CHE553 Chemical Engineering Thermodynamics

4/4/2016

FUGACITY AND FUGACITY COEFFICIENT:

SPECIES IN SOLUTION

The definition of a residual property is

(6.41)
MR M Mig
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 MiR follows from this
equation. Multiplied by n mol of mixture, it becomes

The definition of a species in solution is parallel to the definition of the purespecies fugacity.
For species i in a mixture of real gases or in a solution of liquids,
i i T RT ln fi

(11.46)

nMR nM nMig

where f i is the fugacity of species i in solution, replacing the partial pressure

yiP in eq. (11.29) for ideal gas.
(11.29)
iig G iig i T RT ln y i P
For species in solution, the phase equilibrium criteria is:

fi fi ... fi

i 1, 2, ...,N

Differentiation with respect to ni at constant T, P and nj gives

nMR

ni

(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:
(11.48)
fi fi l
i 1, 2, ...,N

P ,T ,n j

nMig
nM

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

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

CHE553 Chemical Engineering Thermodynamics

4/4/2016

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

G iR G i G iig

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
(11.53)
fi ig y i P
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 G iR 0

(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
(11.46)
i i T RT ln fi
i iig RT ln

fi
yiP

iig G iig i T RT ln y i P

i ig

(11.29)

This result combined with eq. (11.50) and the identity i G i gives
G iR RT lni

fi ig y i P

1
yiP yiP

G iR RT lni ig RT ln 1 0

(11.51)

where by definition,
i

fi
yiP

(11.52)

The dimensionless ratio i is called the fugacity coefficient of species i in

solution.
5

Fugacity Coefficients from the Virial

Equation of State

B y i y j Bij
i

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:
Z 1

BP
RT

(11.61)

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

gives
B y1y1B11 y1y 2B12 y 2 y1B21 y 2 y 2B22

(3.38)

or

The mixture second virial coefficient B is a function of temperature and

composition.
B y i y j Bij

B y12 B11 2 y1y 2 B12 y 2 2 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.

(11.61)

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.

CHE553 Chemical Engineering Thermodynamics

4/4/2016

Eq. (11.62) allows derivation of expressions for ln1 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

B y12 B11 2 y1y 2 B12 y 2 2 B22

Eq. (11.62) for the second virial coefficient may be written:
B y1 1 y 2 B11 2 y1y 2 B12 y 2 1 y1 B22
y1B11 y1y 2 B11 2 y1y 2 B12 y 2 B22 y1y 2 B22

or

nZ
n
P nB

n1 P ,T ,n2 n1 P ,T ,n2 RT n1 T ,n2

B y1B11 y 2 B22 y1y 212

nB ny1B11 ny 2 B22 ny1y212

P nB

RT n1 T ,n

1 P nB
P nB

dP

RT 0 n1 T ,n
RT n1 T ,n
2
2

lni Z i 1
P

dP
P

ln1

1 P nB
P nB

dP

RT 0 n1 T ,n
RT n1 T ,n
2

ln1

Similarly,

ln2

P
1
ln k
Bkk y i y j 2 ik ij
RT
2 i j

P
B11 y2212
RT

P
B22 y1212
RT

(11.63a)
(11.63b)
10

EXAMPLE 11.7

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

mixtures; the general equation is

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:

(11.64)

where i and j run over all species, and

B11 35.2

B22 105.0

B12 59.8 cm3 mol-1

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

ij 2Bij Bii Bij

and

n1n2
12
n

Therefore from previous eqn.,

ii 0, kk 0, etc.,

nB n1B11 n2 B22

B11 1 y1 y 212 B11 y 2212

(11.60)

where the integration is elementary, because B is not function of pressure. All

that remains is evaluation of the derivative.

ik 2Bik Bii Bkk

or

1 n1
1 n1

B11 2 n212 B11 1 n212

n n
n n
n1 T ,n2

From eq. (11.60) yields

with

12 2B12 B11 B22

By differentiation,
nB

ln1

with

Multiplying by n and substituting yi = ni/n gives,

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

Z1 1

(11.62)

ki ik , etc.,

ln1
ln2

Thus,
11

30

35.2 0.6 2 20.6 0.0501

30

105.0 0.4 2 20.6 0.1835

83.14 200

83.14 200

1 0.9511

and

2 0.8324

R=8.314 m3 Pa/mol.K = 83.14 cm3 bar/mol.K

12

CHE553 Chemical Engineering Thermodynamics

4/4/2016

GENERALIZED CORRELATIONS FOR THE

FUGACITY COEFFICIENT

Note that the second virial coefficient of the mixture as given by eq. (11.62) is
B y12 B11 2 y1y 2 B12 y 2 2 B22

