Non-ideal Gas and Liquid Mixtures:
Fugacity and Activity Coefficients
Schema for Non-ideal System VLE Description
Raoult’s Law as starting point
yiP= xi Pis
Retain the form and modify both sides by
corrective factors (CF) that capture non-ideality of each phase
(CFivap) yiP= (CFiliq) xi Pis
Derive both these corrective factors
CFivap,CFiliq from a common
indicator of Non-deal behaviour (FUGACITY)
Derive Fugacity using chemical potential
which describes phase equilibria, and develop expressions for
Fugacity from PVT data or EOS and composition (yi, and xi)
Correcting for gas mixture non-ideal
behaviour
Residual Property Relations:
For a closed system:
d (nG ) (nV )dP (nS )dT (1)
For an open multi-compnent system: G t nG f (T , P, n1 , n2 ...nN )
N
(nG ) (nG ) (nG )
d (nG ) dP dT dni (2)
P T ,n T P ,n i 1 ni
P ,T ,n i
j
Comparing (1) and (2), in general:
(nG )
d (nG ) (nV )dP (nS )dT dni (3)
i ni P ,T , n i
j
Thus: d (nG ) (nV )dP (nS )dT Gi dni (4)
i
(nG )
Note that by definition: i
ni T , P ,n j i
contd:
nG 1 nG
d d (nG ) 2
dT (5)
RT RT RT
But: G H TS (6)
Using (5) and (6) in (4):
nG nV nH Gi
d dP 2
dT dni (7)
RT RT RT i RT
For an ideal gas mixture:
nG ig nV ig nH ig Giig
d dP 2
dT dni (8)
RT RT RT i RT
Subtracting (8) from (7) gives:
nG R nV R nH R GiR
d dP 2
dT dni (9)
RT RT RT i RT
contd:
GiR can be used for correcting for non-ideal gas behaviour
For a pure component or closed (multicomponent)
system eqn (8) reduces to:
nG R nV R nH R
d dP 2
dT (10)
RT RT RT
Thus it follows:
V R (G R / RT )
(11)
RT P T , x
HR (G R / RT )
2
(12)
RT T P,x
Fugacity and Fugacity Coefficient
dGiig Vi ig dP RTdP / P RTd ln P (T const )
dGi (real fluid ) RTd ln f i ( f fugacity )
Fugacity " Fictitious pressure "
It is equal to the pressure of an ideal gas which
has the same chemical potential as the real gas.
Contd..
For exam ple, nitrogen gas ( N 2 ) at 0°C and
a pressure of P = 100 atm has a fugacity= 97 .03atm .
T his m eans that the chem ical potential o f real
nitrogen at a pressure of 100 atm is less than if
nitrogen w ere an ideal gas
T he value of the chem ical potential is that w hich
nitrogen as an ideal gas w ould have at a pressure
of 97.03 atm .
Fugacity and Fugacity Coefficient
ig ig
dGi Vi dP RTdP / P RTd ln P (T const )
dGi (real fluid ) RTd ln f i ( f fugacity )
Fugacity " Fictitious pressure "
It is equal to the pressure of an ideal gas which
has the same chemical potential as the real gas.
fi
dG dG ig
RTd ln RTd ln i (13)
dGiR
P
Fugacity Coefficient (i ): i fi / P
ig R
For an ideal gas : fi P Gi 0; i 1
R
On integrating eqn(12) : Gi RT ln i
V R (G R / RT )
By eqn.(10):
RT P T , x
R ig
R V V V
Or: d (G / RT ) dP dP
RT RT
1 ZRT RT dP
( Z 1) (14)
R
d (G / RT )
RT P P P
On integrating eqn(13)from 0 to P :
GiR GiR GiR P dP
RT P
RT P 0
RT
0
( Z 1)
P
P
dP
Thus : ln i (GiR / RT ) ( Z i 1) (15)
0
P
Eqn.(15) is suitable for volume explicit EOS
Fugacity Coefficient Calculation from EOS
For a pure gas ‘i’ obeying Virial EOS:
Bii P
Zi 1
RT
Bii P
Hence, ln i
RT
Computation of Gas Fugacity Coefficient (pure component)
by generalized Lee-Kessler Charts:
Pr
d Pr
O
ln ( Z 1)
Pr
Pr Pr
d Pr dP
ln ( Z O 1)
Z1 r
O
Pr O
Pr
ln ln 0 ln 1
Pr Pr
0 O d Pr 1 d Pr
1
ln ( Z 1)
ln Z
O
Pr Pr
O
ln 0 and ln 1 are given as function of Tr and Pr
see Tables13 to16 in Appendix VII of e-book
or Smith/Van Ness E.12-E.15
Fugacity Coefficients from Cubic EOS
An alternate form for ln suitable for
pressure explicit (cubic EOSs) is :
1 V
ln ( Z 1) PdV
RT V
For SRK EOS :
a Z B bP
ln Z 1 ln( Z B) ln ; B
bRT Z RT
For PR EOS :
a Z B (1 2) bP
ln Z 1 ln( Z B ) ln ;B
2 2bRT Z B (1 2) RT
Fugacity of a Pure Liquid:
dG = VidP = RTdlnfi
P-------
Psat -------
Ref.
