TKM 406

Termodinamika Teknik Kimia II

Nonideal Behavior

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)
30o
C

P-x-y

1 atm

t-x-y diagram

Effect of Nonideality:
Chloroform(1)/Tetrahydrofuran(2)
30o
C

P-x-y

1 atm

t-x-y diagram

Effect of Nonideality:
Furan(1)/Carbontetrachloride(2)
30o
C

P-x-y

1 atm

t-x-y diagram

Effect of Nonideality:
Ethanol(1)/Toluene(2)
65o
C

P-x-y

1 atm

t-x-y diagram

Effect of Nonideality:
x y Diagram at Constant P = 1 atm

a. Tetrahydrofuran(1)/Carbon-tetrachloride

Chloroform(1)/Tetrahydrofuran(2

c. Furan(1)/Carbontetrachloride(2)
d. Ethanol(1)/Toluene(2)

Partial Molar Properties

Pure-species
Properties:
Solution
Properties:

M i U i , H i , Si , Vi , or G i , etc.

x i Mi
M x i Mi
M

NOT
:
M i U i , H i , Si , Vi , or G i , etc.

Partial
Properties:
.are
properties of component i in the state of
mixtures, which, in general different from
that in the state of pure species

What physical interpretation can be

given for, viz. partial molar volume ?

Methanol Water Mixture, An Example

For pure species at 25oC:
Methanol (1) : V1 = 40.727 cm3/mol
Water (2) : V2 = 18.068 cm3/mol

x i Mi

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
cm3
Volume of water
: 7 moles x 18.068 = 126.476
cm3
Wrong
correct
answer
is
Thus, the total The
volume
: 122.181
+ 126.476=
answer!
240.251 cm3
248.657 cm3
Thus there is 240.251 248.657 = -8.406 cm3 deviation
from expected value

More on Partial Molar

Properties

nM M (T, P, n1 , n 2 , n 3 ,..........)
nM

d nM

nM

n
1

nM

dT

P,n

T , P, n 2 , n 3

nM
dn1

n
2

,...

nM
nM
d nM

dT

dP

T P,n
P T,n

NOT

x i Mi

dP
T,n

dn 2 .....
T ,P, n1 , n 3 ,...

nM
Mi

n
i

T , P,n j

nM
dn i .

n i T,P,n j

x i Mi

Chemical Potential as Partial Molar Property

Criteria for Vapor - Liquid Equilibria

Tg T
g

P P

i g i

The chemical potential of

i-th component is defined
as:

(nG )
i

n i T,P,n j

Chemical Potential as Partial Molar

Property
If we set M =
G:

nG
nG
d nG
dT
dP

T P,n
P T,n

nG
dn i .

n i T,P,n j
nG

n
i

Gi

T , P, n j

(nG )

n
i

The definition of chemical

potential:
Thus
:

i Gi

T ,P, n j

Evaluation of Partial Molar Properties

Methanol Water Mixture Example
M

x i Mi
M1 M x 2

M
x1

M 2 M x1

M
x1

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 oC and 101.3 kPa.

In 96% ethanol

In vodka

V H 2O , L/kg

0.816

0.953

V EtOH , L/kg

1.273

1.243

The specific volume of water at 25oC 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?

Fugacity, f
dG S dT V dP
At constant
T
Ideal gas :

dG ig R T d ln P

Real gas

dG R T d ln f

dG

R T d ln

Residual Gibbs
energy :

G R G G ig

Fugacity
coefficient :

f
P

GR
ln
R T

Residual
RProperty
V V V ig
V R ( Z 1)

RT
P

Evaluation of Pure Component

Fugacity, fi
At constant
T:
Real gas

dG i R Vi R dP

Vi R ( Zi 1)

RT
P

dG i R

RT

Vi R
dP
RT

GiR
dP
( Zi 1)
RT
P

GiR
ln i
R T

Pure Component Fugacity

Coefficient:
The fugacity :f i i P

ln i ( Zi 1)
0

dP
P

Evaluation of Pure Component

Fugacity, fi
From the following compressibility data for
hydrogen at 0oC, determine the fugacity of
hydrogen at 950 atm

