c 2011 Ismail Tosun

Chapter 7

Fugacity of a Component in a Mixture

When two phases of a pure component are in equilibrium, fugacities in each phase must be
the same. The purpose of this chapter is to replace a pure component with a multicomponent
mixture and investigate the conditions under which two phases of a multicomponent mixture
are in equilibrium with each other. For this purpose, first the fugacity definition given in
Chapter 5 will be extended to multicomponent mixtures; then equations to calculate fugacities
of components making up the mixture will be developed.

7.1 FUNDAMENTAL EQUATIONS FOR A MULTICOMPONENT MIXTURE

The combined law for a single-phase, single-component open system, Eq. (4.2-9), is given as
e dn
dU = T dS P dV + G (7.1-1)
By definition, Gibbs energy is expressed as
G = U + PV TS (7.1-2)
In dierential form, Eq. (7.1-2) becomes
dG = dU + P dV + V dP T dS S dT (7.1-3)
Substitution of Eq. (7.1-1) into Eq. (7.1-3) leads to
e dn
dG = V dP S dT + G (7.1-4)
indicating that the Gibbs energy is dependent on pressure, temperature, and number of moles,
i.e.,
G = G(P, T, n) (7.1-5)
The total dierential of G is

G G G
dG = dP + dT + dn (7.1-6)
P T,n T P,n n P,T

Comparison of Eq. (7.1-6) with Eq. (7.1-4) yields

G
V = (7.1-7)
P T,n

G
S= (7.1-8)
T P,n

e G
G= (7.1-9)
n P,T

179
 In the case of a single-phase, multicomponent open system, Gibbs energy of the phase not
only depends on pressure and temperature, but also on the number of moles of each component
existing in the phase, i.e.,
G = G(P, T, n1 , n2 , ..., nk ) (7.1-10)
Therefore, the total dierential of G is expressed in the form
k
X
G G G
dG = dP + dT + dni (7.1-11)
P T,nj T P,nj ni P,T,nj6=i
i=1

The subscript nj in the first two terms of Eq. (7.1-11) implies that the number of moles of
each component is held constant during dierentiation. For a constant number of moles, Eqs.
(7.1-7) and (7.1-8) are still valid. On the other hand, the partial molar Gibbs energy is defined
by
G
Gi = (7.1-12)
ni P,T,nj6=i
Thus, Eq. (7.1-11) becomes

k
X
dG = V dP S dT + Gi dni (7.1-13)
i=1

Historically, for a multicomponent system, the partial molar Gibbs energy has been called the
chemical potential and designated by i , i.e., Gi = i .
The enthalpy is related to the Gibbs energy by

H = G + TS (7.1-14)

Dierentiation of Eq. (7.1-14) gives

dH = dG + T dS + S dT (7.1-15)

Substitution of Eq. (7.1-13) into Eq. (7.1-15) yields

k
X
dH = T dS + V dP + Gi dni (7.1-16)
i=1

The internal energy is related to the enthalpy by

U = H PV (7.1-17)

Dierentiation of Eq. (7.1-17) gives

dU = dH P dV V dP (7.1-18)

The use of Eq. (7.1-16) in Eq. (7.1-18) results in

k
X
dU = T dS P dV + Gi dni (7.1-19)
i=1

180
 The Helmholtz energy is related to the internal energy by
A = U TS (7.1-20)
Dierentiation of Eq. (7.1-20) gives
dA = dU T dS S dT (7.1-21)
Substitution of Eq. (7.1-19) into Eq. (7.1-21) yields
k
X
dA = P dV S dT + Gi dni (7.1-22)
i=1

Equations (7.1-13), (7.1-16), (7.1-19), and (7.1-22) are the fundamental equations for a single-
phase, multicomponent open system. From these equations, partial molar Gibbs energy can
be expressed in dierent forms as

G H U A
Gi = = = = (7.1-23)
ni T,P,nj6=i ni P,S,nj6=i ni V,S,nj6=i ni T,V,nj6=i

Example 7.1 Develop the Gibbs-Duhem equation for the Gibbs energy by the application of
Eulers theorem.

Solution

Equation (7.1-19) indicates that the internal energy of a single phase, multicomponent system
depends on S, V , and the number of moles of each component, i.e.,
U = U (S, V, n1 , n2 , ..., nk ) (1)
Application of Eulers theorem, Eq. (6.2-33), gives
k
X
U U U
U= S+ V + ni (2)
S V,nj V S,nj ni S,V,nj6=i
i=1

From Eq. (7.1-19)

U U U
=T = P = Gi (3)
S V,nj V S,nj ni S,V,nj6=i

Thus, Eq. (2) takes the form

k
X
U = TS PV + Gi ni (4)
i=1
Dierentiation of Eq. (4) yields
k
X k
X
dU = T dS + S dT P dV V dP + Gi dni + ni dGi (5)
i=1 i=1

Subtraction of Eq. (7.1-19) from Eq. (5) results in

k
X
S dT V dP + ni dGi = 0 (6)
i=1

181
which is the most general form of the Gibbs-Duhem equation. It provides the relationship
between temperature, pressure, and the partial molar Gibbs energy.
At constant temperature and pressure, Eq. (6) reduces to
k
X
ni dGi = 0 constant T and P (7)
i=1

Dividing Eq. (7) by the total number of moles gives

k
X
xi dGi = 0 constant T and P (8)
i=1

Comment: For a single-component system, the Gibbs-Duhem equation, Eq. (6), reduces to
e=0
S dT V dP + n dG (9)

Dividing Eq. (9) by the number of moles, n, leads to

e = Ve dP Se dT
dG (10)

which is identical with Eq. (2.2-15).

7.1.1 Criteria for Chemical Equilibrium

Consider an isolated multicomponent system containing - and -phases. Note that although
the overall system is an isolated one each phase may be considered an open system, i.e., there
may be an exchange of mass and/or energy between - and -phases.
In the case of no chemical reaction, the total values of internal energy, volume, and number
of moles of species i can be expressed as

U = U + U = constant dU = dU

V = V + V = constant dV = dV (7.1-24)

ni = ni + ni = constant dni = dni

Suppose that an arbitrary process causes changes in the entropies of the - and -phases. Such
changes can be expressed from Eq. (7.1-19) as

XG k
1 P i
dS = dU + dV dni (7.1-25)
T T T
i=1

XG k
1 P i
dS = dU + dV dni (7.1-26)
T T T
i=1

Summation of Eqs. (7.1-25) and (7.1-26) and making use of the constraints given by Eq.
(7.1-24) lead to
k

!
1 1 P P X Gi Gi
dS = dU + dV dni (7.1-27)
T T T T T T
i=1

182
The condition of equilibrium is satisfied, i.e., dS = 0, if the terms in parentheses in Eq. (7.1-27)
are all equal to zero. Therefore, at equilibrium we have the following conditions:

T = T Thermal equilibrium

P = P Mechanical equilibrium (7.1-28)

Gi = Gi Chemical equilibrium

Equality of partial molar Gibbs energies implies that there are no chemical driving forces to
move species from one phase to another.

7.1.2 The Gibbs Phase Rule

The Gibbs phase rule is given by Eq. (1.1-4), i.e., P + F = C + 2. We are now in a position
to derive this equation theoretically. The number of degrees of freedom, F , is defined by

Total # of independent # of independent equations
F = (7.1-29)
intensive variables relating these variables

Consider a composite system containing P phases and C components. Assume that each
component exists in each phase. Hence,

For each phase : (C 1) independent mole fractions

(7.1-30)
Total mole fractions : P (C 1)

At equilibrium, temperature and pressure must be uniform throughout the phases. Therefore,
the total number of independent intensive variables is 2 + P (C 1). The condition of chemical
equilibrium is designated by the following equations:
1 2 P
At equilibrium Gi = Gi = ... = Gi i = 1, 2, ..., C (7.1-31)

Under these circumstances, we have

For each species : (P 1) independent equations

(7.1-32)
Total # of independent eqns : C(P 1)

Substitution of Eqs. (7.1-30) and (7.1-32) into Eq. (7.1-29) gives

F = 2 + P (C 1) C(P 1) P +F =C +2 (7.1-33)

Note that Eq. (7.1-33) applies only to systems at equilibrium when there is no chemical reaction
taking place.

