4.

The Ideal-Gas Mixture

Prof. Angel Darío González-Delgado
 4. The Ideal-Gas Mixture

We have considered only gases that are just one substance, but how do
we deal with mixtures of gases?

• Gas molecules are separated, so they behave independently.

• The total pressure of the mixture is the sum of pressures that each
gas except if is present alone.
 4. The Ideal-Gas Mixture

Consider the universal law for an ideal gas:

𝑃 𝑉𝑇 = 𝑛 𝑇 𝑅𝑇
𝑛 𝑇 𝑅𝑇
𝑃𝑇 =
𝑉𝑇
For an ideal gas in a mixture:
𝑃𝑖 𝑉𝑇 = 𝑛𝑖 𝑅𝑇
𝑛𝑖 𝑅𝑇
𝑃𝑖 =
𝑉𝑇
 4. The Ideal-Gas Mixture
𝑛𝑖 𝑅𝑇
𝑃𝑖 𝑉𝑇
Dividing Pi by PT : =
𝑃𝑇 𝑛 𝑇 𝑅𝑇
𝑉𝑇

𝑃𝑖 𝑛𝑖
Simplifying terms: = = 𝑦𝑖
𝑃𝑇 𝑛 𝑇

𝑔𝑖 𝜕(𝑛𝑉𝑇 )
Remember that: 𝑉𝑖 =
𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝑖
 4. The Ideal-Gas Mixture
𝑅𝑇
𝜕(𝑛 )
𝑔𝑖 𝑃𝑇
Replacing VT at ni constant: 𝑉𝑖 =
𝜕𝑛𝑖
𝑃,𝑇,𝑛 𝑖

𝑔𝑖 𝑅𝑇 𝑔𝑖
Simplifying terms: 𝑉𝑖 = = 𝑉𝑖
𝑃𝑇

𝑔𝑖 𝑔𝑖
Therefore: 𝑉𝑖 (𝑇, 𝑃) = 𝑉𝑖 (𝑇, 𝑃)
 4. The Ideal-Gas Mixture
Since Vi ig  Vi ig
• The molar volume for a species does not change between its pure state
and in an ideal gas mixture at the same T & P.

• For an ideal gas mixture, the properties of each species are independent
of that of the other ones.

• This may be easy to appreciate as the concept of an ideal gas is premised

on the idea that the intermolecular interaction is non-existent in such a
state.
 4. The Ideal-Gas Mixture
Gibbs Theorem:
“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 pressure
equal to its partial pressure in the mixture”

Thus, for general partial property:

M i
ig
T , P   M T , pi 
i
ig
 4. The Ideal-Gas Mixture
Lets consider the case of enthalpy, according to Gibbs theorem:
H iig T , P   H iig T , pi 

But the enthalpy of an ideal gas is independent of pressure (at T

constant).
3
𝐻 = 𝑈 + 𝑝𝑉 = 𝑛𝑅𝑇 + 𝑛𝑅𝑇 = 𝐶𝑃 𝑇
2
𝜕𝐻
From whence it is obvious =0
𝜕𝑝 𝑇
 4. The Ideal-Gas Mixture
Lets consider the case of enthalpy, according to Gibbs theorem:
H iig T , P   H iig T , pi 

But the enthalpy of an ideal gas is independent of pressure

H iig T , pi   H iig T , P 
Also applies to other
property that are
H i
ig
H i
ig [1] independent of
pressure (U)
 4. The Ideal-Gas Mixture
By definition, the enthalpy of a mixture is:
ig
H mix T , P    yi H iig T , P 
i
Combining:
ig
H mix    i i T , P 
T , P  y H ig

Remember from previous presentation:

M mix (T , P)  M (T , P)   xi M i (T , P)
i

H ig mix (T , P)  H ig (T , P)   yi H ig i (T , P)
i
 4. The Ideal-Gas Mixture
Then:
H ig mix (T , P)   yi H iig T , P    yi H ig i (T , P)  0
i i

