SOLUTION

THERMODYNAMICS: THEORY
FUGACITY AND FUGACITY COEFFICIENT: SPECIES IN SOLUTION
GENERALIZED CORRELATIONS FOR THE FUGACITY COEFFICIENT
THE IDEAL SOLUTION MODEL
FUGACITY AND FUGACITY
COEFFICIENT: SPECIES IN SOLUTION
The definition of a species in solution is parallel to the definition of the
pure-species fugacity.
For species i in a mixture of real gases or in a solution of liquids,

i i T RT ln f i (11.46)
^
where f i is the fugacity of species i in solution, replacing the partial
pressure yiP in eq. (11.29) for ideal gas.
For species in solution, the phase equilibrium criteria is:
f f ... f
i i i i 1, 2, ...,N (11.47)

Multiple phases at the same T and P are in equilibrium when

the fugacity of each constituent species is the same in all
phases.
For the specific case of multicomponent vapor/liquid equilibrium, eq.
(11.47) becomes:

f i
f il i 1, 2, ...,N (11.48)
2
 3

The definition of a residual property is

M R M M ig (6.41)
where M is the molar (or unit mass) value of a thermodynamic
property and Mig is the value that the property would have for an
ideal gas of the same composition at the same T and P.
The defining equation for a partial residual property M iR follows from
this equation. Multiplied by n mol of mixture, it becomes
nM R nM nM ig
Differentiation with respect to ni at constant T, P and nj gives

nM R nM


nM ig



ni ni P ,T ,n j ni
P ,T ,n j P ,T ,n j

Reference to eq. (11.7) shows that each term has the form of a
partial molar property. Thus,
M iR M i M i ig (11.49)

3
 Written for the residual Gibbs energy, eq. (11.49) becomes

GiR Gi Giig (11.50)

an equation which defines the partial residual Gibbs energy.
Subtracting eq. (11.29) from eq. (11.46), both written for the same T
and P, yields i i T RT ln f i (11.46)

f
i RT ln i
ig
i

iig Giig i T RT ln yi P (11.29)
yi P
This result combined with eq. (11.50) and the identity i Gi gives
GiR RT ln i (11.51)

where by definition,
f

i i (11.52)
yi P

The dimensionless ratio i is called the fugacity coefficient of

species i in solution.
4
 Although most commonly applied to gases, the fugacity coefficient
may also be used for liquids, in this case mole fraction yi is
replaced by xi.
Because eq. (11.29) for an ideal gas is a special case of eq. (11.46),
then
f ig y P (11.53)
i i

Thus the fugacity of species i in an ideal gas mixture is equal to its

partial pressure. Moreover, iig 1 , and for an ideal gas GiR 0

f ig
yP
i
ig i
i 1 GiR RT ln i ig RT ln 1 0
yi P yi P

5
 6

Fugacity Coefficients from the Virial

Equation of State
Values of i for species i in solution are readily found from equations
of state.
The simplest form of the virial equation provides a useful example.
Written for a gas mixture it is exactly the same as for a pure species:
BP
Z 1 (3.38)
RT
The mixture second virial coefficient B is a function of temperature
and composition.
B yi y j Bij (11.61)
i j

where y represents mole fractions in a gas mixture, the indices i and j

identify species, and both run over all species present in the mixture.
The virial coefficient Bij characterizes a bimolecular interaction
between molecule i and molecule j, and therefore Bij = Bji.
The summations account for all possible bimolecular interactions. 6
 7

For a binary mixture i = 1, 2 and j = 1, 2; the expansion of eq. (11.61)

then gives
B y1 y1 B11 y1 y2 B12 y2 y1 B21 y2 y2 B22
or
B y12 B11 2y1 y2 B12 y22 B22 (11.62)

B11 and B22 are pure species virial coefficient and B12 is a mixture
property, known as a cross coefficient. Both are function of
temperature only.
Expressions such as eqs. (11.61) and (11.62) relate mixture
coefficients to pure species and cross coefficients. They are called
mixing rules.