point
Poynting factor
l sat
sat sat Vi ( P Pi )
f i (T , P ) i Pi exp[ ]
RT
Estimation of
sat
dG iV RTd ln f iV
dG iL RTd ln f i L
On integration between vapour and liquid states:
V
f
G iV G iL RT ln i L
fi
At equilibrium:G iV G iL 0 (see derivation for Antoine Eq.)
Thus: f iV f i L f i sat
For a pure species coexisting liqu id and vapor
phases are in equilibrium when they have the
same temperature , pressure , and fugacity .
Alternately :
fiV / Pi sat f i L / Pi sat fi sat / Pi sat
V L sat
i i i
sat
sat fi
where : i sat
Pi
Fugacity/Fugacity Coefficient of Species in Mixture:
i ig Giig RT ln yi
d i ig dGiig RTd ln yi
But , dGiig Vi ig dP RTd ln P
Thus : d i ig RTd ln P RTd ln yi RTd ln( yi P )
d i ig RTd ln pi
By extension : d i (real fluid ) dGi RTd ln fˆi
M R M M ig nM R nM nM ig
It follows that:
(nM R ) (nM ) (nM ig )
ni T , P , n j i ni T ,P ,n j i ni T , P , n j i
Or: M iR M i M iig
Thus : GiR Gi Giig i iig (16)
But:d iig = RTd ln pi ; and d i RTd ln fˆi
On integrating between the real and ideal states:
fˆi fˆi
ig
i i RT ln RT ln RT ln ˆi
pi yi P
ˆ
f
Where, ˆi species fugacity coefficient in a mixture i
yi P
Thus, using eqn. (15):
ˆ
f
GiR Gi Giig RT ln i RT ln ˆi (17)
yi P
On comparing eqns.(9) and (17):
ˆ ( nG R
/ RT )
ln i (18)
ni T , P ,n j i
Although most commonly applied to gases,
the fugacity coefficient in eqn. 15 may also
be used for liquids, in which case the mole
fraction yi is replaced by xi .
Contd…
R
G
Since ln ˆi is a partial of , it follows that:
RT
GR
yi ln ˆi
RT i
Further, by Gibbs-Duhem relation for partial
molar properties:
ˆ 0 (const. T and P)
i i
x
i
d ln
Species fugacity coefficients by EOS:
R
ˆ ( nG / RT
ln i
ni P ,T , n j i
where, G R G G ig
R dP
P
Also, (G / RT ) ( Z 1)
0 P
Thus, using eqn. (16). the general expression is:
ˆ
P dP P dP
ln i (nZ n)
( Z i 1)
0 P 0 P
Expression for Z varies with EOS
Contd…
Or, alternately:
V
P RT
RT ln ˆi dV RT ln Z
V n V
i T ,V , n j i
Species Fugacity Expressions by Virial EOS
BP
Z=1+ ; where, Bmixture yi y j Bij
RT i j
ˆ P dP
Using ln i (nZ n) it may be shown that
0 P
for a binary gas mixture obeying virial EOS:
ˆ P 2 ˆ P
ln 1 ( B11 y2 12 ); ln 2 ( B22 y1212 )
RT RT
12 2 B12 B11 B22
Expressions for fugacity coefficient for ‘kth species in a multi-
component mixture:
For Virial EOS :
P 1
ln k [ Bkk y y (2
i j ik ij )]
RT 2 i j
ik 2 Bik Bii Bkk ; ij 2 Bij Bii B jj ; ii jj kk 0
For SRK EOS :
bk am bk ak Z Bm
ln k ( Z 1) ln( Z Bm ) ( 2 ln( ); m mixture
bm bm RT bm am Z
For PR EOS :
bk am bk ak Z Bm (1 2)
ln k ( Z 1) ln( Z Bm ) 2 ln
bm 2 2bm RT bm am Z Bm (1 2)
bm P
For both cubic EOSs above, Bm
RT
Mixing Rules for Cubic EOS
Mixing rules for binary mixtures:
am yi y j aii a jj (1 kij )
i j
kij binary interaction parameter ;where kii k jj 0
bm yi bi
i
m yii
i
For a binary (assuming all k ij 0) :
am y12 a11 2 y1 y2 (a11a22 )1/ 2 y22 a22
bm y1b1 y2b2
m y11 y22
Ideal Liquid Solutions:
For a real liquid mixture: i i (T ) RT ln fˆi
For an ideal liquid mixture (by eqn. 11.42):
iid Giid i (T ) RT ln fˆi id
id id
But in general: i Gi Gi RT ln xi
Also: Gi i (T ) RT ln fi
Thus: iid Giid i (T ) RT ln xi fi
ˆ id
It follows: i xi fi
f Lewis Randall Rule