P,1a
t00m1.0
Z69 P,6a
t00m1.4
Z31
2
0
0
1
.
1
3
8
7
0
0
1
.
5
0
4
3
0
0
1
.
2
0
9
8
0
0
1
.
5
7
7
4
0
0
1
.
2
8
3
9
0
0
1
.
6
4
9
500 1.356 1000 1.720

Evaluation of Pure Component

Fugacity, fi
From the following compressibility data for isobutane,
determine the fugacity of butane at various
temperature and pressure

Evaluation of Pure Component

Fugacity, fi from Equation of State
Virial : PVi
Bi P
Zi 1
RT
RT
B Pc
B 0 B1
R Tc
0

B 0.083

B1 0.139

0.422
Tr1.6

0.172
Tr 4.2

Bi P
ln i
RT

Pr 0
ln i
B B1
Tr
Tr

T
Tc

Pr

P
Pc

Critical Constants & Accentric Factors:

Paraffins

Critical Constants & Accentric Factors:

Olefin & Miscellaneous Organics

Critical Constants & Accentric Factors:

Miscellaneous Organic Compounds

Critical Constants & Accentric Factors:

Elementary Gases

Critical Constants & Accentric Factors:

Miscellaneous Inorganic Compounds

Evaluation of Pure Component Fugacity,

fi 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 50oC and 25 kPa.
The required data:

Evaluation of Pure Component

Fugacity, fi from Equation of State
RedlichKwong:

0.42748 R 2 Tci 2.5

ai
Pci
h

bi P
ZR T

ai
1
h
Z

1 h b i R T1.5 1 h

0.08664 R Tci
Pci

bi

to be solved

simultaneously

ln Z 1 ln (1 h ) Z

1.5

bR T

Evaluation of Pure Component Fugacity,

fi from Redlich-Kwong Equation of State
Using Redlich - Kwong equation of state,
calculate the fugacity and fugacity coefficient of:
1. Pure methyl-ethyl-ketone
2. Pure toluene
at 50oC and 25 kPa.
The required data:

Evaluation of Pure Component Fugacity, fi :

Pitzers Generalized Correlation

i i
i f Pr , Tr
0

P
Pr
Pc

i1

i1 f Pr , Tr

T
Tr
Tc

TPc

Evaluation
of Pure
Component
Fugacity, fi :
Pitzers
Generalized
Correlation

Tr

T
Tc

Evaluation
of Pure
Component
Fugacity, fi :
Pitzers
Generalized
Correlation

i 0

Pr

P
Pc

TPc

Evaluation
of Pure
Component
Fugacity, fi :
Pitzers
Generalized
Correlation

Tr

i1

T
Tc

Evaluation
of Pure
Component
Fugacity, fi :
Pitzers
Generalized
Correlation

Pr

P
Pc

Evaluation of Pure Component

Fugacity, fi : Pitzer Correlation
Using Pitzer Correlation,
calculate the fugacity and fugacity coefficient of:
1. Pure methyl-ethyl-ketone
2. Pure toluene
at 50oC and 25 kPa.
The required data:

Evaluation of Liquid
Pure Component Fugacity, fi
fi

1
ln

sat
R T
fi

Vi dP

Pi sat

Since Vl is a weak function of P at temperatures

well below Tc:

sat

Vi P Pi

sat
sat
f i i Pi exp
R T

Poynting
Fugasity of saturated vapor, factor
calculated exactly as calculating gas

Estimation of Liquid Density

Rackett Equation: V sat V Z (1Tr )0.2857
c
c

Examples of
Evaluation of Liquid Pure Component
Fugacity, fi
11.5
Estimate the fugacity of liquid acetone at
110oC and 275 bar.
At 110oC the vapor pressure of acetone is
4.36 bar and the molar volume of
saturated-liquid acetone is 73 cm3.mol-1
11.6
Estimate the fugacity of liquid n-butane at
120oC and 34 bar.
At 120oC the vapor pressure of n-butane is
22.38 bar and the molar volume of
saturated-liquid n-butane is 137 cm3.mol-1

