4-2-Partial Fugacity in Gas Mixture Continued

3rd Ed. Sandler’s chap 6

Corresponded states (CS) theorem for pure fluids

Before discussing mixtures, we shall focus on pure fluids, CS Theorem is
the method to find generalized correlation of volumetric data for all fluids
by using molecular consideration (i.e. polarity, critical properties,
Equation of state, etc). The first CS theorem is Two-parameter and
Three-parameter corresponding states, then, virial Equation of state that is
only good for gas. Three-parameter CS is not good for some polar or
special substance.
CS Theorem is nothing but using Equation of state (such as
Z = f (Tr , Pr ) , Z = f (Tr , Pr , W ) , generic Redlish-kwong, SRK, or

Peng-Robinson etc EOS) to describe the fluid’s property including that of

liquids. Referred to 4th Sandler chapter 9 (P400 - )

CS Theorem Definition:
All pure fluids obey a universal equation of state, expressed in terms of
dimensionless (reduced) macroscopic variables as following:

T T V
TR = , PR = , V R = *: reference state
T* T* V*

Z = f (TR , PR ) = f (TR ,VR ) = f (VR , PR )

Universal constant is a goal for professionals who try to find a constant

fitting on all fluids, such as the gas constant of R = 0.08205.

99
(1) Two-parameter corresponding state

Z = f (TR , p R ) = f ( PR ,VR ) = f (TR ,VR )

Derive it by using a classic equation likes the vDW equation

RT a
P= − 2 ---EQ(0)
V −b V

At the critical point

RTc a
Pc = − 2
Vc − b Vc

∂Pc − RTc 2a
=0= + ---EQ(1)
∂V T c
( Vc − b )2 Vc3

∂ 2 Pc 2 RTc 6a
= 0 = − ---EQ(2)
∂V 2 T C
( Vc − b )3 Vc4

Solve EQs (1) and (2) simultaneously.

⎧ 9Vc RTc V a ⎫
⇒ ⎨a = , b = c , Pc = 2⎬
⎩ 8 3 27 b ⎭

100
EQ(0)
( Pc )
⎡ ⎛ 1 ⎞ 9Vc RTc ⎤
⎛ RT a ⎞
⎢ RT ⎥
⎜ − ⎟ ⎜ ⎟
P ⎝ V − b V 2 ⎠ 27b 2 ⎢ b ⎜ 3b ⎟ 8 ⎥
= = ． −
Pc ⎛ a ⎞ a ⎢V − 1 ⎜ 1 ⎟ ⎛ 3b ⎞ 2 ⎥
⎜ 2 ⎟ ⎢ b ⎜ V ⎟ ⎜⎜V ⎟⎟ ⎥
⎝ 27b ⎠ ⎢⎣ ⎝ c ⎠ ⎝ Vc ⎠ ⎦⎥

⎡ ⎤
1
⎢ RTVc RT cVc ⎥
27 ⎢ 3
− 8 2⎥
P
⇒ =
Pc 9Vc RTc ⎢ 3 V − 1 ⎛ V ⎞ ⎥
⎢ ⎜⎜ ⎟⎟ ⎥
8 ⎢ Vc
⎣ ⎝ Vc ⎠ ⎥⎦

⎛ 8TR ⎞ 3
⇒ PR = ⎜⎜ ⎟⎟ − ---EQ(3)
⎝ 3VR − 1 ⎠ (VR )
2

It is the two-parameter (i.e. Tc and Pc) CS theorem.

Discussion:
(I): For any pure fluid if their fluid-dependent parameters (i.e. Tc and Pc)
are known, the above dimensionless CS EOS (EQ(3)) is universal for all
pure fluids that obey the vdW equation.

