CHE553 Chemical Engineering Thermodynamics

4/4/2016

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
Vi ig

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

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.

where the final equality depends on the equation n ni n j

j
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:

Vi ig Vi ig V ig

RT
P

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.
y RT
pi i ig y i 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:

This is expressed mathematically for generic partial property Miig Vi ig

by the equation:

(11.20)

Miig T , P Miig T , pi

(11.21)

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

The enthalpy of an ideal gas is independent of pressure; therefore

dSiig C pig

ig
i

H T , P Hiig T , pi Hiig T , P

dSiig Rd ln P
Integration from pi to P gives

More simply,

ig
i

(11.22)

H Hiig

dT
dP
R
T
P

dS

ig
i

where Hiig is the pure species value at the mixture T and P.

An analogous equation applies for Uiig and other properties that are
independent of pressure.

pi

(6.24)

const T

R d ln P

const T

pi

Siig T , P Siig T , pi R ln

P
P
R ln
R ln y i
pi
yiP

Substituting this result into eq. (11.21) written for the entropy yields

Siig T , pi Siig T , P R ln y i
or

Miig T , P Miig T , pi

(11.21)

Siig T , P Siig T , P R ln y i

where Siig is the pure-species value at the mixture T and P.

Siig Siig R ln y i

For the Gibbs energy of an ideal gas mixture, G ig H ig TS ig

the parallel relation for partial properties is

Mig y i Miig 0

From eq. (11.25), enthalpy change of mixing for ideal gas is zero.

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

G Hiig TSiig RT ln y i
or

ig
i

G G RT ln y i
ig
i

ig
i

Hiig Hiig

ig
i

S S R ln y i
ig
i

H ig y i Hiig 0

(11.22)

(11.23)

(11.26)

G ig y i G iig RT y i ln y i

(11.27)

1
yi

Because 1/yi > 1, this quantity is always positive, in agreement with the second
law.
From eq. (11.27), Gibbs free energy change of mixing for ideal gas is:

S ig y i Siig R y i ln y i

From eq. (11.26), entropy change of mixing for ideal gas is:

S ig y i Siig R y i ln

(11.24)

The summability relation, eq. (11.11), with eqs. (11.22), (11.23), and (11.24)
yields
H ig y i Hiig
(11.25)

Property change of mixing for ideal gas is defined as:

Giig Hiig TSiig

ig
i

(11.23)

G ig y i G iig RT y i ln y i
i

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An alternative expression for the chemical potential iig results when G iig
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
dG iig Vi ig dP
dP RTd ln P const T
P
Integration gives
(11.28)
Giig i T RT ln P

FUGACITY AND ITS IMPORTANCE

(6.10)

where i T , the integration constant at constant T, is a species-dependent

function of temperature only.
Eq. (11.24) is now written as

iig Giig Giig RT ln y i (11.24)

iig G iig i T RT ln y i P

(11.29)

where the argument of the logarithm is the partial pressure.

Application of the summability relation, eq. (11.11), produces an expression for
the Gibbs energy of an ideal gas mixture:

G ig y i i T RT y i ln y i P
i

Ideal gases and ideal gas mixtures have analytical and well defined equations
but their applications are limited. They cannot be used to describe the
behavior of real fluids (which deviate significantly from ideal gas behavior).
The concept of fugacity was introduced so that the ideal gas mixture equations
could be used for real fluids.
Fugacity is a property related to chemical potential. Chemical potential cannot
directly measured. Thus fugacity takes the place of chemical potential.
Fugacity measure the tendency of a substance to prefer one phase (liquid,
solid, gas) over another. The phase with the lowest fugacity will be the most
favorable. Therefore, fugacity is useful for predicting the phase state of multicomponent mixtures at various temperatures and pressures.
This chapter will concentrate on the definitions and formula of fugacities. The
next chapter will discuss on the applications of fugacities in vapor liquid
equilibrium.

(11.30)

FUGACITY AND FUGACITY COEFFICIENT:

PURE SPECIES
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)
The concept of fugacity was introduced in order for eq. (11.28) to be valid
for pure species, real fluid at constant temperature.
Thus, for a real fluid, an analogous equation that defines fi, the fugacity of
pure species i is written:
G i 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:
(11.32)
f i ig P
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
f
G i G iig RT ln i
P

10

A residual property is simply the difference of a system property to the

property if the system behaves as an ideal gas (or ideal gas mixture)
(6.41)
MR M Mig
In previous eqn., Gi Giig is the residual Gibbs energy, GiR; thus
(11.33)
G iR RT lni
where the dimensionless ratio fi/P has been defined as fugacity coefficient,
given by the symbol i:
f
(11.34)
i i
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).
Eq. (11.33) may be written for P = 0, and combine with eq. (6.45):
P
GR
dP
J Z 1
0
RT
P

11

const T

GR
lim i lim ln i J
P 0 RT

P 0

(6.45)

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In connection with eq. (6.48), the value of J is immaterial, and is set equal to
zero.
H
G
SR HR G R

R RT RT

and

(6.47)

RT

RT

P Z dP
P
SR
dP
T
Z 1

0 T P
0
R
P
P

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),
Z

(6.48)

f
limlni limln i 0
P 0
P 0
P

Z i 1

f
lim i lim i 1
P 0
P 0 P
The identification of ln i with GiR/RT by eq. (11.33) permits its evaluation by
the integral of eq. (6.49)
P
GR
dP
Z 1
RT 0
P

dP
lni Z i 1
0
P
P

PV
BP
1
RT
RT

const T

const T

(3.38)