Employing the same reasoning:

U ig mix (T , P)  U ig (T , P)   yiU ig i (T , P )
i
 4. The Ideal-Gas Mixture
The entropy of an ideal gas does depend on pressure:

dSiig   Rd ln P (const T)

P P

 i   R  ln P
ig
S
pi pi

S T , P   S T , pi    R ln
P P
i
ig
i
ig
  R ln  R ln yi
pi yi P
Siig T , pi   Siig T , P   R ln yi
 4. The Ideal-Gas Mixture
Siig T , pi   Siig T , P   R ln yi A partial molar property ideal gas
mixture is equal to the molar
property of the species as a pure
Since M iig T , P   M iig T , pi  ideal gas at the mixture
temperature but at pressure equal
to its partial pressure in the

S i
ig
T , pi   S T , P 
i
ig mixture

Thus,
S i
ig
T , P   S T , P   R ln yi
i
ig

or
Siig  Siig  R ln yi [2]
 4. The Ideal-Gas Mixture
For Gibbs energy of an ideal-gas mixture, the partial properties is: G ig  H ig  TS ig

Gi ig  H iig  TSiig
Recall:
Thus, H iig  H iig

Giig  H iig  T  Siig  R ln yi  Siig  Siig  R ln yi

 H iig  TSiig  RT ln yi
Recall:
or
Gi   i
  Gi  G  RT ln yi
ig
i
ig
i
ig
[3]
 4. The Ideal-Gas Mixture
So far, we have derive:
H iig  H iig [1]
Siig  Siig  R ln yi [2]
Giig  Giig  RT ln yi [3]

Substituting [1], [2] & [3] into the summability relation, M   yi M i

i
H   yi H
ig ig
H ig
  yi H i
ig
[4]
i i

S ig   yi S ig S ig   yi Siig  R  yi ln yi [5]
i i i
G ig   yi G ig G ig   yi Giig  RT  yi ln yi [6]
i i i
 4. The Ideal-Gas Mixture
The properties of mixture for enthalpy, entropy and Gibbs energy:
H ig   yi H iig [4]
i
S ig   yi Siig  R  yi ln yi [5]
i i

G ig   yi Giig  RT  yi ln yi [6]
i i

Rearranging [4] & [5] give enthalpy & entropy change of mixing;
H ig   yi H iig  0 For ideal gas, mixing at constant T & P
i
is not accompanied by heat transfer
1
S   yi S
ig
i
ig
 R  yi ln
i i yi
 4. The Ideal-Gas Mixture

Example 1. What is the change in entropy when 0.7 m3 of CO2 and 0.3 m3 of
N2, each one at 1 bar and 25oC, are blended to form a gas mixture at the
same conditions? Assume ideal gases.
 4. The Ideal-Gas Mixture
Solution.
S ig   yi Siig  R  yi ln yi
i i

Reorganizing:
S ig   yi Siig   R  yi ln yi
i i

Multiplying by n:
nS ig  n yi Siig  nR  yi ln yi
i i

nS ig   ni Siig  nR  yi ln yi
i i

S   nR  yi ln yi
i
 S   nR  yi ln yi
i

For an ideal gas:

PVi
n V
yi  i  RT  i
nT PVT VT
Combining: RT

PVT Vi Vi
S   R  ln
RT i VT VT
100kPa *1m3
S    0.7 ln 0.7    0.3ln 0.3 
298 K
kJ
S  0.2049
K
 4. The Ideal-Gas Mixture
Example 2. A nitrogen stream flowing at a rate of 2 kg/s and another stream of
hydrogen flowing at a rate of 0.5 kg/s are mixed adiabatically in a uniform flow process.
If gases are considered ideal, what is the rate of increase of entropy as a result of the
process?
 4. The Ideal-Gas Mixture
Example 2. A nitrogen stream flowing at a rate of 2 kg/s and another stream of
hydrogen flowing at a rate of 0.5 kg/s are mixed adiabatically in a uniform flow process.
If gases are considered ideal, what is the rate of increase of entropy as a result of the
process?