7.2 PARTIAL MOLAR GIBBS ENERGY OF AN IDEAL GAS MIXTURE

An ideal gas mixture is a gas mixture with a density so low that its molecules do not appreciably
interact. The equation of state for an ideal gas mixture containing k species is given by

P V IGM = (n1 + n2 + ... + nk ) RT (7.2-1)

| {z }
n

183
in which the superscript IGM stands for "ideal gas mixture". In an ideal gas mixture, the
partial pressure of species i, pi , is expressed as
pi = P yi (7.2-2)
In other words, the partial pressure of species i in the ideal gas mixture is the pressure exerted
by ni moles of pure species i at the same volume and temperature.
Any total property in an ideal gas mixture is the sum of individual species making up the
mixture, each evaluated at the mixture temperature and its own partial pressure. Therefore,
we can write
X k
U IGM (T, P ) = eiIG (T )
ni U (7.2-3)
i=1
k
X
H IGM (T, P ) = e iIG (T )
ni H (7.2-4)
i=1
k
X
S IGM (T, P ) = ni SeiIG (T, pi ) (7.2-5)
i=1
Equations (7.2-3) and (7.2-4) imply that both the internal energy change on mixing and the
enthalpy change on mixing are zero for an ideal gas mixture.
From Eq. (2.2-41), the change in the entropy of a pure ideal gas with pressure, keeping
temperature constant, is given by
R
dSeiIG = dP at constant T (7.2-6)
P
Integration at constant temperature from P to pi yields
p
i
SeiIG (T, pi ) = SeiIG (T, P ) R ln
P n
i
= SeiIG (T, P ) R ln yi = SeiIG (T, P ) R ln (7.2-7)
n
Substitution of Eq. (7.2-7) into Eq. (7.2-5) gives
k
X k
X n
i
S IGM (T, P ) = ni SeiIG (T, P ) R ni ln (7.2-8)
n
i=1 i=1
The Gibbs energy of an ideal gas mixture is
GIGM (T, P ) = H IGM (T, P ) T S IGM (T, P ) (7.2-9)
Substitution of Eqs. (7.2-4) and (7.2-8) into Eq. (7.2-9) gives
k
X k
X n
eIG (T, P ) + RT i
GIGM (T, P ) = ni Gi ni ln (7.2-10)
n
i=1 i=1

The partial molar Gibbs energy of species i in an ideal gas mixture can be calculated as
IGM
IGM G eIG
Gi (T, P, yi ) = =Gi (T, P ) + RT ln yi (7.2-11)
ni T,P,nj6=i

It is possible to rearrange Eq. (7.2-11) as

Gi
IGM eIG (T, P )
(T, P, yi ) G
Pi i
ln = (7.2-12)
P RT

184
7.3 FUGACITY OF A COMPONENT IN A MIXTURE
Lewis extended the definition introduced by Eq. (7.2-12) to multicomponent systems, and the
fugacity of a component i in a mixture, fbi , is expressed in the form
" # IGM
fbi (T, P, xi ) Gi (T, P, xi ) Gi (T, P, xi )
ln = (7.3-1)
P xi RT

subject to the following constraint

fbi /(xi P ) 1 as P 0 (ideal gas state) (7.3-2)

which applies to solid, liquid, and gas.

bi , is defined by
The fugacity coecient of a component i in a mixture,

b
bi = fi
(7.3-3)
xi P
where the symbol (b) is used to represent properties in the mixture. Although they look similar
to partial properties, their definitions are not the same.
Combination of Eqs. (7.3-1), (7.2-12), and (5.1-5) leads to an alternative expression for the
fugacity of component i in a mixture as
eIG
Gi = G o o b
i (T, P ) RT ln P + RT ln fi (7.3-4)

or
Gi = i (T ) + RT ln fbi (7.3-5)
where i (T ) is the molar Gibbs energy of pure component i at unit fugacity, and is defined by
Eq. (5.2-6). Dierentiation of Eq. (7.3-5) by keeping temperature and the number of moles of
each component constant leads to

dGi = RT d ln fbi at constant T and nj (7.3-6)

When - and -phases of a multicomponent mixture are in equilibrium with each other,
the condition of equilibrium is represented by Eq. (7.1-28), i.e.,

T = T P = P Gi = Gi (7.3-7)

Letting T = T = T and P = P = P , equality of partial molar Gibbs free energies leads to

i (T ) + RT ln fbi (T, P, xi ) = i (T ) + RT ln fbi (T, P, xi ) (7.3-8)

or
fbi (T, P, xi ) = fbi (T, P, xi ) (7.3-9)
Thus, at equilibrium, fugacities of each component are equal in all phases.
Dierentiation of Eq. (7.3-6) with respect to pressure gives
!
Gi ln fbi
= RT (7.3-10)
P T,nj P
T,nj

185
The left-hand side of Eq. (7.3-10) is expressed as
" #
Gi Gmix
= (7.3-11)
P T,nj P ni T,P,nj6=i T,nj

Changing the order of dierentiation leads to

" #
Gi Gmix Vmix
= = =Vi (7.3-12)
P T,nj ni P T,nj ni T,P,nj6=i
T,P,nj6=i

Therefore, at constant temperature and number of moles, Eq. (7.3-10) is expressed as

RT d ln fbi = V i dP (7.3-13)

Subtraction of the term RT d ln(xi P ) from both sides of Eq. (7.3-13) and integration result in
! Z
fbi b =
P
Vi 1
ln = ln i dP at constant T and nj (7.3-14)
xi P 0 RT P

Noting that P V i = Z i RT , it is also possible to express Eq. (7.3-14) in the form

Z P
bi = Zi 1
ln dP at constant T and nj (7.3-15)
0 P

The fugacity of a pure component can be calculated from Eq. (5.2-12) as

Z P e !
fi Vi 1
ln = dP at constant T (7.3-16)
P 0 RT P

Subtraction of Eq. (7.3-16) from Eq. (7.3-14) yields

! Z
fbi 1 P
ln = (V i Vei ) dP at constant T and nj (7.3-17)
xi fi RT 0

Equations (7.3-14), (7.3-15), and (7.3-17) can be used to calculate the fugacity of component i
in a mixture, and all equations are valid for gases, liquids, and solids. Note that the evaluation
of integrals in these equations requires either the equation of state or the volumetric data in
tabular form to be known.

7.4 IDEAL MIXTURE1

A mixture, either gaseous or liquid, is said to be an ideal mixture if it has the following
properties:
i) It is homogeneous,
ii) The sizes of the molecules are equal,
iii) The forces between unlike molecules of the mixture are the same as the forces between like
molecules.
1
In the literature, ideal mixture is also referred to as ideal solution.

186
It follows from properties (ii) and (iii) that

IM
V i (T, P, xi ) = Vei (T, P ) (7.4-1)

On the other hand, property (iii) implies that

IM e i (T, P )
H i (T, P, xi ) = H (7.4-2)

Since U i = H i P V i , then Eqs. (7.4-1) and (7.4-2) indicate that

IM ei (T, P )
U i (T, P, xi ) = U (7.4-3)

Mixtures of two similar substances usually form an ideal mixture, i.e., benzene and toluene,
o-xylene and m-xylene, butane and isobutane, n-butanol and n-pentanol, n-pentane and
n-hexane.
Substitution of Eq. (7.4-1) into Eq. (7.3-17) yields
!
fbiIM
ln =0 (7.4-4)
xi fi

or
fbiIM (T, P, xi ) = xi fi (T, P ) (7.4-5)
indicating that the fugacity of component i in an ideal mixture can be calculated by multiplying
the pure component fugacity by its mole fraction. This relationship is known as the Lewis-
Randall rule. Pure component fugacities, on the other hand, can be calculated by using one of
the methods given in Chapter 5.
The use of Eq. (7.4-5) in Eq. (7.3-3) gives

bIM (T, P, xi ) = i (T, P )

(7.4-6)
i

indicating that the fugacity coecient of i in an ideal mixture is independent of the mixture
composition.
Although the simplicity of the Lewis-Randall rule makes it an attractive tool in the calcula-
tion of mixture fugacities, one should remember the limitations of using it. The Lewis-Randall
rule is applicable under the following conditions:
Component i is present in large excess, i.e., xi > 0.9.
Components are similar,
Gas phase is nearly ideal, i.e., pressure is low.

7.5 CALCULATION OF COMPONENT FUGACITIES IN A GAS MIXTURE

7.5.1 Fugacity of a Component in an Ideal Gas Mixture
Using Eq. (7.2-1), the partial molar volume of an ideal gas mixture is calculated as
IGM
V RT
Vi = = (7.5-1)
ni T,P,nj6=i P

187
Substitution of Eq. (7.5-1) into Eq. (7.3-14) gives
IGM
b
ln =0 bIGM = 1
or fbiIGM = yi P = pi (7.5-2)
i i

Therefore, for an ideal gas mixture, the fugacity coecient of component i is unity and the
fugacity of component i is equal to its partial pressure. At high pressures and low temperatures,
the fugacity coecient of a component in a gas mixture deviates from unity, indicating nonideal
behavior.