7
 Eq. (11.62) allows derivation of expressions for ln 1 and ln2
for a binary gas mixture that obeys eq. (3.38). For n mol of gas mixture,
nBP
nZ n
RT
Differentiation with respect to n1 gives

nZ n P nB

n1 n
P ,T ,n2 1 P ,T ,n2 RT n1 T ,n
2

Because nZ ni Z i and n ni 1 , this reduces to

P nB
Z1 1
RT n1 T ,n
2

From eq. (11.60) yields

1 P nB P nB dP
ln 1 Z 1
P
dP ln i i (11.60)
RT 0
n1 T ,n RT n1 T ,n
0 P
2 2

where the integration is elementary, because B is not function of

pressure. All that remains is evaluation of the derivative.
8
 Eq. (11.62) for the second virial coefficient may be written:
B y1 1 y2 B11 2y1 y2 B12 y2 1 y1 B22
y1 B11 y1 y2 B11 2y1 y2 B12 y2 B22 y1 y2 B22
or
B y1 B11 y2 B22 y1 y212 with 12 2B12 B11 B22
Multiplying by n and substituting yi = ni/n gives,
nB ny1 B11 ny2 B22 ny1 y212 or n1n2
nB n1 B11 n2 B22 12
n
By differentiation,
nB 1 n1 1 n1
B11 n
2 2 12
B11 1 n2 12
n1 T ,n2 n n n n
B11 1 y1 y2 12 B11 y22 12
Therefore,
P
ln 1
RT

B11 y22 12 (11.63a)

Similarly, P
ln 2
RT

B22 y12 12 (11.63b) 9
 10

Eqs. (11.63) are readily extended for application to multicomponent

gas mixtures; the general equation is

P 1
lnk B
kk
RT
i j ik ij
2 i j
y y 2 (11.64)

where i and j run over all species, and

ik 2 Bik Bii Bkk ij 2 Bij Bii Bij
with
ii 0, kk 0, etc., and ki ik , etc.,

10
 11

EXAMPLE 11.7
Determine the fugacity coefficients as given by eqs. (11.63) for
nitrogen and methane in a N2(1)/CH4(2) mixture at 200K and 30
bar if the mixture contains 40 mole % N2. Experimental virial
coefficient data are as follows:
B11 35.2 B22 105.0 B12 59.8 cm 3 mol -1
R=8.314 m3 Pa/mol.K = 83.14 cm3 bar/mol.K
Solution:
By definition,
12 2B12 B11 B22 2 59.8 35.2 105.0 20.6 cm3 mol-1
Substitution of numerical values in eqs.(11.63) yields
30 35.2 0.6 2 20.6 0.0501
ln 1
83.14 200
30 105.0 0.4 2 20.6 0.1835
ln 2
83.14 200
Thus,
1 0.9511 and 2 0.8324 11
Note that the second virial coefficient of the mixture as given by eq.
(11.62) is
B y12 B11 2y1 y2 B12 y22 B22
0.4 35.2 2 0.4 0.6 59.8 0.6 105.0
2 2

72.14 cm 3 mol -1

Substitution in eq. (3.38) yields a mixture compressibility factor,

BP
Z 1
RT

1
72.14 30 0.870
83.14 200

12
 13

GENERALIZED CORRELATIONS
FOR THE FUGACITY COEFFICIENT
Eq. (11.35) is put into generalized form by substitution of the
relations,
P Pc Pr dP Pc dPr

P dP
ln i Zi 1 const T (11.35)
0 P
Hence,
Pr dPr
ln i Z i 1 (11.65)
0 Pr
where the integration is at constant Tr. Substitution for Zi by Eq.
(3.57) yields
Zi Z 0 Z 1 (3.57)

dPr dP
Z 0 1
Pr Pr
ln Z 1 r
0 Pr 0 Pr
where for simplicity i is omitted.
13
 This equation may be written in alternative form:
ln ln 0 ln 1 (11.66)
where
Z 1 dP dPr
Pr Pr
ln
0 0 r
and ln Z 1
1
0 Pr 0 Pr
The integrals in these equations may be evaluated numerically or
graphically for various values of Tr and Pr from data for Z0 and Z1
given in Table E.1- E.4 (Appendix E).
Another method, and the one adopted by Lee and Kesler to extend
their correlation to fugacity coefficients, is based on an equation of
state.
Eq. (11.66) may also be written,

0 1

(11.67)
Table E.13 E.16 present values for these quantities as derived from
the Lee/Kesler correlation as function of Tr and Pr.

14
EXAMPLE 11.8
Estimate from eq. (11.67) a value for the fugacity of 1-butene vapor
at 200oC (473.15K) and 70 bar.

Solution:
From Table B.1,
Tc = 420 K Pc = 40.43 bar = 0.191
Tr = T/Tc = 473.15/420 = 1.127
Pr = P/Pc = 70/40.43 = 1.731
By interpolation in Table E.15 and E.16 at these conditions,
0 = 0.627 and 1 = 1.096
Equation (11.67) then gives
= (0.627)(1.096)0.191 = 0.638
and f = P = (0.638)(70) = 44.7 bar

15
 16
A useful generalized correlation for ln results when the simplest
form of the virial equation is valid.
Eqs. (3.61) and (3.63) combine to give

