SOLUTION

THERMODYNAMICS:
THEORY
THE IDEAL GAS MIXTURE MODEL
FUGACITY AND FUGACITY COEFFICIENT: PURE SPECIES
THE IDEAL GAS MIXTURE
MODEL
The molar volume of an ideal gas is V = RT/P. All ideal
gases, whether pure or mixed, have the same molar
volume at the same T and P.
The partial molar volume of species i in an ideal gas
mixture is found from eq. (11.7) applied to the
volume; superscript ig denotes the ideal gas state:
nV ig nRT / P RT n RT
V
i
ig

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

n ni j n j
where the final equality depends on the equation
This means that for ideal gases at given T and P the
partial molar volume, the pure species molar volume,
and the mixture molar volume are identical:

RT
Viig Viig V ig (11.20)
P 2
 Partial pressure of species i in an ideal gas mixture is define as
the pressure that species i would exert if it alone occupied the
molar volume of the mixture.
yi RT
pi ig
yi P i 1, 2, ..., N
V
where yi is the mole fraction of species i. The partial pressures
obviously sum to the total pressure.
Gibbss theorem statement:

A partial molar property (other than volume) of a constituent

species in an ideal gas mixture is equal to the corresponding
molar property of the species as a pure ideal gas at the
mixture temperature but at a pressure equal to its partial
pressure in the mixture.
This is expressed mathematically for generic partial property

Vthe equation:
M by ig
i i
ig

M iig T , P M iig T , pi (11.21) 3
 The enthalpy of an ideal gas is independent of
pressure; therefore

H iig T , P H iig T , pi H iig T , P

More simply,
H iig H iig (11.22)

whereH iig is the pure species value at the mixture T

and P. U iig
An analogous equation applies for and other
properties that are independent of pressure.

4
 5
The entropy of an ideal gas does depend on pressure, and
by eq. (6.24),

dT dP
dSiig C pig R (6.24)
T P
dSiig Rd ln P const T
Integration from pi to P gives
P P

dS
ig
i R d ln P const T
pi pi

P P
Siig T , P Siig T , pi R ln R ln R ln yi
pi yi P
Siig T , pi Siig T , P R ln yi
Substituting this result into eq. (11.21) written for the

entropy yields

Si T , P Si T , P R ln yi
ig ig
M i T , P M i T , pi
ig ig
(11.21)

S Siig R ln yi
ig (11.23)
i
or
Siig 5
 6
G ig H ig TS ig
For the Gibbs energy of an ideal gas mixture,
the parallel relation for partial properties is

G H TSiig
ig
i
ig
i

In combination with eqs. (11.22) and (11.23) this

becomes

H iig H iig (11.22)
Giig H iig TSiig RT ln yi
(11.23)
Siig Siig R ln yi

G Giig RT ln yi
ig
i
ig
i
(11.24)
or

The summability relation, eq. (11.11), with eqs. (11.22),

(11.23), and H ig
yyields
(11.24) ig
i Hi
i
(11.25)

S ig yi Siig R yi ln yi (11.26)
i i

G ig yi Giig RT yi ln yi (11.27)
i i
6
 7

When eq. (11.25) is written,

H ig yi H iig 0
i

the difference on the left is the enthalpy change

associated with a process in which appropriate amounts
of the pure species at T and P are mixed to form one
mole of mixture at the same T and P. For ideal gases,
this enthalpy change of mixing is zero.
When eq. (11.26) is rearranged as
1
S ig yi Siig R yi ln
i i yi

the left side is the entropy change of mixing for ideal

gases.
Because 1/yi > 1, this quantity is always positive, in
agreement with the second law.
7
 ig
An alternative expression for the chemical potential
i

results
Giigwhen in eq. (11.24) is replaced by an
expression giving its T and P dependence.
This comes from eq. (6.10) written for an ideal gas:
RT dG VdP SdT
dGiig Viig dP dP RTd ln P const T
P (6.10)
Integration gives
Giig i T RT ln P (11.28)
where i T , the integration constant at constant T, is
a species-dependent function of temperature only.
Eq. (11.24) is now written as