7.5.2 Fugacity of a Component in an Ideal Mixture

In this case the Lewis-Randall rule applies and from Eqs. (7.4-5) and (7.4-6)

fbiIM (T, P, yi ) = yi fi (T, P ) and bIM (T, P, yi ) = (T, P )

(7.5-3)
i i

Fugacities of pure components are determined by one of the methods described in Section 5.3.
It is important not to confuse ideal gas mixture with ideal mixture2 . An ideal gas
mixture always behaves as an ideal mixture. However, an ideal mixture does not necessarily
behave as an ideal gas mixture. Note that the compressibility factor for an ideal mixture is
given by !
k k k
IM P Ve IM P X e X P Vei X
Z = = yi Vi = yi = yi Zi (7.5-4)
RT RT RT
i=1 i=1 i=1
On the other hand, Z IGM = 1.0.
Example 7.2 Consider an ideal binary mixture of 35 mol % n-butane (1) and 65% n-hexane
(2) at 373.15 K and 10 bar. Determine the fugacities of n-butane and n-hexane in the mixture
using the Peng-Robinson equation of state.
Solution
From Appendix A
Component Tc ( K) Pc ( bar)
n-Butane 425.0 38.0 0.199
n-Hexane 507.6 30.2 0.299

The Lewis-Randall rule requires pure component fugacities. The use of the Peng-Robinson
equation of state, Eq. (5.3-12), yields the following values:

f
Component Tr A B ZV
( bar)
n-Butane 0.878 1.086 0.170 0.023 0.837 0.8573 8.573
n-Hexane 0.735 1.245 0.349 0.035 0.047 0.2347 2.347

Thus, the fugacities of components in the mixture are

fb1 = (0.35)(8.573) = 3 bar
fb2 = (0.65)(2.347) = 1.53 bar

2
There is no interaction between the molecules of an ideal gas mixture. In the case of an ideal mixture,
however, the molecules interact with each other, the interaction between like molecules being almost equal to
the interaction between unlike molecules.

188
7.5.3 Fugacity from the Virial Equation of State
At low to moderate pressures, the virial equation of state of a multicomponent gas mixture,
truncated after the second term, is given by
Bmix P
Zmix = 1 + (7.5-5)
RT
where the second virial coecient for the mixture, Bmix , is defined by Eq. (6.1-2). The use of
Eq. (7.5-5) in Eq. (7.3-15) gives the fugacity coecient of species i in a mixture as3

Xk
V
b = 2 P
ln i yj Bij Bmix (7.5-6)
RT
j=1

An alternative derivation of Eq. (7.5-6) for a binary system is given in Problem 7.4.
Example 7.3 For a mixture of n-butane (1) and n-hexane (2) at 373 K, determine the fu-
gacity coecients at 1, 10, and 15 bar when y1 = 0.35. The virial coecients at 373 K are
given as
B11 = 422 cm3 / mol
B22 = 103.1 cm3 / mol
B12 = B21 = 650 cm3 / mol
Solution
For a binary system, Eq. (6.1-2) yields
Bmix = y12 B11 + 2 y1 y2 B12 + y22 B22 (1)
Substitution of Eq. (1) into Eq. (7.5-6) leads to
h i
b = exp P B11 + y 2 (2 B12 B11 B22 )
(2)
1 2
RT
i
b P h 2
2 = exp B22 + y1 (2 B12 B11 B22 ) (3)
RT
Fugacity coecients of n-butane (1) and n-hexane (2), calculated from Eqs. (2) and (3), are
tabulated below:

P ( bar) b1
b
2

1 0.976 0.994
10 0.785 0.938
15 0.696 0.909

7.5.4 Fugacity from Cubic Equations of State

Since the cubic equations of state are pressure-explicit, i.e.,
P = P (T, Vmix , n1 , n2 , ..., nk ) (7.5-7)
then it is useful to have an equation relating the fugacity of component i in a mixture to an
integral over volume rather than pressure. To convert Eq. (7.3-14) to the form amenable to
the cubic equations of state, note that the total dierential of Eq. (7.5-7) is

3
See Problem 7.2

189
 k
X
P P P
dP = dT + dV + dni (7.5-8)
T V,nj Vmix T,nj ni T,V,nj6=i
i=1
Dierentiation of Eq. (7.5-8) with respect to ni by keeping T , P , and the number of moles of
each component other than i constant gives

P Vmix P
+ =0 (7.5-9)
Vmix T,nj ni T,P,nj6=i ni T,V,nj6=i
| {z }
Vi
or
P
ni T,V,nj6=i
P Vmix
Vi = = (7.5-10)
P ni T,V,nj6=i P T,nj
Vmix T,nj
On the other hand, integration of the equation of state, P Vemix = Zmix RT , at constant tem-
perature gives
dP dVemix dZmix
+ = (7.5-11)
P Zmix
Vemix
Substitution of Eqs. (7.5-10) and (7.5-11) into Eq. (7.3-14) yields

Z
b = 1 n P RT dVemix ln Zmix
ln i (7.5-12)
RT Vemix ni T,V,nj6=i e
Vmix

van der Waals equation of state

Substitution of the van der Waals equation of state into Eq. (7.5-12) gives the fugacity coe-
cient of species i in a mixture as
P
k
2 yj Aij
Bi
bV
ln = ln V
Zmix Bmix
j=1
(7.5-13)
i V V
Zmix Bmix Zmix

Example 7.4 Show how one can obtain Eq. (7.5-13) by the substitution of the van der Waals
equation of state into Eq. (7.5-12).
Solution
Since Ve = V /n, the van der Waals equation of state takes the form
P
k P
k
n2 yi yj aij
nRT n2 amix nRT i=1 j=1
P= 2
= 2
Vmix nbmix Vmix P
k
Vmix
Vmix n yi bi
i=1
P
k P
k
ni nj aij
nRT i=1 j=1
= 2
(1)
P
k
Vmix
Vmix ni bi
i=1

190
Dierentiation of Eq. (1) with respect to ni gives

X k X k
P RT nRT bi 1
= + 2
2 ni nj aij
ni T,V,nj6=i P
k
Pk Vmix ni
Vmix ni bi i=1 j=1
Vmix ni bi T,V,nj6=i
i=1 i=1
(2)
For the dierentiation of the third term on the right-hand side of Eq. (2), let us carry out the
dierentiation for a binary mixture of components 1 and 2, i.e.,

X 2 X2
2 2

ni nj aij = n a11 + 2 n1 n2 a12 + n2 a22
n1 n1 1 T,V,n2
i=1 j=1
T,V,n2
2
X
= 2 (n1 a11 + n2 a12 ) = 2 nj a1j (3)
j=1

It is possible to generalize Eq. (3) as

Xk X k k
X

ni nj aij =2 nj aij (4)
ni
i=1 j=1 j=1
T,V,nj6=i

Substitution of Eq. (4) into Eq. (2) gives

P
k
2n yj aij
P RT nRT bi j=1
= + (5)
ni T,V,nj6=i Vmix nbmix (Vmix nbmix )2 2
Vmix
Multiplication of Eq. (5) by the total number of moles, n, results in
P
k
2 yj aij
P RT RT bi j=1
n = + (6)
ni 2
T,V,nj6=i Vemix bmix (Vemix bmix )2 Vemix
Substitution of Eq. (6) into Eq. (7.5-12) and integration lead to
P
k
2 yj aij
bV = ln Vemix + bi j=1 V
ln i ln Zmix (7)
Vemix bmix Vemix bmix Vemix RT
Finally, the use of dimensionless parameters reduces Eq. (7) to Eq. (7.5-13).

An alternative derivation of Eq. (7.5-13) is presented in Problem 7.6.

Redlich-Kwong equation of state
The use of the Redlich-Kwong equation of state in Eq. (7.5-12) leads to the following expression
for the fugacity coecient of species i in a mixture:
k
P
!
B A 2 yj Aij
B B
V
b = i mix j=1 i mix
ln i Z V 1 ln ZmixV Bmix ln 1 + V
Bmix mix Bmix Amix Bmix Z mix

(7.5-14)

191
For an alternative derivation of this equation, see Problem 7.7.

Example 7.5 Calculate the fugacity coecients of carbon dioxide (1) in a mixture containing
85 mol % n-butane (2) at 444 K as a function of pressure. The system is represented by the
Redlich-Kwong equation of state with k12 = 0.18.
Solution
From Appendix A

Component Tc ( K) Pc ( bar)
Carbon dioxide 304.2 73.8
n-Butane 425.0 38.0

Once the dimensionless parameters, Amix and Bmix , and the compressibility factor for the
V , are calculated using the equations given in Section 6.1.2, the fugacity
vapor mixture, Zmix
coecient of carbon dioxide in the mixture, bV ,can be determined from Eq. (7.5-14). On the
CO 2
other hand, if the mixture behaves ideally, then the Lewis-Randall rule applies and the fugacity
coecient of CO 2 in the mixture is equal to the fugacity coecient of pure CO2 , VCO 2 . The
fugacity coecient of pure CO2 is calculated by using Eq. (5.3-10). The results are presented
in tabular form and also plotted as shown below:

P ( bar) Amix Bmix V

Zmix bV
VCO2
CO 2

1 8.333 103 1.976 103 0.994 1.002 0.999

10 0.083 0.020 0.934 1.021 0.986
50 0.417 0.099 0.602 1.250 0.931
60 0.500 0.119 0.505 1.392 0.918
70 0.583 0.138 0.453 1.498 0.905
80 0.667 0.158 0.445 1.519 0.892
90 0.750 0.178 0.456 1.498 0.880
100 0.833 0.198 0.474 1.462 0.868
150 1.250 0.296 0.593 1.277 0.813
200 1.667 0.395 0.721 1.151 0.767
250 2.083 0.494 0.847 1.069 0.730
300 2.500 0.593 0.970 1.015 0.701

1.6
1.519

1.4

1.2
x

y
1

0.8

0.701
0.6
0 100 200 300
1 P 300

192
As can be seen from the figure, the fugacity coecient of CO2 is strongly dependent on pressure
with a maximum point. An ideal mixture assumption fails at all pressures, since the mole
fraction of carbon dioxide is small. For more details on this problem see Chueh and Prausnitz
(1967).