101
 3
(II) Since E (internal energy) = kT (Temperature is index for energy).
2
Therefore

9Vc RTc
a= = f (T ) , it relates to molecular attractive force.
8

Vc
b= = f (V ) , it relates to molecular volume.
3

(III) For all substances (if fluids obey vDW EOS), the resulting of this
two-parameter corresponding gives:

a
．3b
PcVc 27b 2 ⎛ a ⎞ ⎛ 1 ⎞⎟
Z cVDW = = = ⎜ ⎟ ⎜⎜
RTc RTc ⎝ b ⎠ ⎝ 9 RTc ⎟⎠

3
⇒ Z cVDW = = 0.375
8
The above value should be true for all substances that obeyed the vdW
EOS. But most real fluids are not like to have their values of
Z cVDW = 0.375 .

102
Trouble #1:
For AR, KR, XR (noble gases) that is not spherical and not monoatom.

Z c = 0.293 ± 0.001

Hence, the VDW fluids are only true for spherical and mono-atomic
substances. Only molecules with the same spherically symmetric
intermolecular force field obey the two-parameter CS EOS.

Trouble #2:
Two-parameter CS EOS also not works for complex substances (e.g.
organic gases). Since complex substance follows

Z= f (TR, PR, shape of molecule, poly-atomicity, polar forces, etc.)

Therefore, Z = f (TR , PR ) should be revised by adding one extra parameter

for accounting each new variation in the intermolecular force interaction.

103
(2) Three-parameter corresponding state

Z = f (TR , RR , ω ) = f (TR ,VR , ω ) = f ( PR ,VR , ω )

Accentric factor (ϖ) represents a difference in intermolecular forces.

⎛ ∂Z ⎞ ⎛ 2
2 ∂ Z
⎞
Z (TR , PR , ω ) = Z (TR , PR , ω = 0) + ω ⎜
0
⎟ + ω ⎜⎜ 2 ⎟ + ......
⎟
⎝ ∂ω ω = 0 ⎠ ⎝ ∂ω ω = 0 ⎠

⇒ Z (TR , PR , ω ) = Z 0 (TR , PR ) + ωZ ' (Tn , PR ) ---EQ(1)

⎡ P sat ( T = 0.7Tc ) ⎤
ω = −1 − log ⎢ ⎥
⎣ PC ⎦

The ω is called an accentric factor and it accounts for forces arising from
points away from molecular center. It is often for molecules having
different molecular shape and spherical poly-atomicity.

104
Discussion:
(I) Vapor pressure is a good indicator of intermolecular force because
that different molecules possess different shape and spherical
poly-atomicity.
(II) Accentric factor does handle the following two different molecules:

H
H C H
H
H H CH
H C H H H
CH H CH H C C CH
H H H
H CH HC H
H H

These two molecules have different shape and spherical poly-atomicity.

But the following two molecules have different dipole moments and the
accentric factor ( ω ) does not handle it.

δ H
δ
O －
O
Net diple moment

+
H H H C H
+
δ δ H
δ+
Net diple moment

105
The following equation (i.e. EQ(1)) is good for any substance if they obey
the three-parameter CS theorem:

Z (TR , PR , ω ) = Z ° + Z'ω

When you plot the values of Z versus ω for every substance, you could get
a generic correlation equation. Professor Pitzer found the following
equation in his PhD work at University of Berkeley. In general, it is good
for every substance.

Z c = 0.291 − 0.08ω

(III) It is possible to include 3-parameter CS in Two-parameter EOS (if

in the vdW form) by collecting a lot of experimental PVT data and
getting both a and b values as functions of the accentric factor (ω):

a = f (Tr , Pr , ω ) b = f (Tr , Pr , ω )

Then, the renewed vdW EOS with those a and b values could fit
experimental data much better.

RT a
However, the vdW EOS of P = − 2 is not a good EOS
V −b V
basically.

106
(IV)
When the L-V phase equilibrium happened, the following 2D P-V diagram
(bold curve) represents the true 3D P-V-T relationship for real fluid.

