi Chemical
(UNIQUAC)
(Abrams & Prausnitz)

UNIquac
Functional-
group
Activity
Coefficient
(UNIFAC)
(Aa Fredenslund,
Rl Jones & JM
Prausnitz)
Models for Multicomponent Mixtures Activity Coefficient:
R
i
C
i i
ln ln ln + =
UNIFAC: R
k
& Q
k

UNIFAC: R
k
& Q
k

Example
UNIFAC: a
mk


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