Soave-Redlich-Kwong equation of state

The use of the Soave-Redlich-Kwong equation of state in Eq. (7.5-12) leads to the following
expression for the fugacity coecient of species i in a mixture:

P
k
!
Bi V V Amix 2 yj Aij
B B
bV j=1 i mix
ln i = Zmix 1 ln Zmix Bmix ln 1 + V
Bmix Bmix Amix Bmix Zmix

(7.5-15)
In terms of dimensionless parameters, Eq. (7.5-15) is identical with the one given for the
Redlich-Kwong equation of state, Eq. (7.5-14).
Peng-Robinson equation of state
The use of the Peng-Robinson equation of state in Eq. (7.5-12) leads to the following expression
for the fugacity coecient of species i in a mixture:

V
b = Bi V V
ln i Zmix 1 ln Zmix Bmix
Bmix

P
k
(7.5-16)
" V #
Amix 2 yj Aij
Bi Zmix + (1 + 2) Bmix
j=1
ln
8 Bmix Amix Bmix V
Zmix + (1 2) Bmix

Example 7.6 Determine the fugacity coecients of n-butane (1) and n-hexane (2) in a
35 mol % n-butane, 65% n-hexane mixture at 373.15 K and 10 bar using the Peng-Robinson
equation of state. Take k12 = 0.006.

Solution

The properties at the critical point as well as the acentric factors were given in Example 7.2.
The values of the reduced temperature and pressure are

Component Tr Pr
n-Butane 0.878 0.263
n-Hexane 0.735 0.033

a) Using the equations given in Table 6.3, the dimensionless parameters are calculated as

A11 = 0.170 A12 = A21 = 0.245 B1 = 0.023

A22 = 0.349 B2 = 0.035

193
The dimensionless parameters for the mixture are calculated from Eqs. (6.1-10) and (6.1-11)
as
Amix = 0.279 and Bmix = 0.031
Therefore, Eq. (6.1-9) becomes
3 2 V
Zmix 0.969 Zmix + 0.215 Zmix 0.0077 = 0 Zmix = 0.662
Therefore, the fugacity coecients of components are calculated from Eq. (7.5-16) as
b1 = 0.886
b2 = 0.692

Comment: The fugacities of components in the mixture are
fb1 = (0.886)(10)(0.35) = 3.1 bar
fb2 = (0.692)(10)(0.65) = 4.5 bar
Comparison of these values with the ones calculated in Example 7.2 indicates that the use of
the Lewis-Randall rule introduces a serious error, especially for n-hexane.

7.6 CALCULATION OF COMPONENT FUGACITIES IN A LIQUID MIXTURE

Cubic equations of state can also describe P -Ve -T relations of liquid mixtures. However, es-
timation of mixture parameters is not a straightforward task. Depending on the components
making up the mixture, dierent mixing rules may be used. When van der Waals mixing rules,
i.e., Eqs. (6.1-6) and (6.1-10), are used, the equations given in Section 7.5.4 are also applicable
for liquid mixtures.

van der Waals equation of state

P
k
2 xj Aij
Bi L
bL =
ln ln Zmix Bmix
j=1
(7.6-1)
i L L
Zmix Bmix Zmix

Redlich-Kwong equation of state

P
k
!
Bi L L Amix 2 xj Aij
Bi Bmix
bL j=1
ln i = Zmix 1 ln Zmix Bmix ln 1 + L
Bmix Bmix Amix Bmix Zmix

(7.6-2)

Soave-Redlich-Kwong equation of state

P
k
!
Bi L L Amix 2 xj Aij
B B
bL j=1 i mix
ln i = Zmix 1 ln Zmix Bmix ln 1 + L
Bmix Bmix Amix Bmix Zmix

(7.6-3)

194
 Peng-Robinson equation of state

L
b = Bi L L
ln i Zmix 1 ln Zmix Bmix
Bmix

P
k
(7.6-4)
2 x A " L #
Amix j ij
Bi Zmix + (1 + 2) Bmix
j=1
ln
8 Bmix Amix Bmix Z
L
+ (1 2) Bmix
mix

Example 7.7 Shibata and Sandler (1989) reported the following data for the coexisting vapor
and liquid phases of nitrogen (1) and cyclohexane (2) mixture:

T = 366.4 K P = 138.76 bar x1 = 0.1286 y1 = 0.9721

The system is represented by the Peng-Robinson equation of state with k12 = 0.109.
a) Show that the vapor and liquid phases are indeed in equilibrium with each other.
b) Estimate the densities of vapor and liquid phases.

Solution

From Appendix A

Component M ( g/ mol) Tc ( K) Pc ( bar)

Nitrogen 28.01 126.2 34.0 0.039
Cyclohexane 84.16 554.0 40.7 0.212

a) The condition of equilibrium is given by

fbiV = fbiL bV = xi
yi bL (1)
i i

Using the equations given in Table 6.3, the dimensionless parameters are calculated as
A11 = 0.107 A12 = A21 = 0.620 B1 = 0.109
A22 = 4.541 B2 = 0.401
Vapor Phase
Using y1 = 0.9721 and y2 = 0.0279, the dimensionless parameters for the mixture are calculated
from Eqs. (6.1-10) and (6.1-11) as

X 2
2 X 2
X
Amix = yi yj Aij = 0.138 and Bmix = yi Bi = 0.118
i=1 j=1 i=1

The compressibility factor for the vapor phase is calculated from Eq. (6.1-9) as
V
Zmix = 1.019

Substitution of the numerical values into Eq. (7.5-16) leads to

bV = 1.021
bV = 0.493

1 2

195
 Liquid Phase
Using x1 = 0.1286 and x2 = 0.8714, the dimensionless parameters for the mixture are calculated
from Eqs. (6.1-10) and (6.1-11) as

X 2
2 X 2
X
Amix = xi xj Aij = 3.589 and Bmix = xi Bi = 0.364
i=1 j=1 i=1

The compressibility factor for the liquid phase is calculated from Eq. (6.1-9) as
L
Zmix = 0.471

Substitution of the numerical values into Eq. (7.6-4) leads to

bL = 7.623
bL = 0.017

1 2

The use of Eq. (1) gives

V L
b = (0.9721)(1.021) = 0.993
y1 b = (0.1286)(7.623) = 0.980
x1
1 1

V L
b = (0.0279)(0.493) = 0.014
y2 b = (0.8714)(0.017) = 0.015
x2
2 2

bV ' xi
Since yi bL , vapor and liquid phases are in equilibrium with each other.
i i

b) The molar volume of the vapor phase is

V RT
Zmix (1.019)(83.14)(366.4)
Vemix
V
= = = 223.7 cm3 / mol
P 138.76
The molecular weight of the vapor mixture is

M V = (0.9721)(28.01) + (0.0279)(84.16) = 29.577 g/ mol

The density of the vapor is

29.577
V = = 0.132 g/ cm3
223.7
The molar volume of the liquid phase is
L RT
Zmix (0.471)(83.14)(366.4)
Vemix
L
= = = 103.4 cm3 / mol
P 138.76
The molecular weight of the liquid mixture is

M L = (0.1286)(28.01) + (0.8714)(84.16) = 76.939 g/ mol

The density of the liquid is

76.939
L = = 0.744 g/ cm3
103.4

In most applications, however, liquid mixtures cannot be expressed by equations of state. In

that case, component fugacities in liquid mixtures are determined by using activity coecients
as will be explained in the next chapter.