P C.P. True PVT form

at T and x
L
V
＋ Consistency curve obtained by
L+V
S given (T,x) pairs.
Psat S
Large volume for vapor and small
volume for liquid.

V
O

However, any cubic equations of state do not give the bold curve, instead
they give a sharp curve with three roots (points at 1, 3, 5) as the curve
shown in the following plot. A good cubic equation can accurately fit
experimental PVT data for a real fluid.

P
(atm) ∞
Cubic EOS gives three roots (1, 3, 5),
only 1(liquid) and 5(vapor) are real at
given saturated pressure.
22 4
1 3 5
sat
P

O
b Volume

Cubic EOS gives unreal points (2, 3, 4),

because thermodanamic stability said
volume decrease at pressure increase for
2 whole range.

107
Cubic equations of state (cubic in volume or density)

1. Advantage and disadvantage:

Cubic EOS is simplest form to show realistic behavior of the PVT data (or
real fluid) but it is limited by a cubic behavior in volume.

Explain it by a generic Redlich-kwong EOS (a proposed RK EOS) for

teaching:

RT θ
P= − EQ(0)
V − b V (V + b)
b, θ = f (T, x)

Expressing EQ(0) in terms of the cubic volume:

RT 2 bRT θ bθ
⇒ V3 − V − (b 2 + − )V − =0 ---EQ(1)
P P P P

At constant T and x and P, EQ(1) should have 3 roots of volume.

108
Plot of P versus V (only curve I has physical significant.
Please refer to Sandler’s figure 4-15. [4th Ed. Sandler chapter 7]

P
(atm) ∞
Cubic EOS gives three roots (1, 3, 5),
only 1(liquid) and 5(vapor) are real at
given saturated pressure.
22 4
1 3 5
Psat

O
b Volume

Cubic EOS gives unreal points (2, 3, 4),

because thermodanamic stability said
volume decrease at pressure increase for
2 whole range.

At small volume (i.e. P is rising steeply),

⇒ P→∞ at V = b
Look it also from the EQ(1) at V = b.

At V ≥ b, P = negative, i.e. curve part of ○

1 →○
2 , then ○
2 ○
3 ○
4 ○
5 .

Since at phase equilibrium: f L ( T , P sat ) = f V ( T , P sat )

Hence, any cubic EOS model results in the P = Psat line intercepted with the
cubic curve to give three volume roots. Concluding that at 0 < p < 22 bar,
there is a large positive roots for gas volume, and a small positive root for
liquid volume.

109
2. Inspiration of EOS models by statistical perturbation theory

R A
⎛ PV ⎞ ⎛ PV ⎞
Z total
=Z repulsive
+Z attraction
=⎜ ⎟ +⎜ ⎟
⎝ RT ⎠ ⎝ RT ⎠

Z R : is due to "repulsive forces" between molecules (when they approach

each other). It is called the excluded volume effect.

Z A : is due to "attractive forces" between molecules, it is called energy

effect created by molecular interaction.

Intermolecular energy ( U ij ) represented by an attractive well model.

Repulsive force
U ij

Intermolecular forces are negative, so two

molecules attracts each other
γ min
γ ij

110
Discussion:
(I) Intermolecular forces ( F ij )
∂U ij
Fij = −
∂rij
At large distance, Fij is negative, so molecules attract each other

(II) Usually, repulsive force can be solved by a hard sphere theorem, i.e.
At two molecules touch each other
U ij = ∞
At other condition
U ij = 0

This hard sphere theorem solution for repulsive force is analytical, and can
also be solved by a statistical theory (stated in physical chemistry).