Solution. The equation for the change in entropy of an ideal gas mixture is as follows:
∆𝑆𝑔𝑖 = −𝑛𝑅 𝑦𝑖 𝑙𝑛𝑦𝑖 [1*]

𝑘𝑔
We have two mass flows: 𝑚𝑁2 = 2
𝑠
𝑘𝑔
𝑚𝐻2 = 0.5
𝑠
 4. The Ideal-Gas Mixture
1. Determine the moles of each species as follows:
𝑚𝑖
𝑛𝑖 =
𝑀𝑖
Where, n are moles, m is molecular weight and m is mass (taking one
second as basis calculation)

2000 𝑔
𝑛𝑁2 = = 71.42 𝑚𝑜𝑙 𝑁2
28 𝑔/𝑚𝑜𝑙
500 𝑔
𝑛𝐻2 = = 250 𝑚𝑜𝑙 𝐻2
2 𝑔/𝑚𝑜𝑙
 4. The Ideal-Gas Mixture
2. Determine the total moles
𝑛 𝑇 = 𝑛𝐻2 + 𝑛𝐻2
𝑛 𝑇 = 71.42 𝑚𝑜𝑙 + 250 𝑚𝑜𝑙
𝑛 𝑇 = 321.42 𝑚𝑜𝑙

3. Determine the molar fraction 𝑛𝑖

𝑦𝑖 =
𝑛𝑇
71.42 𝑚𝑜𝑙
𝑦𝑁2 = = 0.23
321.42 𝑚𝑜𝑙
250 𝑚𝑜𝑙 𝐻2
𝑦𝐻2 = = 0.77
321.42 𝑚𝑜𝑙
 4. The Ideal-Gas Mixture
4. Taking as basis calculation the time in seconds and developing equation [1*], we
obtain equation [2*]
∆𝑆 𝑔𝑖 = −𝑛𝑅 𝑦𝑖 𝐿𝑛𝑦𝑖 [1*]

∆𝑆𝑔𝑖 = −𝑛𝑅 𝑦𝑁2 𝐿𝑛𝑦𝑁2 + 𝑦𝐻2 𝐿𝑛𝑦𝐻2 [2*]

Replacing the terms:

𝐽
∆𝑆𝑔𝑖 = −321.42 𝑚𝑜𝑙 8.314 0.23𝐿𝑛(0.23) + 0.77𝐿𝑛(0.77)
𝑚𝑜𝑙 𝐾
𝑔𝑖
𝐽
∆𝑆 = 1441.1
𝐾
 4. The Ideal-Gas Mixture
Alternatively, Giig in equation [3] (Giig  Giig  RT ln yi ) can be expressed by
giving its T and P dependence:
dG ig  Vi ig dP (const T)
RT
dG ig
 dP Integration
P
Integration gives, constant at
constant T

G ig  i T   RT ln P[7]

Thus equation [3] becomes: Gi ig  i T   RT ln P  RT ln yi

 i T   RT ln  yi P  [8]
 4. The Ideal-Gas Mixture

Gi ig  i T   RT ln  yi P  [8]
Substituting equation [8] into summability relation, G ig   yi G ig
i
ig
Thus, Gibbs energy of an ideal-gas mixture,G becomes:

G ig   yi i T   RT ln  yi P 
i

G ig   yi i T   RT  yi ln  yi P 
i i
 4. The Ideal-Gas Mixture
To do:
What is the ideal work for the separation of an equimolar mixture of
methane and ethane at 175oC and 3 bar in a steady-flow process into
product streams of the pure gases at 35oC and 1 bar if the surroundings
temperature Ts = 300K?
 4. The Ideal-Gas Mixture
1. Read section 5.8 of book Smith, Van Ness, Abbott, seventh edition
(calculation of ideal work).