196
7.7 VARIATION OF COMPONENT FUGACITY WITH PRESSURE AND
TEMPERATURE
The variation of component fugacity with pressure by keeping temperature and composition
constant can be easily obtained from Eq. (7.3-13) as
!
ln fbi Vi
= (7.7-1)
P RT
T,xj

On the other hand, dierentiation of Eq. (7.3-1) with respect to temperature by keeping
pressure and composition constant gives
! ! IGM !
ln fbi 1 Gi 1 Gi
= (7.7-2)
T R T T R T T
P,xj P,xj P,xj

The Gibbs-Helmholtz equation developed for pure components, Eq. (5.7-8), is also valid for
partial molar properties, i.e., !
Gi Hi
= 2 (7.7-3)
T T T
P,xj

Therefore, Eq. (7.7-2) reduces to

! IGM
ln fbi Hi Hi
= (7.7-4)
T RT 2
P,xj

or
!
ln fbi e IG
Hi Hi
= (7.7-5)
T RT 2
P,xj

Variation in ln fbi is expressed in the form of an exact dierential as

! !
ln fbi ln fbi
d ln fbi = dP + dT (7.7-6)
P T
T P

Substitution of Eqs. (7.7-1) and (7.7-5) into Eq. (7.7-6) gives

! !
Vi e IG
Hi Hi
d ln fbi = dP dT (7.7-7)
RT RT 2

Note that Eq. (7.7-7) is analogous to Eq. (5.8-5) in which molar quantities are replaced by
partial molar quantities.

7.8 THE USE OF FUGACITY IN PHASE EQUILIBRIUM CALCULATIONS

When two phases of a pure component are in equilibrium with each other, compositions of
the phases are the same. For example, when water vapor is in equilibrium with liquid water
at 373 K under atmospheric pressure, there is no dierence in compositions of phases. In the
case of multicomponent mixtures, on the other hand, compositions of the phases that are in
equilibrium with each other are not the same. Estimation of the compositions of components
in each phase is of practical interest to chemical engineers.

197
7.8.1 Vapor-Liquid Equilibrium
When pure liquid A evaporates into vapor B, evaporation takes place as long as

fAL (T, P ) > fbAV (T, P, yA ) Mass transfer from liquid to vapor (7.8-1)

In writing Eq. (7.8-1) it is implicitly assumed that the solubility of B in the liquid is negligible,
i.e., liquid exists as pure A. The mass transfer of A to the vapor phase stops when the system
reaches equilibrium, i.e.,

fAL (T, P ) = fbAV (T, P, yA

) Condition of equilibrium (7.8-2)

Under these conditions vapor is saturated with A, yA being the corresponding mole fraction. In

other words, when vapor is saturated with A, it contains the maximum amount of A at a given
temperature and pressure. The use of Eqs. (5.4-8) and (7.3-4) for the left- and right-hand sides
of Eq. (7.8-2), respectively, results in

VeAL (P PAvap )
PAvap VA (T, PAvap ) exp = yA
bV (T, P, y )
P (7.8-3)
A A
RT

If pressure is not very high, the following simplifying assumptions are plausible:

Poynting correction factor is unity,

The vapor of A at T and PAvap is ideal, i.e., VA (T, PAvap ) = 1,
bV (T, P, y ) = 1.
Vapor is an ideal gas mixture, i.e., A A

Under these circumstances, Eq. (7.8-3) simplifies to

PAvap = yA

P (7.8-4)

indicating that vapor is saturated with A when its partial pressure equals vapor pressure at
the given temperature.
For example, vapor pressure of liquid water at 298 K is 3.169 kPa. Air at 298 K and 101.3 kPa
is saturated with water vapor (or relative humidity is 100%) when the partial pressure of water
vapor equals 3.169 kPa. Under these conditions, air holds the maximum water with a mole
fraction of
PHvap
2O 3.169

yH 2 O = = = 0.0313
P 101.3

Example 7.8 Three liters of toluene accidentally spills on the laboratory floor. Determine
the fraction of toluene vaporized over a long period of time, say 24 h, if the volume of the
laboratory is 180 m3 . Assume that the laboratory temperature remains constant at 298 K.

Solution

From Appendix A
Tc = 593 K Pc = 41 bar = 0.263
From Appendix C
3096.52
ln P vap = 9.3935
T 53.67

198
The toluene spilled on the floor will vaporize into air as long as
L
ftoluene (T, P ) > fbtoluene
V
(T, P, ytoluene ) (1)
In writing Eq. (1) it is implicitly assumed that air has a negligible solubility in liquid toluene so
that the liquid phase is pure toluene. Under equilibrium conditions, i.e., when air is saturated
with toluene, vaporization stops and we have
L
ftoluene (298 K, 1.013 bar) = fbtoluene
V
(298 K, 1.013 bar, ytoluene ) (2)

where ytoluene represents the mole fraction of toluene in air saturated with toluene at 298 K and
atmospheric pressure, i.e., 1.013 bar. Using the same assumptions in simplifying Eq. (7.8-3),
Eq. (2) reduces to
vap
vap
Ptoluene

Ptoluene = P ytoluene ytoluene = (3)
P
At 298 K, the vapor pressure of toluene is

vap 3096.52
Ptoluene = exp 9.3935 = 0.038 bar
298 53.67
Substitution of numerical values into Eq. (3) gives
0.038
ytoluene = = 3.75 102
1.013
In other words, liquid toluene vaporizes until its mole fraction in the vapor phase reaches
3.75 102 .

Now it is necessary to determine whether the spilled toluene causes air saturated with toluene
or not. From Table 5.2, the molar volume of liquid toluene is approximately 107 cm3 / mol.
Therefore, the number of moles of toluene is
Vbottle 3000
ntoluene = = = 28.04 mol
Ve L 107
The number of moles of air is
P Vlab (1.013)(180)
nair = = = 7359.6 mol
RT (8.314 105 )(298)
If all toluene were evaporated, then its mole would be
28.04
ytoluene = = 3.8 103
28.04 + 7359.6
which is less than the saturation value of 3.75 102 . Therefore, all toluene is evaporated.

It should be kept in mind that Eq. (7.8-3) simplifies to Eq. (7.8-4) as long as pressure
is low. When pressure is moderate or high, then it is necessary to use Eq. (7.8-3) as will be
shown in the next example.

Example 7.9 A cylinder contains propylene (1) and nitrogen (2) at 298 K and 18 bar. Esti-
mate the vapor phase composition if the solubility of nitrogen in liquid propylene is negligible.
Assume that the vapor phase is represented by the virial equation of state. Critical molar vol-
umes of propylene and nitrogen are 1.81 104 m3 / mol and 0.895 104 m3 / mol, respectively.
The vapor pressure of propylene at 298 K is 11.53 bar.

199
Solution

From Appendix A

Component Tc ( K) Pc ( bar)
Propylene 365.2 46 0.144
Nitrogen 126.2 34 0.039

Since the solubility of nitrogen in liquid propylene is negligible, the liquid phase consists of pure
propylene and the condition of equilibrium is given by Eq. (7.8-2) as

f1L (T, P ) = fb1V (T, P, y1 ) (1)

or, from Eq. (7.8-3),

Ve1L (P P1vap )
P1vap V1 (T, P1vap ) exp bV (T, P, y )
= y1 P (2)
1 1
RT

Calculation of the fugacity coecients requires virial coecients, B11 , B22 , and B12 , to be
calculated.
Calculation of second virial coecients for pure components

From Eqs. (3.1-10)-(3.1-13)

(83.14)(365.2) 0.422 0.172
B11 = 0.083 + (0.144) 0.139
46 (298/365.2)1.6 (298/365.2)4.2
= 356 cm3 / mol

(83.14)(126.2) 0.422 0.172
B22 = 0.083 + (0.039) 0.139
34 (298/126.2)1.6 (298/126.2)4.2
= 5.7 cm3 / mol

Calculation of second virial cross coecient

The parameters defined by Eqs. (6.1-3) and (6.1-4) are calculated as

q
ec Vec p

8 V 1 2 8 (1.81 104 ) (0.895 104 )
k12 =1 1/3 1/3
= 1 h i3 = 0.020
(Vec1 + Vec2 )3 (1.81 104 )1/3 + (0.895 104 )1/3

p p
Tc12 = (1 k12 ) Tc1 Tc2 = (1 0.020) (365.2)(126.2) = 210.4 K
1 + 2 0.144 + 0.039
12 = = = 0.092
2 2

(4)(210.4) (46)(1.81 104 ) (34)(0.895 104 )
Pc12 = h i3 +
365.2 126.2
(1.81 104 )1/3 + (0.895 104 )1/3
= 37.98 bar

200
 (0) (1)
The parameters B12 and B12 are calculated from Eqs. (3.1-11) and (3.1-12), respectively, as

(0) 0.422
B12 = 0.083 = 0.159
(298/210.4)1.6

(1) 0.172
B12 = 0.139 = 0.099
(298/210.4)4.2
Finally, the second virial cross coecient B12 is calculated from Eq. (3.1-10) as
(83.14)(210.4) h i
B12 = 0.159 + (0.092) (0.099) = 69.04 cm3 / mol
37.98
Calculation of fugacity coecients
The fugacity coecient of pure propylene vapor is calculated from Eq. (5.3-5) as
!
vap
B11 P1vap ( 356)(11.53)
V
1 (T, P1 ) = exp = exp = 0.847
RT (83.14)(298)

The fugacity coecient of propylene in the vapor phase is calculated from Eq. (7.5-6) as
i
b V P h 2
1 (T, P, y1 ) = exp B11 + (1 y1 ) (2 B12 B11 B22 )
RT
n h io
(18) 2
= exp 356 + (1 y1 ) (2)( 69.04) + 356 + 5.7
(83.14)(298)
h i
= exp 0.259 + 0.162 (1 y1 )2 (3)

The molar volume of liquid propylene is calculated from the Rackett equation, Eq. (5.4-9), as

ZRA = 0.29056 (0.08775)(0.144) = 0.278

(83.14)(365.2) 2/7
Ve1L = (0.278)1+[1(298/365.2)] = 83.3 cm3 / mol
46
Substitution of the numerical values into Eq. (2) gives
h i
(83.3)(18 11.53)
(11.53)(0.847) exp = y1 (18) exp 0.259 + 0.162 (1 y1 )2 (4)
(83.14)(298)

R
The solution of Eq. (4) by MATHCAD gives y1 = 0.404.