U ij

γ ii γ jj
γ ij
⎛ rii + r jj ⎞
γ ij = ⎜ ⎟
⎝ 2 ⎠

111
3. General form of the EOS model:
R
PV ⎛ PV ⎞ ∞ ∞
Z= =⎜ ⎟ − ∑ ∑ aij ( x) f i (T ) g j (V , x)
RT ⎝ RT ⎠ i =1 j =1

EX #1:
Van der Waal's EQ (2 parameters)

R
⎛ PV ⎞ V 1 1 a( x)
⎜ ⎟ = ， f1 = ， g1 = ， a11 = and
⎝ RT ⎠ V − b(x) T V R
aij = 0 (i, j > 1)
R
⎛ PV ⎞ a( x)
⎜ ⎟ =
⎝ RT ⎠ VRT

EX #2:

Redlich-Kwong EQ (2 parameters)

R
⎛ PV ⎞
3
V − 1 a( x)
⎜ ⎟ = ， f 1 = T 2 ， g1 = a11 =
⎝ RT ⎠ V − b(x) V + b( x ) R
aij = 0 (i, j > 1)
A
⎛ PV ⎞ a ( x)
⎜ ⎟ =
⎝ ⎠
3
Rt
T R(V + b( x))
2

112
Ex#3

Peng-Robinson EQ (3 parameters)

R
⎛ PV ⎞ V
⎜ ⎟ =
⎝ RT ⎠ V − b(x)
1
1
f1 = (1 + K1T ) 2 ， g1 =
2
V 2 + 2Vb( x) − b 2 ( x)
a( x)
a11 =
R
aij = 0 (i, j>1)

a ( x)(1 + K1T )
A
⎛ PV ⎞ 2 2
⎜ ⎟ =
⎝ RT ⎠ R[V 2 + 2Vb( x) − b 2 ( x)]m

b( x) = Σxi bi
a ( x) = ΣΣxi x j (aii aij )

a( x ), b( x ) are parameters for a mixture.

113
4. Mixture parameters ( a( x ),b( x ) ) for the EOS model
(i) b( x ) obtained from pure component bii by mixing rules, bii

represents the size of a molecule of component i if it was a hard sphere.

(ii) a ( x ) obtained from pure component aii by mixing rule and used a
binary interactional parameter kij , a( x ) represents an averages energy of

interaction.

An quadratic mixing rule can be used for mixture parameters of a( x ), b( x ) :

a ( x) = ΣΣxi x j ( aii a jj ) (1 − k ij ) kij = 0 if i = j

⎛ bii + b jj ⎞
b( x) = Σxi bi = ΣΣxi x j ⎜⎜ ⎟⎟
⎝ 2 ⎠

5. Criticize the EOS model:

Basically, all EOS is good for vapor and liquid equilibrium calculation
for a mixture. In principle, it can be used for estimation of liquid volume,
but accuracy is poor. Many correlations have been developed for
estimation of liquid volume or (density). One can be done by using
another interactional parameter ( δ ij ) for the volume parameter of the

b( x ) correction, i.e.

b( x) = Σxibi (1 − δ ij )

114
Discussion:
R
⎛ PV ⎞ V
(i) ⎜ ⎟ =
⎝ RT ⎠ V − b(x)
It is a simple but basically incorrect expression for ZR for hard spheres.

(ii) The correct exact expression is given by the Massouri, Carnahan,

Starling, and Leland equation for hard spheres (means small molecules and
nonpolar).

6 ⎡ ξ0 3ξ1ξ 2 ξ 23 ( 3 − ξ 3 ) ⎤
HS ,repulsive
⎛ PV ⎞
⎜ ⎟ = ⎢ + + ⎥
⎝ RT ⎠ π ⎣( 1 − ξ 3 ) ( 1 − ξ 3 )2 ( 1 − ξ 3 )3 ⎦

π moleccule
ξk = ∑ ρi aiik k=0,1,2,3
6 i =1

⎡ Ni ⎤
ρi : density of moleculer of i ≡ ⎢
⎣ V ⎥⎦

a ii = hard sphere diameter of molecule i = f(T)

At k = 3, ξ k ≡ dimensionless.