Bii P
RT

Because the second virial coefficient, Bii is a function of temperature only for a
pure species, substitution into eq. (11.35) gives

(6.49)

lni

Bii P
dP
RT 0

ln i

Bii P
RT

const T
(11.36)

(11.35)
13

DETERMINATION OF FUGACITY
COEFFICIENT

14

FUGACITY COEFFICIENTS FROM THE

GENERIC CUBIC EQUATION OF STATE

There are a few methods for the determination of fugacity coefficient of pure
species:

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 of eqs. (11.33) and (6.66b):

Compressibility factor method, useful for academic purpose

Generalized correlations (e.g. Lee-Kesler), easy and practical
Derived from Equation of States (e.g. Virial, etc.), useful especially in computer
simulation

(11.33)

G iR RT lni
R

where

(6.66b)

lni Z i 1 ln Z i i qi Ii

(11.37)

bP
RT

(3.50)

a T
bRT

(3.51)

I
15

G
Z 1 ln Z qI
RT

1 b
ln
(6.65b)
1 b

where:
a and b are positive constant
and are pure numbers, same
for all substances

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VAPOR/LIQUID EQUILIBRIUM FOR PURE

SPECIES

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 1 q

Z
Z Z

Eq. (11.31) may be written for species i as saturated vapor and as a saturated
liquid at the same temperature:

(3.52)

1 Z
Z Z Z

Gi i T RT ln f i

(11.38a)

G i T RT ln f i

(11.38b)

l
i

By difference,

(3.56)

Gi G il RT ln

fi
fil

This eqn applies to the change of state from saturated liquid to saturated vapor,
both at temperature T and at the vapor pressure Pisat.

17

According to eq. (6.69), Giv - Gil = 0; therefore:

G G

(6.69)

f i f i l f i sat

(11.39)

18

An alternative formulation is based on the corresponding fugacity

coefficients:
f sat
isat i sat
(11.40)
Pi
whence
(11.41)
l sat

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:

This equation, expressing equality of fugacity coefficients, is an equally valid

criterion of vapor/liquid equilibrium for pure species.

For a pure species coexisting liquid and vapor phases are in

equilibrium when they have the same temperature, pressure
and fugacity.

19

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FUGACITY OF A PURE LIQUID

The basis of its calculation is eq. (6.10), integrated at constant T to give
dG VdP SdT

G i G isat sat Vi l dP

The fugacity of pure species i as a compressed liquid may be calculated from

the product of easily evaluated ratios:
fil P

Another expression for this difference results when eq. (11.31) is written for
both Gi and Gisat; subtraction then yields

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

Pi
Pi sat f i Pi sat f i l Pi sat
A

G i G isat RT ln

(6.10)

Pi

The two expressions for Gi

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,
Pisat
dP
lnisat Zi 1
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.

Gisat

ln

Ratio (C) is then

fi
f i sat

fi
f i sat

G i i T RT ln f i

(11.31)

are set equal:

1 P l
Vi dP
RT Pisat

fil P
1 P l
exp
Vi dP
RT Pisat
f i l Pi sat

Substituting for the three ratios in the initial equation yields

f i isat Pi sat exp

1 P l
Vi dP
RT Pisat

(11.43)

21

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,
Vi P Pi
l

f i isat Pi sat exp

sat

22

If Ziv is given by eq. (3.38), the simplest form of the virial equation, then

Zi 1

(11.44)

Bii P
RT

and eq. (11.44) becomes

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.

f i Pi sat exp

23

and

isat exp

Bii Pi sat Vi l P Pi sat

RT

Bii Pi sat
RT

(11.45)

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EXAMPLE 11.5
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:

300oC

For H2O at a temperature of

(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.

Gi i T RT ln f i

and

G i* i T RT ln f i *

Subtraction eliminates i (T), and yields

ln

fi
1

Gi Gi*
f i * RT

By definition Gi = Hi TSi and Gi* = Hi* - TSi*; substitution gives

ln

fi
1 Hi Hi*

Si Si*
f i * R T

(A)

25

The lowest pressure for which data at 300 oC (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

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):
ln

Si* = 10.3450 J g-1 K-1

18.015 g mol-1 2962.0 3076.8 J g -1

fi

6.3642 10.3450 J g -1K-1

f i * 8.314 Jmol-1K-1
573.15K

8.1917

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.

fi
3611.0
fi*
f i 3611.0 f i * 3611.0 1 kPa 3611.0 kPa

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

Thus the fugacity coefficient at 4000 kPa is

Hi = 2962.0 J g-1

Si = 6.3642 J g-1 K-1

i
27

f i 3611.0

0.9028
P
4000
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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 300oC:

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
Substitution in eq. (A) yields
f i sat 6738.9 kPa
and

Vi l 1.404 cm3 g -1 18.015 g mol-1

isat 0.7843

25.29 cm3 mol-1

At 10 000 kPa, for example, eq. (11.44) becomes
25.29 cm3mol-1 10000 8592.7 kPa 6789.8 kPa
f i 0.7843 8592.7kPa exp
8314 cm3kPamol-1K-1 573.15K
29

The fugacity coefficient of liquid water at these condition is

i f i P 6789.8 /10000 0.6790

30

REFERENCE

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
decrease in the liquid region is a
consequence of the near-constancy of the
fugacity itself.

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

31

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