Condensation is the reverse of vaporization. Let us calculate the temperature at which

condensation starts when the vapor composition and pressure are known. Suppose that air
at 298 K and 101.3 kPa has a relative humidity of 80%. The partial pressure of water vapor,
PH 2 O , in air is
pH 2 O = yH2 O PHvap
2O
= (0.80)(3.169) = 2.535 kPa
Condensation, or mass transfer from the vapor to the liquid, takes place if

fbHV2 O (T, P, yH 2 O ) > fHL2 O (T, P ) pH 2 O > PHvap

2O

In writing the above equation, it is implicitly assumed that the solubility of air in water is
negligible. In our case since pH 2 O < PHvap
2O
, no condensation occurs. As the temperature is

201
decreased, the amount of water vapor in air does not change. The first liquid droplet appears
when the temperature drops to T , at which point4

pH2 O = PHvap
2O
= 2.535 kPa

In other words, air becomes saturated with water vapor. The use of the Antoine equation gives
the dew point temperature as
3816.44
T = 46.13 + = 294.6 K (21.6 C)
11.6834 ln(2.535/100)

Figure 7.1 illustrates the dew point temperature of an air-water system.

Saturation Line
Pressure

PHvap
O 2

PH O
2

Tdew T
Temperature

Figure 7.1 Dew point temperature of an air-water system.

Example 7.10 A piston-cylinder arrangement holds a gas mixture of 20 mol % chloroform

(1) and 80% nitrogen (2) at 340 K and 1.013 bar. The system is cooled under constant pressure.
Estimate the temperature at which condensation of chloroform takes place.

Solution

From Appendix C
2696.79
ln P1vap = 8.3530
T 46.16

Let T be the temperature at which the first liquid droplet of chloroform appears. If the solubility
of nitrogen in liquid chloroform is assumed negligible, i.e., the liquid phase is pure chloroform,
then the condition of equilibrium is expressed as

f1L (T , 1.013 bar) = fb1V (T , 1.013 bar, y1 ) (1)

or,
( )
h i Ve1L 1.013 P1vap (T ) V
P1vap (T ) V1 T
, P1vap (T ) exp b (T , 1.013 bar, y1 )
= (1.013) y1 1
RT
(2)
Since the pressure is atmospheric, the following simplifying assumptions are plausible:
Poynting correction factor is unity,
Vapor phase is an ideal gas mixture, i.e., bV (T , 1.013 bar, y1 ) ' 1

1
V1 T , P1vap (T ) ' 1
4
This is known as the dew point temperature. Such calculations will be covered in detail in Chapter 9.

202
Therefore, Eq. (2) simplifies to

P1vap (T ) = 1.013 y1 = (1.013)(0.2) = 0.203 bar

The temperature, T , is calculated from the Antoine equation as

2696.79
T = 46.16 + = 317.3 K
8.3530 ln(0.203)

Comment: Since the pressure is atmospheric, simplifying assumptions lead to a straightfor-

ward calculation of T . In the case of high pressures, one should use a trial-and-error procedure
to estimate T , i.e., assume T and check whether Eq. (2) is satisfied.

7.8.2 Solid-Liquid Equilibrium

Let us add a small amount of sugar to a cup filled with tea. If we stir the tea in the cup,
the sugar will disappear. This means the tea is unsaturated with sugar or, in other words, the
fugacity of the solid sugar is greater than the fugacity of the sugar in the tea, i.e.,
S
fsugar (T, P ) > fbsugar
L
(T, P, xsugar ) Mass transfer from solid to liquid (7.8-5)

If we keep continue adding sugar to the tea at constant temperature, a point comes where the
liquid is saturated with sugar

S
fsugar (T, P ) = fbsugar
L (T, P, xsugar ) Condition of equilibrium (7.8-6)

The saturated condition, i.e., xsugar = xsugar , represents the maximum amount of sugar that
can be present in the tea at the given temperature and pressure. After this point, any additional
sugar will not dissolve and will appear as a solid phase within the cup. Solid-liquid equilibrium
will be discussed in detail in Chapter 12.

7.8.3 Solid-Vapor Equilibrium

Consider sublimation of species A into vapor B. Sublimation takes place as long as

fAS (T, P ) > fbAV (T, P, yA ) Mass transfer from solid to vapor (7.8-7)

In writing Eq. (7.8-7) it is implicitly assumed that the solid phase is pure A, i.e., solubility of
B in the solid phase is negligible. Sublimation stops when vapor B is saturated with A, i.e.,
yA = yA , at the given temperature and pressure. Under these conditions

fAS (T, P ) = fbAV (T, P, yA

) Condition of equilibrium (7.8-8)

The use of Eqs. (5.5-8) and (7.3-4) for the left- and right-hand sides, respectively, of Eq. (7.8-8)
leads to " S #
VeA (P PAsub )
PAsub exp
= yA PbV (T, P, y ) (7.8-9)
A A
RT
or !
PAsub

yA = E (7.8-10)
P

203
where the enhancement factor, E, is defined by
" S #
VeA (P PAsub )
exp
RT
E= (7.8-11)
bV
A

As stated in Section 5.6, supercritical fluids are at a temperature and pressure greater than
or equal to the critical temperature and pressure of fluids. At high pressures, supercritical fluids
possess solvent properties that are superior to those of liquid solvents. As a result, they may
be an alternative to replace toxic and environmentally hazardous solvents used in separation
and/or purification processes. Being nontoxic, inexpensive, and nonflammable, and having a
low critical temperature, carbon dioxide is one of the most widely used supercritical fluids for
extraction purposes. The design of extraction processes involving supercritical solvents requires
the understanding of solid-vapor equilibrium.

Example 7.11 It is required to estimate the solubility of naphthalene (2) in carbon dioxide
(1) at 118.6 bar and 328 K for a supercritical extraction. Assume that the vapor phase is
represented by the Peng-Robinson equation of state with k12 = 0.08246. For naphthalene, the
sublimation pressure at 328 K and the molar volume are 15.9 104 bar and 111.9 cm3 / mol,
respectively.

Solution

From Appendix A

Component Tc ( K) Pc ( bar)
Carbon dioxide 304.2 73.8 0.239
Naphthalene 748.0 41.0 0.302

Note that the given temperature is less than the triple point temperature of naphthalene, which
is 353.42 K from Table 5.3. Therefore, when the naphthalene content of vapor exceeds its
solubility limit, solid naphthalene is formed by desublimation. If the solid phase consists of pure
naphthalene, the condition of phase equilibrium states that the fugacity of pure solid naphthalene
is equal to the fugacity of naphthalene in the gas phase. Thus, Eq. (7.8-9) is expressed as
" #
Ve2S (P P2sub )
P2sub exp bV (T, P, y )
= y2 P (1)
2 2
RT

or
4 (111.9)(118.6 15.9 104 ) bV (T, P, y )
15.9 10 exp = y2 P 2 2 (2)
(83.14)(328)
| {z }
2.587103

Since the fugacity coecient of component 2 is dependent on the mole fraction, determination
of y2 from Eq. (2) requires a trial-and-error solution. Once the value of y2 is assumed, bV
2
is determined from Eq. (7.5-16). If the assumed y2 value is correct, then the right-hand side
(RHS) of Eq. (2) should be equal to 2.587 103 . The calculation procedure is tabulated below:

204
 y2 103 Amix Bmix V
Zmix bV
RHS of Eq. (3)
2

7.00 0.622 0.119 0.383 2.877 103 2.388 103

9.30 0.631 0.120 0.373 2.541 103 2.803 103
8.01 0.626 0.119 0.379 2.723 103 2.587 103

Therefore, the mole fraction of naphthalene in CO2 at 118.6 bar and 328 K is 8.01 103 . The
experimental value reported by McHugh and Paulaitis (1980) is 12.29 103 .
Comment: When the mole fraction of one of the components is very small, i.e., y1 ' 1 (or
y2 ' 0), the following simplifying assumptions are plausible:
V
Amix = A11 Bmix = B1 Zmix = Z1V (3)

and the fugacity coecient of component 2 takes the form

" #
V B2 V A11 2 A12 B2 Z1V + (1 +
2) B1
b
ln = Z1 1 ln Z1V B1 ln
2 V
approx B1 8 B1 A11 B1 Z1 + (1 2) B1
(4)
which is independent of composition. Thus, Eq. (2) becomes
V
2.587 103 = y P b (5)
2 2
approx

The numerical values of the parameters in the Peng-Robinson equation of state are

A11 = 0.597 B1 = 0.116

A12 = 2.372 B2 = 0.513

For pure CO2 , Eq. (6.1-9) becomes

Z13 0.884 Z12 + 0.325 Z1 0.054 = 0 Z1V = 0.414

The approximate value of the fugacity coecient of component 2 is calculated from Eq. (4) as
V
b
= 4.195 103
2
approx

Substitution of the numerical values into Eq. (5) gives

2.587 103 = y2 (118.6)(4.195 103 ) y2 = 5.2 103

As far as the order of magnitude is concerned, this value is not very far from the previously
calculated one.