It is only a hard sphere theorem that can be solved by the analytical

form for repulsive forces.

115
Since the formulation of Z can be made by the perturbation theory,
equation of state application for phase equilibrium basically depends on the
ZR and ZA terms.
It is only ZR can be solved by hard sphere theorem analytically.
ZA = f (ρ,T,x) was usually obtained from correlation of experimental data.

(iii) A much letter approach is to use above hard sphere expression of ZR

and a suitable form of ZA in terms of Bij ( T ) such as (Mathrias and

O'Connell) as following.

aij ( x) = xi x j ， f i (T ) f j (V , x) = ρ [ Bij (T ) − Bij ]

HS

aij = 0 [when i, j > m (# of components)]

HS , R
PV ⎛ PV ⎞ m m
=⎜ ⎟ − ρ ∑ ∑ xi x j [ Bij ( T ) − Bij HS ]
RT ⎝ RT ⎠ i =1 j =1

4 3
Bij (T ) = πaij N i
3
N i : # of molecules i
1
aij = (aij + a jj )
2
Bij (T ) = weak function of T, usually correlated from experimental data of
real mixture.

The above EOS can predict that gases dissolved in liquids.

116
6. Comments on cubic EOS used for pure substance or for mixture:
It is usually needed to modify the repulsive term and the attractive
term in the calculation of the compressibility factor (Z). Attraction term
needed more experimental data to be correlated the interactional parameter
such as Bij ( T ) , etc. It is also true that more experimental data were
required to correlate interactional values of δ ij and k ij in the mixing

rule for a mixture.

117
Corresponding states (CS) and equations of states (EOS) for mixtures

In applying CS theory and EOS model to mixtures, it is generally

RT a
assumed that the PVT relational form of ( P = − 2 ) is valid for pure
V −b V
substance and is also valid for mixture. If the parameters (a, b) of
components are properly defined. It is also called "one fluid theory"
because the mixture is treated as a pseudo-one-component system, whose
parameters of (a, b, TPC, PPC, VPC, etc) are average of the parameters for the
componential species.

How we can calculate a mixture of TPC, PPC, VPC and WM?

Supposed that a three-parameter corresponding state do represent an

equation of state for a mixture as following:

Z= Z (TPR, PPR, WM)

In which
T
TPR = = pseudo-reduced temperature
TPC (x)

T
PPR = = pseudo-reduced pressure
PPC (x)

WM = WM (x) = pseudo-reduced accentric factor

118
Once if you obtain values of TPR, PPR, WM, the volumetric PVT data of the
whole system (it can also be a mixed system of vapor and liquid phases for
a pure substance) could be calculated by using the Z = Z (TPR, PPR, WM)
form. It is called pseudo-one-component corresponding state EOS.

How to define these pseudo-critical properties (TPR, PPR, WM) of mixture?

(1) Kay's law (The simplest one )

Tci , Pci , Vci , Wi : Critical properties of component i

m
TPC = ∑ xiTci
i =1

PPC = Σxi Pci

VPC = ΣxiVci

WM = Σxi wi

Kay's law can fit for any like pairs (such as C8H18 and C5H10) but can not
fit for unlike pairs (such as CH3OH and H2O).

Like pairs means f mol1 = mol 2 = f mol1 = mol1 = f 2 − 2

Unlike pairs means f1− 2 ≠ f1−1 ≠ f 2− 2

119
(2) Quadratic Rules (very useful)

m m
TPC = ∑ ∑ xi x jTcij
i =1 j =1

PPC = ΣΣxi x j Pcij

VPC = ΣΣxi x jVcij

m ⎡1 ⎤
WM = ∑ xi wi (or WM = ∑ ∑ xi x j ⎢ ( wi + w j )⎥ )
i =1 i= j= ⎣2 ⎦

if i=j ⇒ Tcij = Tci ; Pcij = Pci (or Vcij = Vci )

120
If i ≠ j you need the following recipe to get interaction critical parameters
(Tcij , Pcij ,Vcij )

For relatively similar components

1

Tcij = (TciiTcjj ) 2

1 1
Pcij = ( Pcii + Pcjj ) (or Vcij = (Vcii + Vcjj ) )
2 2
Tcii , Tcjj , Pcii , Pcjj ,Vcii ,Vcjj are critical properties of pure component i
and j.