G i T RT ln yi P
ig
i
ig
i
(11.29)

where the argument of the logarithm is the partial

pressure.
Application of the summability relation, eq. (11.11),
producesig an expression for the Gibbs energy of an ideal
G yi i T RT yi ln yi P
gas mixture: (11.30)
i i 8
 FUGACITY AND FUGACITY
COEFFICIENT: PURE SPECIES
From eq. (11.6), the chemical potential i provides the
fundamental criterion for phase equilibria as well as for
chemical reaction equilibria. i i ... i i 1,2,..., N

However, the Gibbs energy, and hence i is defined in

GH
relation to the internal energy TS
and entropy. H U PV
Because absolute values of internal energy are unknown,
the same is true for i.
Moreover, eq. (11.29) shows that iig approaches negative
infinity when either P or yi approaches zero. This is true not
just for ideal gas but for any gas.

G i T RT ln yi P
ig
i
ig
i
(11.29)

Although these characteristics do not preclude the use of

chemical potentials, the application of equilibrium criteria is
facilitated by introduction of the fugacity, a property that
takes the place of i but which does not exhibit its less 9
 The concept of fugacity was introduced so that the ideal gas
mixture equations could be used for real fluids (which
deviate from ideal gas behavior).
The origin of the fugacity concept resides in eq. (11.28),
valid only for pure species i in the ideal gas state.

Giig i T RT ln P (11.28)
For a real fluid, an analogous equation that defines fi, the
fugacity of pure species i is written:

Gi i T RT ln f i (11.31)
This new property fi, with units of pressure, replaces P in eq.
(11.28). If eq. (11.28) is a special case of eq. (11.31), then:

f iig P (11.32)
and the fugacity of pure species i as an ideal gas is
necessarily equal to its pressure.
Subtraction of eq. (11.28) from eq. (11.31), both written for
the same T and P, gives
fi
Gi Gi RT ln
ig

P 10
 M R M M ig
By definition of eq. (6.41), ; Gi Giig is
the residual Gibbs energy, GiR; thus
GiR RT ln i (11.33)

where the dimensionless ratio fi/P has been defined as

fugacity coefficient, given by the symbol i:
f
i i (11.34)
P
Eq. (11.34) apply to pure species i in any phase at any
condition.
As a special case they must be valid for ideal gases, for
which GiR = 0, i = 1, and eq. (11.28) is recovered from
eq. (11.31).
GR P dP (6.45)
Eq. (11.33) may be Z 1 for

J written P = 0, and
const T combine with
eq. (6.45): RT 0 P
Pg 209 GiR
lim lim ln i J
P 0 RT P 0
11
 12

In connection with eq. (6.48), the value of J is

immaterial, and is set equal to zero.
SR P Z dP P dP
R
T
0
T P P
0 Z 1
P (6.48)

f i
lim ln i lim ln 0
P 0 P 0
P

and f i
lim i lim 1
P 0 P
P 0

The identification of ln i with GiR/RT by eq. (11.33)
permits its evaluation by the integral of eq. (6.49)
GR P dP
Z 1 const T (6.49)
RT 0 P
P dP
ln i Z i 1 const T (11.35)
0 P
12
 13

Fugacity coefficients (and therefore fugacities) for pure

gases are evaluated by eq. (11.35) from PVT data or
from a volume explicit equation of state.
For example, when the compressibility factor is given
by eq (3.38), PV BP
Z 1 (3.38)
RT RT

Bii P
Zi 1
RT

Bii P
Because Bii is
ln ai
function const T
dPof temperature only for a pure
RT 0
species, substitution into eq. (11.35) gives
B P (11.36)
ln i ii
RT
13
 FUGACITY COEFFICIENTS FROM THE
GENERIC CUBIC EQUATION OF STATE
Evaluation of fugacity coefficients through cubic
equations of state (e.g. the Van der Waals,
Redlich/Kwong, and Peng Robinson eqs) follows directly
from combination ofeqs. (11.33) and (6.66b):
G R RT ln (11.33)
i i

