SOLUTION

THERMODYNAMICS:THEORY
• THEIDEAL 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:

ig
nV ig nRT / P RT n RT
Vi
ni ni T , P ,n j
P ni nj
P
T , P ,n j

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:
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 yi P i 1, 2, ..., N
V ig
where yi is the mole fraction of species i. The partial pressures
obviously sum to the total pressure.
• Gibbs’s 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

M iig Viig by the equation:

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)

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

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

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— 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
ig
dS 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

(11.21)
Siig T , P Siig T , P R ln yi Miig T , P Miig T , pi

or
Siig Siig R ln yi (11.23)
where Siig is the pure-species value at the mixture T and P.
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• For the Gibbs energy of an ideal gas mixture, G ig H ig TS ig

the parallel relation for partial properties is

Giig H iig TSiig

• 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

or ig (11.24)
i Giig Giig RT ln yi

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

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

G ig yi Giig RT yi ln yi (11.27)
i i
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• 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.

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— An alternative expression for the chemical potential iig results when
Giig 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

ig
i Giig i T RT ln yi 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 yi i T RT yi ln yi P (11.30)
i i 8
FUGACITY AND FUGACITY
COEFFICIENT: PURE SPECIES
— From eq. (11.6), the chemical potential µi 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 µi is defined in relation to

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

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

— 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 µi
but which does not exhibit its less desirable characteristics. 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
ig fi
Gi Gi RT ln
P 10
— By definition of eq. (6.41), M R M M ig ; 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 fi:
fi (11.34)
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,
fi = 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):
GR P dP
J Z 1 const T (6.45)
RT 0 P
GiR
lim lim ln i J
P 0 RT P 0

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— In connection with eq. (6.48), the value of J is immaterial, and is set

equal to zero.

SR P Z dP P dP
T Z 1 (6.48)
R 0 T P P 0 P

fi
lim ln i lim ln 0
P 0 P 0 P

and fi
lim i lim 1
P 0 P 0 P

— The identification of ln fi with GiR/RT by eq. (11.33) permits its

evaluation by the integral of eq. (6.49)
GR P dP (6.49)
Z 1 const T
RT 0 P
P dP
ln i Zi 1 const T (11.35)
0 P
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— 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
— Because Bii is a function of temperature only for a pure species,
substitution into eq. (11.35) gives
Bii P
ln i dP const T
RT 0

Bii P
ln i (11.36)
RT

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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 of eqs. (11.33) and (6.66b):
(11.33)
GiR RT ln i
GR (6.66b)
Z 1 ln Z qI
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 constant
a T s and e are pure numbers, same
q (3.51) for all substances
bRT
1 1 b
I ln (6.65b)
1 b
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— This eqn. written for pure species i (for the van der Waals equation,
Ii = βi/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

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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,
fi
Gi Gil RT ln
f il
— This eqn applies to the change of state from saturated liquid to
saturated vapor, both at temperature T and at the vapor pressure
Pisat.

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

G G (6.69)

fi 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.

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

— This equation, expressing equality of fugacity coefficients, is an

equally valid criterion of vapor/liquid equilibrium for pure species.

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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:

l
f i Pi sat f il Pi sat f il P
fi P Pi sat
Pi sat f P sat
f l
P sat
1 4 2 43 1 4 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 fisat. It is given by eq.
(11.35), written,

sat
Pisat dP
ln i 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.

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

— Another expression for this difference results when eq. (11.31) is

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

— Ratio (C) is then

f il P 1 P
exp Vil dP
f il Pi sat RT Pisat

— Substituting for the three ratios in the initial equation yields

sat 1 P
fi i Pi sat exp V l
i dP (11.43)
RT Pi sat
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— 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,

sat
Vil P Pi sat
fi i Pi sat exp (11.44)
RT
— The exponential is known as Poynting factor. Data required for
application of this equation:
◦ Values of Ziv for calculation of fisat 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.

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

Bii P sat Bii Pi sat

Zi 1 and i exp
RT RT

and eq. (11.44) becomes

Bii Pi sat Vil P Pi sat

fi Pi sat exp (11.45)
RT

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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 fi from data in
the steam tables and plot them vs. P.

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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 Гi (T), and yields

fi 1
ln Gi Gi* G H TS
f i* RT

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

f 1 H i H i*
ln i* Si Si* (A)
fi R T
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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

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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):

f 18.015g mol -1 2962.0 3076.8 J g -1

ln i* 6.3642 10.3450 J g -1K -1
fi 8.314 J mol -1K -1 573.15K
8.1917
fi
3611.0
f i*

fi 3611.0 f i* 3611.0 1 kPa 3611.0 kPa

Thus the fugacity coefficient at 4000 kPa is

fi 3611.0
i 0.9028
P 4000
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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
sat
i 0.7843

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 i i
l
i
sat 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 fi 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:
Vil 1.404cm 3 g -1 18.015g mol -1
25.29 cm 3 mol -1

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

Vil P Pi sat
fi i Pi sat exp
3 -1
RT
25.29cm mol 10000 8592.7 kPa
fi 0.7843 8592.7 kPa exp 3 -1 -1
6789.8 kPa
8314cm kPa mol K 573.15K

The fugacity coefficient of liquid water at these condition is

i fi P 6789.8/10000 0.6790
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Such calculations allow completion of
Fig. 11.3, where the solid lines show
how fi and fi 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 fi 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.
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Using the Steam Tables, determine
the fugacity of steam at 300°C and
70 bar.
Two approaches are possible:
a. Use of the enthalpy and entropy values; and
b.Graphically, using the PVT data directly

30
From the Steam Tables
at 300°C and 70 bar
H =2839.3 kJ/kg; S=5.9327 kJ/kg K;

and at P=0.1 bar and 300°C:

H*=3076.6 kJ/kg; S*=10.3450 kJ/kg K.

31
Estimate the fugacity of propane gas at 220 F and 500 psia.
You will proceed in several ways, show any possibilities.
Calculation Method Calculated f/P
(a) Directly from measured PvT data
(b) Ideal gas law
(c) EOS
(d) Z vs T diagram
others

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

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