For dissimilar components (very useful)

1

Tcij = (TciiTcjj ) (1 − k ij )
2
kij = 0 if i = j

1 1
Pcij = ( Pcii + Pcjj ) or Vcij = (Vcii + Vcjj )
2 2
Usually, knowing of Tcij ,Pcij , x (or Tcij ,Vcij , x ) values is enough to

calculate the mixed critical property.

This dissimilar equation is adequate for "complex" mixture.

－kij is a binary parameter obtained from binary mixture data.
－This approach generally predicts multi-component solution behavior
from pure component and binary solution data.

121
(3) Van der Waal's rules:

TPC = ΣΣxi x j Tcij It is the same for PPC.

VPC = ΣΣxi x jVcij

if i = j ⇒ Tcij = Tci ; Vcij = Vci

if i ≠ j ⇒ similar to the quadratic mixing rule

Tcij = (TciiTcjj ) (1 − k ij )

Vcij =
1
2
(
3 Vcii + 3 Vcjj )
3

(4) Quadratic "mixing rule" for calculating a and b of EOS are as follows:
a = ΣΣxi x j aij aij = aii a jj (1 − k ij )

b = ΣΣxi x j bij bij = (bii + b jj )(1 − δ ij ) / 2

If δ ij = 0 ⇒ b = Σxi bi

122
(5) Comments on mixing rules of the CS and EOS models
(a) Liquid properties at V-L phase equilibrium are very sensitive to the
energy related interactional parameter of kij.
(b) In the calculation of mixture parameters of a(x) and b(x) that come
from aii and bii of pure substance. aii represent the energy of hard sphere
molecule i, thus related to temperature; bii represent the size of hard sphere
molecule i, thus related to molecular volume that is represented by Vcii.

In any EOS model, the volume related mixture parameter of b( x ) can be

represented by:
b( x) = ΣΣxi x j bij
(bii + b jj )
bij = (1 − δ ij )
2
It is similar to the VPC calculation in the quadratic rule of corresponding
state. Volumetric related interactional parameters (i.e.Vcij ) are additive
1
and can be an average form, i.e. Vcij = ( Vcii + Vcjj ) . Supposed that it is
2
not a hard sphere molecule, a binary interactional parameter ( δ ij ) can be

used in accounting for the dissimilar components.

3
(c) Since E = kT follows the gas energy dynamics, hence, an
2
arithmetic average of Tcij should be formulated as notes page 121. The

energy related interactional parameter (kij) is usually employed to make a

correction for Tcij .

123
 (6) Representation of the cubic equation of state in the Z form
Recalled the Z in terms of pressure, it is good to use the form of
⎛ Z −1⎞
Ln(φi ) = ∫0P ⎜ ⎟dP
⎝ P ⎠
However, usually EOS is pressure explicit, e.g. Peng-Robinson EOS:
RT a
P= − ---EQ(1)
V − b V ( V + b ) + b( V − b )

ZRT ⎛ aP ⎞ ⎛ bP ⎞
V= and A = ⎜ 2 2 ⎟，B = ⎜ ⎟
P ⎝R T ⎠ ⎝ RT ⎠
Substitute three terms into EQ(1) become:
⇒ Z 3 + ( B − 1) Z 2 + ( Z − 2 B − 3B 2 ) Z + ( B 3 + B 2 − AB) = 0

It is similar to the cubic equation in terms of V. It should have three Z

roots and large Z value for vapor, small Z value for liquid.