GR
Z 1 ln Z qI (6.66b)
RT
ln i Z i 1 ln Z i i qi I i (11.37)

where bP
(3.50) where:
RT a and b are positive
a T constant
q (3.51) and are pure numbers,
bRT
same for all substances
1 1 b
I ln (6.65b)
1 b
14
 This eqn. written for pure species i (for the van der
Waals equation, Ii = i/Zi).
Application of eq. (11.37) at a given T and P requires
prior solution of an equation of state for Zi by eq.
(3.52) for a vapor phase or eq. (3.56) for a liquid
phase. Z
Z 1 q (3.52)
Z Z
1 Z
Z Z Z (3.56)
q

15
 16

VAPOR/LIQUID EQUILIBRIUM
FOR PURE SPECIES
Eq. (11.31) may be written for species i as saturated
vapor and as a saturated liquid at the same
temperature:
Gi i T RT ln f i (11.38a)

Gil i T RT ln f il (11.38b)

By difference, f
Gi Gil RT ln i l
fi

This eqn applies to the change of state from saturated

liquid to saturated vapor, both at temperature T and
at the vapor pressure Pisat.

16
 According to eq. (6.69), Giv - Gil = 0; therefore:
G G (6.69)
f i f il f i sat (11.39)

where fisat indicates the value for either saturated

liquid or saturated vapor.
Coexisting phases of saturated liquid and saturated
vapor are in equilibrium; eq. (11.39) therefore
expresses a fundamental principle:
For a pure species coexisting liquid and vapor
phases are in equilibrium when they have the
same temperature, pressure and fugacity.

17
 An alternative formulation is based on the
corresponding fugacity coefficients:
f i sat
i sat
sat
(11.40)
Pi
whence i il isat (11.41)

This equation, expressing equality of fugacity

coefficients, is an equally valid criterion of
vapor/liquid equilibrium for pure species.

18
FUGACITY OF A PURE LIQUID
The fugacity of pure species i as a compressed liquid may be
calculated from the product of easily evaluated ratios:

fi l
P
f P f P
f i Pi sat
P
i
l
i
sat
i
l
sat

f P f P
sat i
P sat l sat
14 2 43 14 i
2 43 14 2 43
i i i i
A B C
Ratio (A) is the vapor phase fugacity coefficient of pure vapor i
at its vapor/liquid saturation pressure, designated isat. It is
given by eq. (11.35), written,
dP
Z i 1
Pisat
ln i
sat
const T (11.42)
0 P

In accord with eq. (11.39) ratio (B) is unity.

Ratio (C) reflects the effect of pressure on the fugacity of pure
liquid i.

19
 The basis of its calculation is eq. (6.10), integrated at
constant T to give
P dG VdP SdT (6.10)
Gi Gisat sat
Vil dP
Pi

Another expression for this difference results when eq.

(11.31) is written for both Gi and Gisat; subtraction then yields
fi Gi i T RT ln f i (11.31)
Gi Gisat RT ln sat
fi
The two expressions for Gi Gisat are set equal:
fi 1 P
ln
fi sat

RT Pisat
Vil dP
Ratio (C) is then

f il P 1 P

f il Pi sat
exp
RT Pisat
Vil dP

Substituting for the three ratios in the initial equation yields

1 P
f i isat Pisat exp
l
Vi dP (11.43)
RT Pi sat
20
 Because Vil, the liquid phase molar volume, is a very
weak function of P at temperatures well below Tc, an
excellent approximation is often obtained when Vil is
assumed constant at the value for saturated liquid. In
this case,
f i isat Pisat exp
V i
l
P Pi
sat

(11.44)
RT

The exponential is known as Poynting factor. Data

required for application of this equation:
Values of Ziv for calculation of isat by eq. (11.42).
These may come from an equation of state, from
experiment, or from a generalized correlation.
The liquid phase molar volume Vil, usually the value
for saturated liquid.
A value for Pisat. 21
 If Ziv is given by eq. (3.38), the simplest form of the
virial equation, then

B P Bii Pi sat
Z 1 ii
i and i
sat
exp
RT RT

and eq. (11.44) becomes

f i Pi sat
exp

Bii Pi sat Vil P Pi sat (11.45)
RT

22
EXAMPLE 11.5
For H2O at a temperature of 300oC (573.15K) and for
pressures up to 10 000 kPa (100 bar) calculate values
of fi and i from data in the steam tables and plot
them vs. P.