In the above examples, our analysis is restricted to cases in which equilibrium takes place
between a pure component in one phase and a multicomponent mixture in another phase.
Obviously, this is not necessarily the case in general.

205
REFERENCES

Chueh, P.L. and J.M. Prausnitz, 1967, Ind. Eng. Chem. Fundam., 6 (4), 492-498.

Eggeman, T. and S. Chafin, 2005, Chem. Eng. Prog., 101 (3), 39-44.

Firoozabadi, A., 1999, Thermodynamics of Hydrocarbon Reservoirs, McGraw-Hill, New York.

Giauque, W.F. and C.J. Egan, 1937, J. Chem. Phys., 5 (1), 45-54.

Gurdial, G.S. and N.R. Foster, 1991, Ind. Eng. Chem. Res., 30 (3), 575-580.

McHugh, M. and M.E. Paulaitis, 1980, J. Chem. Eng. Data, 25, 326-329.

Mendes, R.L., B.P. Nobre, J.P. Coelho and A.F. Palavra, 1999, J. Supercritical Fluids, 16,
99-106.

Shibata, S.K. and S.I. Sandler, 1989, J. Chem. Eng. Data, 34, 419-424.

ZareNezhad, B. and T. Eggeman, 2006, Cryogenics, 46, 840-845.

PROBLEMS

Problem related to Section 7.2

7.1 Derive Eq. (7.2-11).

Problems related to Section 7.5

7.2 Derive Eq. (7.5-6) as follows:

a) By definition, the partial molar compressibility factor of component i is given by

(nZmix )
Zi = (1)
ni T,P,nj6=i

Show that the substitution of Eq. (7.5-5) into Eq. (1) and rearrangement give

n2 Bmix P
Zi = n+ (2)
ni nRT T,P,nj6=i

Carry out the dierentiation to obtain

k X
X k
Bmix P P
Zi = 1 + ni nj Bij (3)
RT nRT ni
i=1 j=1
T,P,nj6=i

b) To dierentiate the third term on the right-hand side of Eq. (3), first consider a binary
mixture of components 1 and 2, and show that

X2 X 2 2
X
ni nj Bij = 2 (n1 B11 + n2 B12 ) = 2 nj B1j (4)
n1
i=1 j=1 j=1
T,P,n2

206
Generalize Eq. (4) as

k X
X k k
X

ni nj Bij =2 nj Bij (5)
ni
i=1 j=1 j=1
T,P,nj6=i

Therefore, Eq. (3) takes the form

k
X
P
Zi = 1 + 2 yj Bij Bmix (6)
RT
j=1

c) Show that the substitution of Eq. (6) into Eq. (7.3-15) leads to Eq. (7.5-6).

7.3 Derive an expression to represent the overall fugacity coecient of the mixture, mix , as
follows:
a) Start with
k
X
emix =
G xi Gi (1)
i=1

and show that

k
X k
X
emix =
G xi i + RT xi ln fbi (2)
i=1 i=1

b) The fugacity of the mixture, fmix , is defined by

emix = mix + RT ln fmix
G (3)

with the following constraint

mix = fmix /P 1 as P 0 (4)

Equate Eqs. (2) and (3) to get

k
X k
X
mix + RT ln fmix = xi i + RT xi ln fbi (5)
i=1 i=1

Since Eq. (5) is valid at all pressures, evaluate Eq. (5) as P 0 to conclude that
k
X k
X
mix = xi i + xi ln xi (6)
i=1 i=1

c) Show that the use of Eq. (6) in Eq. (5) leads to

k
X
ln mix = b
xi ln (7)
i
i=1

or
k
Y
mix = bxi
(8)
i
i=1

207
Note that the form of Eq. (3) is similar to the one given for a pure component, Eq. (5.2-6).
Therefore, the pure component fugacity coecient equations given in Chapter 5 can also be
used to express the overall fugacity coecient of mixtures.

7.4 Equation (7) of Problem 7.3 suggests that the term ln bi can be interpreted as the partial
molar property of ln mix , i.e.,

b
ln i = (n ln mix ) (1)
ni T,P,nj6=i

Therefore, for a binary mixture, show that the application of Eqs. (6.1-24) and (6.1-25) gives

b = ln d ln mix
ln 1 mix x2 (2)
dx2

b = ln d ln mix
ln 2 mix x1 (3)
dx1
a) Note that Eq. (5.3-5) can be extended to mixtures as
Bmix P
ln mix = (4)
RT
b) Use Eq. (4) in Eqs. (2) and (3) to obtain
h i
b = P B11 + y 2 (2 B12 B11 B22 )
ln (5)
1 2
RT
h i
b = P B22 + y 2 (2 B12 B11 B22 )
ln (6)
2 1
RT

7.5 In the case of a pressure-explicit equation of state, the use of Eq. (1) in Problem 7.4, i.e.,

b = (n ln )
ln (1)
i mix
ni T,P,nj6=i

is not practical in the calculation of component fugacities. An alternative expression can be

developed as follows:

a) In general
n ln mix = f (T, P, Vmix , n1 , n2 , ..., nk ) (2)
In Eq. (1), temperature, pressure, and the number of moles of each component other than i
are kept constant during dierentiation. Therefore, Eq. (2) can be expressed as
n ln mix = g(Vmix , ni ) (3)
b) First express the total dierential of Eq. (3) as

(n ln mix ) (n ln mix )
d(n ln mix ) = dVmix + dni (4)
Vmix T,P,nj ni T,P,Vmix ,nj6=i

and then dierentiate Eq. (4) with respect to ni , by keeping T , P , and nj6=i constant, to obtain

(n ln mix ) (n ln mix ) Vmix (n ln mix )
= +
ni T,P,nj6=i Vmix T,P,nj ni T,P,nj6=i ni T,P,Vmix ,nj6=i
| {z }
Vi
(5)

208
c) Note that Eq. (5.3-1) can be extended to mixtures as
Z P e !
Vmix 1
ln mix = dP at constant T and nj (6)
0 RT P

Hence, conclude that

(n ln mix )
=0 (7)
Vmix T,P,nj

d) Combine Eqs. (1), (5), and (7) to obtain

bi = (n ln mix )
ln (8)
ni T,P,Vmix ,nj6=i

7.6 From Eq. (5.3-9), the overall fugacity coecient of the mixture obeying the van der
Waals equation of state is given by
Amix
ln mix = Zmix 1 ln(Zmix Bmix ) (1)
Zmix
a) Show that the substitution of Eq. (1) into Eq. (8) of Problem 7.5 and rearrangement give
2
bi = (nZmix )
ln 1
n Amix
ln(Zmix Bmix )
ni T,P,Vmix ,nj6=i ni nZmix T,P,Vmix ,nj6=i
( )
n nZmix nBmix
(2)
Zmix Bmix ni n T,P,Vmix ,nj6=i ni n T,P,Vmix ,nj6=i

b) Show that
(nZmix )
=0 (3)
ni T,P,Vmix ,nj6=i

P
k
xj Aij 2
n2 Amix j=1
= (4)
ni nZmix T,P,Vmix ,nj6=i Zmix

nZmix Zmix
= (5)
ni n T,P,Vmix ,nj6=i n

nBmix Bi Bmix
= (6)
ni n T,P,Vmix ,nj6=i n
Substitute Eqs. (3) - (6) into Eq. (2) to obtain Eq. (7.5-13).