If T and V in the EQ(1) are independent variables, i.e. Ln(φi ) in terms of

dT and dV (it is similar to note page 82), then in the calculation of mole
fractions of xi and yi for the vapor and liquid phases at constant T, the
following equations for the calculation of (φi ) are useful:

⎛ fi ⎞ ⎡
∞ ⎛ ∂P ⎞ RT ⎤
RTlnφi = RTln⎜⎜ ⎟⎟ = ∫ V ⎢⎜⎜ ⎟⎟ − ⎥ dV − RT lnZ
V ,L

⎝ yi P ⎠ ⎢⎣⎝ ∂ni ⎠T ,V ,n
j
V ⎥
⎦
Referred to 2nd Ed. Prausnitz et al. (Ch3) 3.4-14
or 3rd Ed. (3-53) page 45

124
 (7) How mixing rules affect fugacity coefficients
Since f i L = f iV is an phase equilibrium necessity, we could calculate the
fugacity coefficient of component i (φi) by using P or T as the measurable
variable in the employment of bubble (dew) point P or bubble (dew) point
T method.

Supposed to use PR-EOS model for calculation of φi:

⎛2∑
m
xa ⎞
bi A ⎜ j =1 j ji bi ⎟ ⎛ Z + 2.414 B ⎞
lnφi = ( Z − 1) − ln( Z − B) − − ⎟ln⎜
L ,V
⎜ ⎟
b 2.828 B ⎜ a b ⎟ ⎝ Z − 0.414 B ⎠
⎝ ⎠
---EQ(2)
or
⎛2∑m
x j a ji ⎞
b a ⎜ b ⎟ ⎛ v + 2.414b ⎞
lnφi = i ( Z − 1) − ln( Z − B) − j =1
− i ⎟ l n⎜
L ,V
⎜ ⎟
b 2.828 RTb ⎜ a b ⎟ ⎝ v − 0.414b ⎠
⎝ ⎠

Note:
In the transformation of EQ(1) to EQ(2), the following good mixing rules
are required:

a = ΣΣxi x j aii a jj (1 − k ij )
b = Σxi bii
aP bP
A= 2 2 ,B =
RT RT

125
Example #1: referred to 3rd Ed. Prausnitz’s book chapter 3.6 (p52)
A V-L equilibrium system with m components, assuming that a pressure
explicit EOS is an available over entire density range, we want to find T, yi,
with given P and xi by using the bubble point T method.

Please describe how to formulate this problem!

Soultion:
(a) The number of unknown variables:

y1 ,......., ym (m−1) variables

T 1
VL, VV 2
⇒ Total = (m+2) unknowns

(b) The number of independent equations:

f i L = f iV m equations
P = F (v L , x1 ,......xm , T ) 1 any Equation of state for L
P = F (vV , y1 ,...... ym , T ) 1 any Equation of state for V

⇒ Total = (m+2) equations

A simultaneous solution of the above equations results in the unknown

variables.

126
 Example #2:
Please calculate the fugacity coefficient of component i using the following
EOS model. Berthelot EOS:
⎛ a ⎞
⎜ P + 2 ⎟
(V − b ) = RT
⎝ TV ⎠

a = ΣΣxi x j ai a j b = Σxi bi

transfer it to the total volume form

⎛ nRT ⎞ n a
2
P=⎜ ⎟−
⎝ V − nb ⎠ TV
2

Referred to 2nd Ed. Prausnitz book (3.4-14) [3rd Ed. (3-53) page 45]:

1 ∞⎡⎛ ∂P ⎞ RT ⎤
lnφi = ∫ V ⎢⎜⎜ ⎟⎟ − ⎥ dV − lnZ for total property
RT ⎢⎝ ∂ni ⎠T ,V ,n V ⎥
⎣ ⎦ j ≠i