23
Solution:
Eq. (11.31) is written twice:
First, for a state at pressure P;
Second, for a low pressure reference state, denoted
by *,
Both for temperature T:
Gi i T RT ln f i and Gi* i T RT ln f i *

Subtraction eliminates i (T), and yields

fi 1
ln
f i* RT
Gi Gi
*

By definition
f i G1i =H iHi H
*TSi and G i* = Hi* - TSi*;
ln * gives
substitution
i
Si S i
*
(A)
f iR T
24
The lowest pressure for which data at 300oC
(573.15K) are given in the steam table is 1 kPa.
Steam at these conditions is for practical purposes an
ideal gas, for which fi* = P* = 1 kPa. Data for this
state provide the following reference values:

Hi* = 3076.8 J g-1 Si* = 10.3450 J g-1 K-1

Eq. (A) may now be applied to states of superheated

steam at 300oC (573.15K) for various values of P from
1 kPa to the saturation pressure of 8592.7 kPa.

For example, at P = 4000 kPa and 300oC (573.15K):

Hi = 2962.0 J g-1 Si = 6.3642 J g-1 K-1

25
 26

Values of H and S must be multiplied by the molar mass of water

(18.015 g mol-1) to put them on a molar basis for substitution into eq.
(A):

18.015g mol -1 2962.0 3076.8 J g

-1
fi
ln * -1 -1
6.3642 10.3450 J g K
-1 -1

fi 8.314 J mol K 573.15K

8.1917
fi
3611.0
f i*

f i 3611.0 f i* 3611.0 1 kPa 3611.0 kPa

Thus the fugacity coefficient at 4000 kPa is

f i 3611.0
i 0.9028
P 4000
26
Similar calculations at
other pressures lead to the
values plotted in Fig. 11.3
at pressures up to the
saturation pressure Pisat =
8592.7 kPa. At this
pressure,
Hi = 1345.1 J g-1
Si = 3.2552 J g-1 K-1
f i 6738.9 kPa
sat

Substitution in eq. (A)

and
yields
isat 0.7843

27
 28
According to eqs. (11.39) and
(11.41), the saturation values are
unchanged by condensation.
Although the plots are therefore
continuous, they do show
discontinuities in slope.

Values of fi and i for liquid water at

higher pressures are found by
application of eq. (11.44), with Vil
equal to molar volume of saturated
liquid water at
3 300
oC:
Vi 1.404cm g 18.015g mol -1
l -1

25.29 cm 3 mol -1

At 10 000 kPa, for example, eq. (11.44) becomes

fi 0.7843 8592.7 kPa exp

25.29cm mol 10000 8592.7 kPa
3 -1

6789.8 kPa
8314cm3
kPa mol -1
K
-1
573.15K
The fugacity coefficient of liquid water at these condition is
i f i P 6789.8/10000 0.6790
28
 29
Such calculations allow
completion of Fig. 11.3, where
the solid lines show how fi and i
vary with pressure.
The curve for fi starts at the
origin, and deviates increasingly
from the dashed line for an ideal
gas (fi = P) as the pressure rises.
At Pisat there is discontinuity in
slope, and the curve then rises
very slowly with increasing
pressure, indicating that the
fugacity of liquid water at 300oC
(573.15K) is a weak function of
pressure.
This behavior is characteristic of
liquids at temperatures well
below the critical temperature.
The fugacity coefficient i
decreases steadily from its zero
pressure value of unity as the
pressure rises. Its rapid 29
REFERENCE
Smith,J.M., Van Ness, H.C., and Abbott, M.M.
2005. Introduction to Chemical
Engineering Thermodynamics. Seventh
Edition. Mc Graw-Hill.

30
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
[email protected]
03-55436333/019-2368303