Eq. (11.35) is put into generalized form by substitution of the relations,

0.4 35.2 2 0.4 0.6 59.8 0.6 105.0

2

P Pc Pr

72.14 cm3 mol-1

dP Pc dPr

dP
lni Z i 1
0
P
P

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

Hence,

BP
Z 1
RT
72.14 30
1
0.870
83.14 200

const T

(11.35)

dPr
(11.65)
Pr
where the integration is at constant Tr. Substitution for Zi by Eq. (3.57) yields
lni

Pr

Z i 1

Z i Z 0 Z1
ln

Pr

(3.57)

dPr
dP
Z1 r
0
Pr
Pr
Pr

where for simplicity i is omitted.

13

14

EXAMPLE 11.8
This equation may be written in alternative form:
ln ln 0 ln1

where
ln 0

Pr

dPr
Pr

and

(11.66)
Pr

ln1 Z1
0

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

dPr
Pr

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

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.

15

16

CHE553 Chemical Engineering Thermodynamics

4/4/2016

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
BP
P
(3.61)
Z 1
1 B r
Z 1

Pr 0
B B1
Tr

RT
B B 0 B1

Tr

(3.63)

Substitution in eq. (11.65) and integration yield

ln

Pr 0
B B1
Tr

Pr 0

B B1
Tr

exp

or

where
B0 0.083

0.422
Tr1.6

and

B1 0.139

(11.68)

0.172
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.
17

18

Extension to Mixtures
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
(11.69a)
B ij B0 ij B1
where

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

P
1
Bkk y i y j 2 ik ij
RT
2 i j

(11.64)

Bij Pcij
B ij
RTcij

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).
BP
B c
RTc
B B 0 B1

0.422
B 0.083 1.6
Tr
0.172
1
B 0.139 4.2
Tr
0

(11.69b)

and B0 and B1 are the same functions of Tr as given by eqs. (3.65) and (3.66).
Thus,
Bij Pcij

(3.62)

RTcij

(3.63)

Bij

(3.65)

B 0 ij B1
RTcij
Pcij

ij B1

(3.66)
19

20

CHE553 Chemical Engineering Thermodynamics

4/4/2016

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 lni .

The combining rules for calculation of ij, Tcij, and Pcij are
ij

i j
2

Tcij Tci Tcj

1/ 2

Pcij
Z cij

11.70

1 k

11.71

ij

Z cij RTcij

11.72

Vcij
Z ci Z cj

11.73

Vci1/ 3 Vcj1/ 3
Vcij

Bij Pcij
B ij
RTcij

(11.69b)

B y i y j Bij

(11.61)

11.74

P
1
ln k
Bkk y i y j 2 ik ij
RT
2 i j

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.
21

(11.64)

ln1

P
B11 y2212
RT

(11.63a)

ln2

P
B22 y1212
RT

(11.63b)

22

EXAMPLE 11.9
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:
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:
Pcij/bar

Vcij/cm3 mol-1

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

Zcij

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

ij

Tcij/K

ij

ij

Trij

T
Tcij

0.422
Tr1.6
0.172
1
B 0.139 4.2
Tr
B 0 0.083

Values in the last row have been calculated by eqs. (11.70) (11.74).

3.65
3.66

R = 83.14 cm3 bar mol-1 K-1

23

B ij B0 ij B1

(11.69a)

Bij Pcij

(11.69b)

B ij

Bij Pcij
RTcij
Bij

RTcij

B 0 ij B1
RTcij
Pcij

ij B1

24

CHE553 Chemical Engineering Thermodynamics

4/4/2016

THE IDEAL SOLUTION MODEL

Calculating 12 according to its definition gives:

12 2B12 B11 B22 2 1610.4 1378.6 1873.9 31.7 cm3 mol-1

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

Eq.(11.63) then yield:

iig G iig G iig T , P RT ln y i

P
ln1
B11 y 2212 8314 25323.15 1378.6 0.52 31.7 0.0128
RT
P
ln2
B22 y1212 8314 25323.15 1873.9 0.52 31.7 0.0174
RT