⎛ ∂P ⎞ ⎛ RT ⎞ nRT ⎛ ∂nb ⎞ 1 ⎛ ∂ (n 2 a) ⎞
⎜⎜ ⎟⎟ =⎜ ⎟+ ⎜
2 ⎜
⎟⎟ − ⎜
2 ⎜
⎟⎟
⎝ ∂ni ⎠T ,V ,n
j ≠i
⎝ V − nb ⎠ (V − nb) ⎝ ∂ni ⎠ n TV ⎝ ∂ni ⎠ n
j ≠i j ≠i

Using
nb = Σni bi
∂ (nb) ∂
B’= = (Σni bi ) = ∂ (n1b1 + .....ni bi + nm bm ) = bi
∂ni ∂ni ∂ni
∂ (n 2a) ∂
n a = ΣΣni n j aij
2
A' = = [ΣΣni n j aij ] = 2i∑m=1 n j aij
∂ni ∂ni

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 Substitute above three terms into the EQ(3-53) of 3rd Ed. Prausnitz book:

1 ∞⎡⎛ RT ⎞ nRT B' A' RT ⎤

lnφi = ∫ ⎜ ⎟ + − − dV − lnZ
RT V ⎢⎣⎝ V − nb ⎠ ( V − nb )2 TV 2 V ⎥⎦

1 ⎡ ∞ ⎛ 1 ⎞
∞
A'
∞
∞⎤
= ⎢ RTln(V − nb) V − nRTB ' ⎜ ⎟ + − RTlnV V ⎥ − lnZ
RT ⎢⎣ ⎝ V − nb ⎠V TV V ⎥⎦

∞ ∞ ∞
⎛ V − nb ⎞ ⎛ nB ' ⎞ A'
= ln⎜ ⎟ − ⎜ ⎟ + − lnZ
⎝ V ⎠V ⎝ V − nb ⎠V RT V
2
V

⎛ v ⎞ b 2
⇒ lnφi = ln⎜ ⎟+ i − Σx j aij − lnZ
⎝ v − b ⎠ v − b RT v
2

Remembered that
Pv v a
Z= = − v: molar volume
RT v − b RT 2v
The above equation is similar to EQ (3-70) of the 3rd Ed. Prausnitz book
(p50), which was derived for the vdW EOS model.

(8) Combined EOS and Excess Gibbs Energy Model

Referred to 4th Sandler book chapter 9.9 (Page 462-465), as has already
been mentioned, simple cubic equations of state with the van der Waals
one-fluid mixing rules of Eqs. 9.4-8 and 9.4-9 are applicable at all densities
and temperatures, but only to mixtures of hydrocarbons or hydrocarbons
with inorganic gases. That is, this model is applicable to relatively simple
128
mixtures. On the other hand, excess Gibbs energy or activity coefficient
models were developed to describe mixtures of any degree of solution
nonideality including mixtures involving polar organic chemicals, but only
in the liquid state. Further, the parameters in activity coefficient models
are very temperature dependent, these models are not applicable to
expanded liquids (as occurs at high temperatures) or to the vapor phase,
and there is also the problem of defining a hypothetical standard state and
the standard-state properties for a component that exists as a gas in the pure
component state at the temperature and pressure of the mixture, especially
if the component is above its critical temperature (see Sec. 9.7). The
latter problem results in difficulties in, for example, describing the
solubility of hydrogen or nitrogen in liquids. The absence of an accurate
gas-phase model for polar organic compounds has resulted in difficulties in
describing the vapor-liquid equilibrium of polar mixtures at high
temperatures and pressures, and for describing supercritical extraction
processes.
Recently Wong-Sandler mixing rule methods have been developed
that combine an equation of state with an excess Gibbs energy (or,
equivalently, activity coefficient) model and that allow simple equations of
state to accurately describe all mixtures, including highly nonideal
mixtures over large ranges of temperature and pressure without having to
deal with hypothetical standard states and the other shortcomings of the
direct use of activity coefficient models.

129