Examples of
Evaluation of Liquid Pure Component
Fugacity, fi
11.10
The normal boiling point of nbutane is 0.5oC.
Estimate the fugacity of liquid nbutane at this temperature and
11.11
200 bar.
The normal boiling point of 1pentene is 30.0oC.
Estimate the fugacity of liquid 1pentene at this temperature and
11.12
350 bar.
The normal boiling point of isobutane
is -11.8oC.
Estimate the fugacity of liquid

Examples of
Evaluation of Gas & Liquid Pure Component Fugacity, fi

11.13
Prepare plots of f vs P and vs P for isopropanol
at 200oC for the pressure range from 0 to 50
bar. For the vapor phase, values of Z are given
by:
Z 1 9.86 10 3 P 11.41 10 5 P 2
Where P is in bars. The vapor pressures of
isopropanol at 200oC is 31.92 bar, and the
liquid-phase isothermal compressibility at
200oC is 0.3.10-3 bar-1, independent of P.
Hint:
1 V

V P

Examples of
Evaluation of Gas & Liquid Pure Component Fugacity, fi

11.14
Prepare plots of f vs P and vs P for 1,3butadiene at 40oC for the pressure range from
0 to 10 bar. At 40oC 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 1,3butadiene at 40oC is 90.45 cm3.mol-1

Fugacity of Steam and Water,

Using Steam Table
Up to Pisat, i.e. gas phase water
(steam): f 1 H H *
ln

P*

(Si Si )

P* : lowest value of P in
steam table
At P >= Pisat, i.e. liquid phase
water:
V P P sat

sat
sat
i
f i i Pi exp i
R T

Example of Steam and Water Fugacity

Calculation Using Steam Table
11.7
From data in the steam tables, determine a good
estimate for f/fsat of liquid water at 100oC and 100
bar, where fsat is the fugacity of saturated liquid
at 100oC.
11.8
Steam at 13000 kPa and 380oC 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 700oF undergoes an
isothermal change of state to a pressure of 40
psia. Determine the ratio of the fugacity in the

Fugacity of Mixtures

Virial
:B P
Are formulated exactly as calculation for pure
ln i

component, but we use Mixing Rules to

obtain the parameters
B

yi y j Bij
i

Bii Bi B of pure component i

For binary mixtures, i = 1,2 and j

= 1,2
B y12 B11 2 y1 y 2 B12 y 2 2 B 22
Bij B ji

Z cij

R Tcij
Pcij

Z ci Z cj
2

B0 ij B1

1
3

ij

1
3

Vcij

V V
ci
cj

Tcij Tci Tcj

Pcij

i j

Z cij R Tcij
Vcij

(1 k ij )

RT

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 50oC and 25 kPa
The required data are as follows:

Fugacity of Components in
Mixture

f i
i
yi P
GiR
ln i
R T

Thus:

Gi R
ln i
R T

ln( i ) is partial molar

property of

n ln

n
i

T, P, n j

ln i

Virial, binary
mixtures:

12 2 B12 B11 B12

ln(i )

P
(B11 y 2 2 12 )
RT
P
ln 2
( B 22 y12 12 )
RT
ln 1

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 50oC and 25 kPa.
Set all kij = 0
The required data are as follows:

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 200oC and 20 bar.
Set all kij = 0

More on Virial Eqn:

Fugacity of Ternary and Multicomponent
Mixtures

Mixing
B Rules
yi :y j Bij
i

For ternary mixtures, i = 1,2,3

and j = 1,2,3
Bii Bi B of pure component i

Bij B ji

P
1

B kk
ln k
R T
2
i

R Tcij
Pcij

B 0 ij B1

yi y (2 ik i)

ik 2 B ik Bii B kk
i 2 B i Bii B

ii 0
kk 0
ki ik

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 40oC and 20 bar with
the composition of 17% methane and 35% ethane
Set all kij = 0

Evaluation of Mixture Fugacity, f,

from Equation of State
RedlichKwong:

yi y j a ij
i

bP
ZR T

1
a
h
Z

1 h b R T1.5 1 h

yi bi
i

to be solved

simultaneously

ln Z 1 ln (1 h ) Z

1.5

bR T

Evaluation of Mixture Fugacity, f , using

Redlich-Kwong Equation of State
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 50oC and 25 kPa