For real xixture: GE G Gid GiE Gi Giid
Molar Excess Property Relations
M E M M id
Thus: H E H H id ; S E S S id ; G E G G id
Further: H E H x H i i H mix
i
E
S S
x S
i
i i R i
xi ln xi
S mix R x ln x
i
i i
E
G G
x G RT
i
i i
i
xi ln xi
Gmix RT x ln x
i
i i
Excess Property Relations
nG nV nH Gi
d dP 2
dT dni (19)
RT RT RT i RT
For an ideal solution:
id
nG id nV id nH id
Gi
d dP 2
dT dni (20)
RT RT RT i RT
Subtracting (8) from (7) gives:
E
nG E nV E nH E
Gi
d dP 2
dT dni (21)
RT RT RT i RT
Contd…
For a pure component or closed (multicomponent)
system eqn (21) reduces to:
nG E nV E nH E
d dP 2
dT (22)
RT RT RT
Thus it follows:
V E (G E / RT )
(23)
RT P T , x
HE (G E / RT )
2
(24)
RT T P, x
GiE can be used for correcting for non-ideal
liquid solution behaviour
Molar Excess Gibbs Energy and the Activity Coefficient (for
liquid mixtures):
G iE Gi G iid RT ln fˆi RT ln fˆi id RT ln( fˆi / fˆi id ); fˆi id xi f i
id E fˆi fˆ
Gi G i G i RT ln ( Activity coefficient )
i
i
xi f i xf i i
E (nG E / RT )
Thus, G RT ln i
i ln i (25)
ni T , P ,n
j 1
i.e., G E / RT xi ln i
i
By Gibbs Duhem relation : xi d ln i 0 (const T & P)
lim i i & lim i 1
xi 0 xi 1
Obtain suitable models for GE/RT and hence get γi
Effect of T & P on Excess Gibbs free energy
For an equimolar mixture of benzene and cyclohexane
at 298K and 1 bar:
V E 0.65cm3 / mol
H E 800cm3 / mol
Thus it follows:
(G E / RT ) VE 0.65 5 1
2.62 x10 bar
P T , x RT 83.14 x 298
(G E / RT ) HE 800 3 1
2
2
1.08 x10 K
T P, x RT 83.14 x 298
G E ( for T 1K ) G E ( for P 40bar )
Activity Coefficients from Low pressure VLE Data
• Carry out VLE experiments at low pressure
• Measure vapour phase compositions at
various starting and liquid phase mole fractions
• Use modified Raoult’s Law for calculating activity
coefficients as function of liquid phase
composition
• Fit activity coefficient data to appropriate activity
coefficient model for GE/RT
• Note that G E / RT xi ln i
The activity coefficient model is derived next (see following slide)
Obtaining the Activity Coefficient Model
It follows : G E / x1 x2 RT A21 x1 A12 x2
or G E / RT x1 x2 ( A21 x1 A12 x2 )
(nG E / RT )
Using ln i
ni T , P ,n j 1
Margules Equations:
ln 1 x22 [ A21 2( A21 A12 ) x1 ]
ln 2 x12 [ A12 2( A12 A21 ) x2 ]
Also : ln 1 ( x1 0) A21 & ln 2 ( x2 0) A12
Other Activity Coefficient Models
Applicability of Activity Coefficient Models
System Type Models
Species similar is size and shape One-constant Margules
Moderately non-ideal mixtures Two-constant Margules, Van Laar,
Regular Solution
Strongly non-ideal mixtures Wilson, NRTL, UNIQUAC
(Alcohols+Hydrocarbons)
Solutions with miscibility gap NRTL, UNIQUAC
Regular Solution (RS) Model (for moderately non-
ideal solutions)
2 2 2
G E / RT x1V1 x2V2 1 2 1 2 ln 1 V1 22 1 2 ; ln 2 V212 1 2
where, i = volume fraction =
xiVi
Vm
Vi = molar volume of pure ith species, Vm = ΣxiVi , and
δi = solubility parameter
i
U H
i
vap
i
vap
RT
Vi Vi
For Multi-component Solutions
2 x jV j
R T ln i Vi 1 ; ; x V
j j j
j j j
j
Method of Group Contribution
UNIQUAC (Universal Quasi-chemical) based
Activity Coefficients:
ln i ln iC (combinatorial ) ln iR ( residual )
END