Partial volume,

R = 8314 cm3 kPa mol-1 K-1

Thus,
1 0.987

and

(11.24)

For an ideal solution,

iid G iid G i T , P RT ln x i

(11.75)

G id
G
Vi id i i
P T , x P T

By eq. (11.4), G i / P T Vi ; thus,

2 0.983

Vi id Vi

(11.76)

25

As a result of eq. (11.19),

By eq. (11.5),

Application to eqs. (11.75) (11.78) yields

G id
G
Si id i i R ln x i
T P
T P , x
Si id Si R ln x i

Because
or

26

11.79

S x i Si R x i ln x i

11.80

V x iVi

11.81

id

(11.77)

id

Hiid G iid TSi id , substitution by eqs. (11.75) and (11.77) yield

H x i Hi
id

Hiid G i RT ln x i TSi RT ln x i
Hiid Hi

G id x i G i RT x i ln x i

11.82

(11.78)

The summability relation, eq. (11.11), applied to the special case of an ideal
solution, is written:
Mid x i Miid
i

27

28

CHE553 Chemical Engineering Thermodynamics

4/4/2016

The Lewis/Randall Rule

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

From eqs. (11.46) and (11.31),

i i T RT ln fi

(11.46)

G i i T RT ln f i

(11.31)

fi
yiP
f
i i
P

Subtraction yields the general equation:

i G i RT ln fi f i

For the special case of an ideal solution,

iid Giid Gi RT ln fi id f i

Comparison with eq. (11.75) gives:

fi id x i f i

(11.83)

iid G iid G i T , P RT ln x i

(11.75)

fi id x i f i

Px i Px i
id

11.52
11.34

(11.84)

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.

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

ideal solution at all conditions of temperature, pressure and composition.
29

EXCESS PROPERTIES

The Excess Gibbs Energy and the Activity

Coefficient

Residual properties are used to measure the deviation of real fluid properties
to ideal gas properties. Although residual properties can be used for all fluid
(both gases and liquids), it is more convenient to measure the deviation of real
solution (liquid mixtures) to that of ideal solution. This is accomplished through
the use of excess properties.
Hence, excess properties are analogous to residual properties (residual for
deviation from ideal gas and excess for deviation from ideal solution).
Excess properties is defined as:
ME M Mid

30

Eq. (11.46) may be written as

G i i T RT ln fi

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

By difference,

G iid i T RT ln x i f i
G i G iid RT ln

11.85

fi id x i f i

(11.83)

fi
xif i

The left side of this equation is the partial excess Gibbs energy G iE ; the
dimensionless ratio on the right side is the activity coefficient of species i in
solution, i.
By definition,
i
31

So,

fi
xifi

G iE RT ln i

(11.90)
(11.91)

32

CHE553 Chemical Engineering Thermodynamics

4/4/2016

For ideal gas mixture model,

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 G iE
exactly as eq. (11.51) relates i to G iR .

For non-ideal solution,

(11.51)
For an ideal solution, G iE 0, and therefore i = 1.
A further relation results from combination of eq. (11.91) with eq. (11.88)
RT ln i G i G iid
(11.88)
MiE Mi Miid
Elimination of the final term by eq. (11.75) and rearrangement gives

(11.24)

iid G i RT ln x i

(11.75)

i G i RT ln i x i

(11.92)

For ideal solution model,

G iR RT lni

iid G iid G i T , P RT ln x i

iig G iig RT ln y i

(11.75)

(11.92)
G i i G i RT ln i x i
This equation is an alternative definition of the activity coefficient.
33

34

REFERENCE
From summability relation (eq. 11.11),
G E x i G iE
i

Substitution of eq. (11.91),

G RT ln i (11.91)
E
i

G
x i ln i
RT
i
These relation is very important in determining activity coefficient, i.
From Gibbs/Duhem eqn. at constant T and P (eq. 11.14):
G E RT x i ln i

or

(11.99)

Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to
Chemical Engineering Thermodynamics. Seventh Edition. Mc GrawHill.

x dG
i

E
i

Substitution of eq.(11.91),

x d RT ln 0
i

For constant T and P,

x d ln
i

(11.100)

This eqn. is very important to check the thermodynamic consistency of binary

liquid-vapor equilibrium.
35

36

CHE553 Chemical Engineering Thermodynamics

4/4/2016

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

10