2. Think about the process: separation of gases and change of state

First calculate DH and DS for methane and for ethane changing their
state from P1, T1, to P2T2

Second, calculate DH for de-mixing and DS for de-mixing from a mixture

of ideal gases.
4. The Ideal-Gas Mixture
ig
H i   Cp (T ) dT
ig T2

T1
ig
dT P2
S i  
T2
 R ln
ig
Cp (T )
T1 T P1
H deig  mix  0
S deig  mix  R  yi ln yi
i

H   yi H iig  H deig  mix = -7228 J/mol

i

S   yi S iig  S deig  mix = -15.813 J/mol K

i
𝑊𝑖𝑑𝑒𝑎𝑙 = 𝐷𝐻 − 𝑇𝑠 𝐷𝑆 = −2484 𝐽/𝑚𝑜𝑙
5. Fugacity & Fugacity Coefficient: Pure Species
Prof. Angel Darío González-Delgado
 5. Fugacity & Fugacity Coefficient: Pure Species
• Chemical potential provides a fundamental description of phase
equilibria, it also proves an effective tool for representing chemical reaction
equilibria. Nevertheless, its direct usage is restricted, as it is not easy to
directly relate the chemical potential to thermodynamic properties
amenable to easy experimental determination, such as the volumetric
properties.

• We introduce the concept of fugacity that for a pure component is the

analogous (but is not equal) to the pressure, the definition of fugacity, itself
related to the chemical potential, helps bridge the gap.
5. Fugacity & Fugacity Coefficient: Pure Species
It is clear that, Gi   i

i  i   ...  i  i  1,2..., N  G  H  TS

However, absolute values for H(U) and S are unknown

So, application of equilibrium criteria can be eased introducing the

Fugacity.
5. Fugacity & Fugacity Coefficient: Pure Species

G ig   yi i T   RT  yi ln  yi P 
i i

• For ideal Pure fluid i, based on eq. 7, Gi

ig
  i T   RT ln P

• For real Pure fluid i, based on eq. 7,

Gi  i T   RT ln fi Fugacity of pure
species i, with
units of pressure
• Subtracting these two equations…
5. Fugacity & Fugacity Coefficient: Pure Species

 fi 
Gi  G  RT ln  
i
ig

P
fi
G  RT ln i
i
R i 
Residual Fugacity
P
Fugacity: Pressure
Gibbs coefficient fi  P
ig
of an ideal
energy
gas which has the
same chemical
potential as the
real gas.
5. Fugacity & Fugacity Coefficient: Pure Species

GiR  RT ln i
GiR
 ln i
RT
P
GiR
  Z i  1
dP
From previous chapter,
RT 0 P
P

0 Zi  1 P (const T)
Thus, ln i 
dP
 5. Fugacity & Fugacity Coefficient: Pure Species
P
ln i   Z i  1
dP
0
P
Zi for pure gases can be evaluated from PVT data, or from an EOS explicit in
volume. For example, Virial, Van der Waals, etc.
PV
From previous course:  Z  1  B ' P  C ' P 2  .... B,C,D…= Virial
RT coefficients, directly
related to the
or intermolecular forces
between molecules
PV B C
 Z  1   2  .... groups. function of T
RT V V
 5. Fugacity & Fugacity Coefficient: Pure Species
PV B C
 Z  1   2  ....
RT V V
Coefficient B describes interactions between pairs of molecules, C between groups of
three molecules and so on. Can be expressed as complicated integrals of intermolecular
forces. Thus, if the intermolecular forces between any combinations of molecules based
on the molecular separations were known, it would be possible to obtain integrations
and expressions for the coefficients without taking up experimental data; however
these calculations are too complicated and have not yet been completed, except for
simplified potential forces (even with this simplified calculations have only been
feasible for the second and third virial coefficient occasionally).
5. Fugacity & Fugacity Coefficient: Pure Species
PV BP B= Second virial
 Z  1 coefficient, function
RT RT of T
Or,
BP
Z 1  Zi=compressibility factor of pure
species (i)
RT Bii= Second virial coefficient,
Bii P interaction between 2 molecules
Z i 1  of pure species (i)
RT
P
Thus, ln i   Z i  1
dP
becomes:
0
P
P Bii P
Bii ln i 
ln i 
RT 0  dP (const T)
RT
5. Fugacity & Fugacity Coefficient: Pure Species
𝑅𝑇 𝑎
Van der Waals EOS: 𝑃= − 2
𝑉−𝑏 𝑉