7.7 From Eq. (5.3-9), the overall fugacity coecient of the mixture obeying the Redlich-
Kwong equation of state is given by

Amix Bmix
ln mix = Zmix 1 ln(Zmix Bmix ) ln 1 + (1)
Bmix Zmix

209
a) Show that the substitution of Eq. (1) into Eq. (8) of Problem 7.5 and rearrangement give

b = (nZmix )
ln 1 ln(Zmix Bmix )
i
ni T,P,Vmix ,nj6=i
( )
n nZmix nBmix

Zmix Bmix ni n T,P,Vmix ,nj6=i ni n T,P,Vmix ,nj6=i
2
Bmix n Amix nAmix Zmix nBmix
ln 1 +
Zmix ni nBmix T,P,Vmix ,nj6=i Bmix (Zmix + Bmix ) ni nZmix T,P,Vmix ,nj6=i
(2)

b) Show that
P
k
2 xj Aij
n2 Amix j=1 Amix Bi
= 2 (3)
ni nBmix T,P,Vmix ,nj6=i Bmix Bmix

nBmix Bi
= (4)
ni nZmix T,P,Vmix ,nj6=i nZmix
Substitute Eqs. (3) and (4) together with Eqs. (3), (5), and (6) of Problem 7.6 into Eq. (2) to
obtain

b Bi Amix Bi
ln i = ln (Zmix Bmix )
Zmix Bmix Bmix Zmix + Bmix
k
P
2 xj Aij
Amix j=1 Bi
Bmix
ln 1 + (5)
Bmix Amix Bmix Zmix

c) Combining the first two terms on the right-hand side of Eq. (5) and making use of the
Redlich-Kwong equation of state, i.e.,
3 2 2
Zmix Zmix + (Amix Bmix Bmix )Zmix Amix Bmix = 0 (6)

show that Eq. (5) reduces to Eq. (7.5-14).

7.8 Twenty-eight moles of methane (1), 16 moles of ethane (2), and 36 moles of carbon dioxide
(3) are mixed in a rigid tank at 320 K and 10 bar. Calculate the fugacities of each component
in the gas mixture using
a) The Lewis-Randall rule if pure gases obey the Peng-Robinson equation of state,
b) The virial equation of state with

B11 = 35.17 cm3 / mol B22 = 159.42 cm3 / mol B33 = 104.54 cm3 / mol
B12 = 76.71 cm3 / mol B13 = 54.02 cm3 / mol B23 = 105.65 cm3 / mol

(Answer: a) fb1 = 3.440 bar, fb2 = 1.867 bar, fb3 = 4.305 bar b) fb1 = 3.467 bar, fb2 = 1.902 bar,
fb3 = 4.341 bar)

7.9 A ternary mixture consisting of 50 mol % methane (1), 30% ethane (2), and 20% propane
(3) is at 380 K and 200 bar. The mixture is represented by the van der Waals equation of state.

210
a) Estimate the fugacities of each component in the mixture.
b) Repeat the calculations for an ideal mixture.
(Answer: a) fb1 = 92.132 bar, fb2 = 31.860 bar, fb3 = 14.875 bar b) fb1 = 86.362 bar,
fb2 = 31.209 bar, fb3 = 13.572 bar)

7.10 A gaseous mixture consisting of 15 mol % methane (1), 25% ethylene (2), 20% ethane
(3), and 40% propane (4) is at 400 K and 150 bar. Calculate the component fugacities in the
mixture using the Peng-Robinson equation of state with

k12 = 0.022 k13 = 0.003 k14 = 0.016 k23 = 0.010 k24 = 0 k34 = 0.001

(Answer: fb1 = 25.935 bar, fb2 = 27.508 bar, fb3 = 19.058 bar, fb4 = 24.077 bar)

7.11 A rigid tank is divided into two parts by a rigid semi-permeable membrane through
which carbon dioxide can pass. One side contains a gaseous mixture consisting of 70 mol %
carbon dioxide (1) and 30% methane (2) at 323 K and 60 bar. The other side contains pure
carbon dioxide at 323 K. Estimate the pressure of pure carbon dioxide so as to stop diusion
of carbon dioxide through the membrane if the gas phase obeys the Peng-Robinson equation
of state with k12 = 0.09.
(Answer: 38.3 bar)

7.12 This is the continuation of Problem 4.3 for a multicomponent system.

a) For a multicomponent system, show that Eq. (3) of Problem 4.3 takes the form
k
X
dG = V dP S dT + mg dz + (Gi + Mi gz) dni (1)
i=1

b) Under equilibrium conditions, i.e., dG = 0, conclude that

dT = 0 T is uniform (2)

dP
V dP + mg dz = 0 = g (3)
dz
Gi + Mi gz = 0 (4)
Keep in mind that the distance z is measured in the direction opposite to gravity.
c) Dierentiate Eq. (4) by keeping temperature constant to obtain

dGi = RT d ln fbi = Mi g dz (5)

which is known as the Gibbs sedimentation expression (Firoozabadi, 1999).

d) Show that the integration of Eq. (5) gives

Mi gz
ln fbi = +C (6)
RT
where C is an integration constant. If the temperature is uniform in a well of depth H, show
that Eq. (6) takes the form

fbi,bottom Mi gH
= exp (7)
fbi,top RT

211
e) The composition at the top of a natural gas well of depth 3 km is 90 mol % methane (1)
and 10% ethane (2). The temperature within the well is uniform at 310 K and the pressure at
the top of the well is 120 bar. It is required to estimate the composition and the pressure at
the bottom of the well.
i) Assuming natural gas to be an ideal gas mixture, show that Eq. (7) reduces to

y1 y1 (M1 M2 )gH
= exp (8)
y2 bottom y2 top RT

First use Eq. (8) with y1 + y2 = 1 and estimate the composition at the bottom of the well.
Then calculate the pressure at the bottom of the well.
ii) Assuming natural gas to be an ideal mixture, show that Eq. (7) takes the form

(f1 P )top M1 gH
y1,bottom = y1,top exp (9)
(f1 P )bottom RT

(f2 P )top M2 gH
y2,bottom = y2,top exp (10)
(f2 P )bottom RT
First assume the pressure at the bottom of the well and calculate pure component fugacities
using the Peng-Robinson equation of state. Then determine the mole fractions using Eqs. (9)
and (10). Repeat this procedure until y1 + y2 = 1.
(Answer: e) y1 = 0.8847 P = 146.5 bar; y1 = 0.85 P = 139.7 bar)

Problems related to Section 7.8

7.13 Since the sublimation pressure of solids is very small, its determination by experimental
techniques is often dicult. One way of determining the sublimation pressure is to use the
solubility data. Mendes et al. (1999) reported that the solubility of -carotene (2) in carbon
dioxide (1) at 313.15 K and 201 bar is y2 = 13 108 . Using the following data for -carotene

Tc = 1177 K Pc = 12.4 bar = 1.04 Ve S = 536.5 cm3 / mol

and the Peng-Robinson equation of state with k12 = 0.1013, estimate the sublimation pressure
of -carotene at 313.15 K. Mendes et al. reported the sublimation pressure as 1.72 1019 bar.
(Answer: 1.68 1019 bar)

7.14 Determine the solubility of salicylic acid (2) in supercritical carbon dioxide (1) at 313 K
and 192.5 bar. Assume that the vapor phase is represented by the Peng-Robinson equation of
state with k12 = 0.233. For salicyclic acid

Tc = 864.79 K Pc = 50.24 bar = 0.785

At 313 K, the sublimation pressure and the molar volume of solid salicyclic acid are 2.86
106 bar and 95.70 cm3 / mol, respectively. The experimental value reported by Gurdial and
Foster (1991) is y2 = 3.64 104 .
(Answer: 3.50 104 )

7.15 A natural gas mainly consists of methane. Cryogenic processes are used in natural gas
plants for the separation of methane from heavier alkanes. The presence of carbon dioxide, due
to its relatively high triple point, in a methane stream causes freezing, leading to clogging of

212
pipes and other operational problems. Consider a mixture of methane (1) and carbon dioxide
(2) in which the mole fraction of CO2 is 0.1. If the pressure is 50 bar, estimate the temperature
at which carbon dioxide freezes out using the Peng-Robinson equation of state. The following
data are provided by ZareNezhad and Eggeman (2006):

S2 = 1562 kg/ m3

3108.2
P2sub 6
= 9.44 10 exp
T
where P2sub is in bar and T is in K. The interaction parameter is given as a function of
temperature in the form
5.4835 36.134
k12 = 0.0998 +
T T2
Repeat the calculations when y2 = 0.01. For more details on the problem, see Eggeman and
Chafin (2005).
(Answer: 189.8 K, 152 K)

7.16 Consider vapor-liquid equilibrium between nitrogen (1) and water (2) in a rigid container
at low temperature. The vapor phase nonideality is represented by the virial equation of state.
Note that the following assumptions are plausible for this problem:
Solubility of nitrogen in liquid water is negligible, i.e., x2 ' 1.
Since the temperature is low, then the vapor pressure of water is also low, i.e., y2 y1 .
Under these circumstances, show that the equality of water fugacities in the liquid and vapor
phases leads to h i
vap
(Ve L + B11 ) 2B12 P

P2 2
y2 = exp
P
RT

213
214