The required data:

Evaluation of Component Fugacity in

Mixture Fugacity, f, from Equation of State
RedlichKwong:

1.5

bR T

b1
b1
a

ln 1 ( Z 1) ln Z (1 h )

1
.
5

b
b
b RT

ln 2

ln Z 1 ln (1 h ) Z

b2
b
a
( Z 1) ln Z (1 h )
2
b
b RT 1.5 b

x k a1k

ln(1 h )

x k a 2k

ln(1 h )

Evaluation of Mixture Fugacity, f , using

Redlich-Kwong Equation of State
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 50oC
and 25 kPa

The required data:

UTS 1

Excess Gibbs Energy

M i U i , H i , Si , Vi , or G i , etc.
Pure-species
Properties:
M x i Mi
Solution
Properties:
M i U i , H i , Si , Vi , or G i , etc.
Partial
Properties:
R
ig
G GG
Residual
R
ig
Property
Partial
Property of the Excess
Gi Gi Gi
Property

G E G G id
Excess
Property
E
id
Partial
Property of the Excess
Gi Gi Gi
Property

Excess Gibbs Energy

M i U i , H i , Si , Vi , or G i , etc.
Pure-species
Properties:
M x i Mi
Solution
Properties:
M i U i , H i , Si , Vi , or G i , etc.
Partial
Properties:
R
ig
G GG
Residual
R
ig
Property
Partial
Property of the Excess
Gi Gi Gi
Property

G E G G id
Excess
Property
E
id
Partial
Property of the Excess
Gi Gi Gi
Property

Definition of
fugacity:
dG R T d ln f

Activity Coefficient
Integrati
fi on

G i G i R T ln

fi

G i id G i R T ln( x i )

G i G i id R T ln

n G E / RT

n i

fi
x i fi

(Ideal
solution)

fi
Gi E
ln
x i fi
R T

The definition of activity

coefficient i

ln i
T , P, n j

GE

R T

x i ln i

Models for Binary Mixtures Activity Coefficient:

Margules(1856 1920)
GE
A 21 x1 A12 x 2
x1 x 2 RT

n G E / RT
ln i
n i

ln 1 x 2 2 A12 2 (A 21 A12 ) x1
ln 2 x12 A 21 2 (A12 A 21 ) x 2

T , P, n j

Models for Binary Mixtures Activity Coefficient:

van Laar
A12 ' A 21'
GE

x1 x 2 RT A12 ' x1 A 21' x 2

n G E / RT
ln i
n i

'
ln 1 A12
1

ln 2 A '21 1

'
A12
x1

'
A 21 x 2

A '21 x 2
'
A12
x1

T ,P,n j

Models for Binary Mixtures Activity Coefficient:

Wilson

V2
a12
12
exp

V1
RT
21

V1
a
exp 21
V2
RT

V1 , V2 molar volume of pure liquid 1 & 2

a12 , a 21 cons tan ts, independent of T & x i

Models for Binary Mixtures Activity

Coefficient:

Renon: NonRandom Two-Liquid (NRTL)

Models for Multicomponent Mixtures

Activity Coefficient:

Wilson
GE

RT

x i ln x j ij
i

ln i 1 ln

x j ij

x k ki

x j kj
k

a ij

ij
exp

Vi
RT
ij 1
Vj

(i j)
(i j)

Vi molar volume of pure liquid i

a ij cons tan ts, independent of T & composition

Models for
Multicomponent
Mixtures Activity
Coefficient:

UNIversal
QUAsi
Chemical
(UNIQUAC)
(Abrams & Prausnitz)

Models for Multicomponent Mixtures

Activity Coefficient:

ln i ln i C ln i R

UNIquac
Functional
group
Activity
Coefficient
(UNIFAC)
(Aa Fredenslund,
Rl Jones & JM
Prausnitz)

Models for Multicomponent Mixtures

Activity
UNIFAC: Rk &Coefficient:
Qk

Models for Multicomponent Mixtures

Activity Coefficient:

UNIFAC: Rk & Qk
Example

Models for Multicomponent Mixtures

Activity Coefficient:
UNIFAC: amk