P Z 1
BP Pr
1 B
Z 1 r B 0 B1 RT Tr
(3.61)
Tr
B0 B1
B (3.63)
Substitution in eq. (11.65) and integration yield
P Pr 0 1

Tr

ln r B0 B1 or exp
T

B B (11.68)
r
where
0.422 0.172
B0 0.083 and B1 0.139
Tr1.6 Tr4.2
This equation provides reliable values of for any nonpolar or
slightly polar gas when applied at conditions where Z is
approximately linear in pressure. E.g. H2, N2, O2, CO2, CH4, C2H4
Figure 3.14 serves as a guide to its suitability.

16
Extension to Mixtures
The general expression for calculation of ln k from the second
virial coefficient data is given by eq. (11.64).

P 1
lnk B
kk
RT
i j ik ij
2 i j
y y 2 (11.64)

Values of the pure species virial coefficients Bkk, Bii, etc., are found
from the generalized correlation represented by eqs. (3.62), (3.63),
(3.65), and (3.66).
BPc
B (3.62)
RTc
B0 B1
B (3.63)
0.422
B0 0.083 (3.65)
Tr1.6
0.172 (3.66)
B1 0.139
Tr4.2 17
 The cross coefficients Bik, Bij, etc., are found from an extension of the
same correlation.
For this purpose, eq. (3.63) is rewritten in the more general form
B B0 B1
ij ij
(11.69a)
where
Bij Pcij

B (11.69b)
ij
RTcij
and B0 and B1 are the same functions of Tr as given by eqs. (3.65) and
(3.66).
Thus,
Bij Pcij
B 0 ij B 1
RTcij
RTcij
Bij
Pcij
B 0
ij B 1

18
 The combining rules for calculation of ij, Tcij, and Pcij are
i j
ij 11.70
2
Tcij TciTcj 1 k 11.71
1/2
ij

Z cij RTcij
Pcij 11.72
Vcij
Z ci Z cj
Z cij 11.73
2
3
Vci1/ 3 Vcj1/ 3
Vcij
11.74
2
In eq. (11.71), kij is an empirical interaction parameter specific to an
i-j molecular pair.
When i=j and for chemically similar species, kij = 0. Otherwise, it is
a small positive number evaluated from minimal PVT data or in the
absence of data set equal to zero.
When i=j, all equations reduce to the appropriate values for a pure
species. 19
 When ij, these equations define a set of interaction parameters
having no physical significance.
Reduced temperature is given for each ij pair by Trij T/Tcij.
For a mixture, values of Bij from eq. (11.69b) substituted into eq.
(11.61) yield the mixture second virial coefficient B, and substituted
into eq. (11.64) [eq. (11.63) for a binary] yield values of ln i .
Bij Pcij

Bij
RTcij (11.69b)

B yi y j Bij (11.61)
i j

P 1
lnk B
kk
RT
i j ik ij
2 i j
y y 2 (11.64)

P
ln 1
RT

B11 y22 12 (11.63a)

P
ln 2
RT

B22 y12 12 (11.63b)
20
 21

EXAMPLE 11.9

Estimate 1 and 2 by eqs. (11.63) for an equimolar mixture of

methyl ethyl ketone(1)/toluene(2) at 50oC (323.15 K) and 25 kPa.
Set all kij = 0.

Solution:
From Table B.1, the required data are as follows:

ij Tcij/K Pcij/bar Vcij/cm3 mol-1 Zcij ij

11 535.5 41.50 267 0.249 0.323
22 591.8 41.06 316 0.264 0.262
12 562.9 41.30 291 0.257 0.293
Values in the last row have been calculated by eqs. (11.70)
(11.74).

21
 22

The values of Trij, B0, B1 and Bij calculated for each ij pair by eqs.
(3.65), (3.66) and (11.69), are as follows:

ij Trij B0 B1 Bij/cm3 mol-1

11 0.603 -0.865 -1.300 -1378.6
22 0.546 -1.028 -2.045 -1873.9
12 0.574 -0.943 -1.632 -1610.4

T B0 B1
B (11.69a)
Trij ij ij
Tcij
Bij Pcij
0.422
B (11.69b)
B 0.083 1.6
0
3.65 ij
RTcij
Tr
0.172
B1 0.139 3.66 Bij Pcij
B 0 ij B 1
Tr4.2 RTcij
RTcij
R = 83.14 cm3 bar mol-1 K-1 Bij
Pcij
B 0
ij B 1
22
 Calculating 12 according to its definition gives:

1212 2B1212 B1111 B22

22 2 1610.4 1378.6 1873.9 31.7 cm33
mol -1
-1

Eq.(11.63) then yield:

P 25
ln 1
RT
B11 y2 12
2

8314 323.15
1378.6 0.5
2
31.7 0.0128

P 25
ln 2
RT
B22 y12 12 1873.9 0.5 2 31.7 0.0174
8314 323.15

R = 8314 cm3 kPa mol-1 K-1

Thus,
1 0.987 and 2 0.983

23
 24

THE IDEAL SOLUTION MODEL

The chemical potential for ideal gas mixture model is given by eq.
(11.24)

G Giig T , P RT ln yi
ig
i i
ig
(11.24)

For an ideal solution,

(11.75)
G Gi T , P RT ln xi
id
i i
id

Partial volume, Eq (11.18)

Giid Gi
Vi id

P T , x P T
By eq. (11.4), Gi / P T Vi ; thus,
Viid Vi (11.76)

24
 As a result of eq. (11.19),
Giid Gi
S
i
id
T R ln xi
T P ,x P
By eq. (11.5),
Siid Si R ln xi (11.77)

Because H iid Giid TSiid , substitution by eqs. (11.75) and (11.77)

yield
H iid Gi RT ln xi TSi RT ln xi
or
H iid H i (11.78)

The summability relation, eq. (11.11), applied to the special case of an

ideal solution, is written:
M id xi M iid
i

25
 Application to eqs. (11.75) (11.78) yields
G id xi Gi RT xi ln xi 11.79
i i

S id xi Si R xi ln xi 11.80
i i

V id xiVi 11.81
i

H id xi H i 11.82
i

26
The Lewis/Randall Rule
From eqs. (11.46) and (11.31),

i i T RT ln fi (11.46)
Gi i T RT ln fi (11.31)
Subtraction yields the general equation:

i Gi RT ln fi fi
For the special case of an ideal solution,

iid Giid Gi RT ln fiid fi
Comparison with eq. (11.75) gives:

f id x f (11.83) G Gi T , P RT ln xi (11.75)
id
i i
id
i i i

This equation, known as the Lewis/Randall rule, applies to each

species in an ideal solution at all conditions of temperature,
pressure and composition. 27
 It shows that the fugacity of each species in an ideal solution is
proportional to its mole fraction.
Division of both sides of eq. (11.83) by Pxi gives
f f id x f

i i 11.52 i
i i
yi P Pxi Pxi
fi (11.84)
i 11.34 iid i
P

The fugacity coefficient of species i in an ideal solution is equal to

the fugacity coefficient of pure species i in the same physical state as
the solution and at the same T and P.
Raoults law is based on assumption of ideal solution behavior for
the liquid phase, the same system that obey Raoults law form ideal
solution.
Ideal solutions are liquid phases whose molecules are of similar size
and which are of similar chemical nature.

28
The Excess Gibbs Energy and the Activity
Coefficient
Eq. (11.46) may be written as

Gi i T RT ln f i

In accord with eq. (11.83) for an ideal solution, this becomes

Giid i T RT ln xi fi f id x f
i i i
(11.83)
By difference,
f
Gi G RT ln i
id
i
xi f i
E
The left side of this equation is the partial excess Gibbs energy Gi ;
the dimensionless ratio on the right side is the activity coefficient of
species i in solution, i.
By definition,
f
i i (11.90)
xi fi
29
 So,
GiE RT ln i (11.91)
These equation establish a thermodynamic foundation for the activity
coefficient, as a factor introduced into Raoults law to account for
liquid phase non-idealities.
Comparison with eq. (11.51) shows that eq. (11.91) relates i to GiE
exactly as eq. (11.51) relates i to GiR .

GiR RT ln i (11.51)
For an ideal solution, Gi 0, and therefore i = 1.
E

A further relation results from combination of eq. (11.91) with eq.

(11.88)
RT ln i Gi Giid M iE M i M iid (11.88)

Elimination of the final term by eq. (11.75) and rearrangement gives

G Gi T , P RT ln xi
id
i i
id
(11.75)

Gi i Gi RT ln i xi (11.92)
This equation is an alternative definition of the activity coefficient.
30
 For ideal gas mixture model,
iig Giig RT ln yi (11.24)

For ideal solution model,

iid Gi RT ln xi (11.75)

For non-ideal solution,

i Gi RT ln i xi (11.92)

31
REFERENCE
Smith, J.M.,Van Ness, H.C., and Abbott, M.M. 2005.
Introduction to Chemical Engineering Thermodynamics.
Seventh Edition. Mc Graw-Hill.

32
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303