Some algebra: 𝑃(𝑉 − 𝑏)𝑉 2 = 𝑅𝑇𝑉 2 − 𝑎(𝑉 − 𝑏)

𝑃𝑉 3 − 𝑃𝑏𝑉 2 = 𝑅𝑇𝑉 2 − 𝑎𝑉 + 𝑎𝑏

27 2 𝑇02
Where: 𝑎= 𝑅
64 𝑃0
1 𝑇𝐶
𝑏= 𝑅
8 𝑃𝐶
5. Fugacity & Fugacity Coefficient: Pure Species
• For any cubic EOS (general form)
 1  V
 V  PdV
V∞ = Ideal gas
ln i  Zi  1   volume
 RT 

• From Van der Waals EOS

 P(V  bi )  ai a,b= Parameters of
ln i  Zi  1  ln   cubic equations of
 RT  RTV state
5. Fugacity & Fugacity Coefficient: Pure Species
• For RK-EOS and SRK-EOS
ai  Zi  Bi  bi P
ln i  Zi  1  ln  Zi  Bi   ln   ; Bi 
bi RT  Zi  RT

• From PR-EOS
ai  Zi  Bi (1  2)  bi P
ln   Zi  1  ln  Zi  Bi   ln   ; Bi 
2 2bi RT  Zi  Bi (1  2)  RT

a,b= Parameters of
cubic equations of
state
5. Fugacity & Fugacity Coefficient: Pure Species

The acentric factor is said to be a measure of the non-sphericity (centricity)

of molecules. it measures the deviation in the vapor pressure of a
compound, compared to noble gases for which the acentric factor takes the
value of zero.
5. Fugacity & Fugacity Coefficient: Pure Species
• For vapor/liquid equilibrium in pure specie;
Giv  i T   RT ln f i v For pure specie i as saturated vapor

Gil  i T   RT ln f i l For pure specie i as saturated liquid

at the same temperature
• By difference:
 f v

Gi  Gi  RT ln  l 
v l i

 fi 
• This equation applies for a change of state from a saturated liquid
to a saturated vapor at same T and saturation pressure of specie i.

• At equilibrium, Giv  Gil or Giv  Gil  0

5. Fugacity & Fugacity Coefficient: Pure Species
Indicates the value for any of both, saturated
Therefore, f i sat
 fi v  liquid or saturated vapor, because both
RT ln  l   0 phases coexists in equilibrium
 fi 
 fi v 
ln  l   0 So, we can define a fundamental principle:
 fi  For a pure species coexisting liquid & vapor
phases, they are in equilibrium when they
fi v have the same temperature, pressure &
l
1 fugacity.
fi
f i v  f i l  f i sat f i sat
isat  sat iv  il  isat
Pi
 5. Fugacity & Fugacity Coefficient: Pure Species

How can be calculated the fugacity of a pure liquid?

 5. Fugacity & Fugacity Coefficient: Pure Species
• The fugacity of pure specie I as a compressed liquid is calculated in two steps:
1. Calculate fugacity coefficient of saturated vapor i  i from an integrated
v sat

form of: P
ln i   Z i  1
dP
0
P

Evaluated in P  P sat
i , then, find
fi sat  Pi satisat ,which is the fugacity as
saturated liquid as saturated vapor at system temperature.
2. Calculate the change of fugacity as result of a pressure change from saturation
pressure to P, which changes the estate from saturated liquid to compressed
liquid.
 5. Fugacity & Fugacity Coefficient: Pure Species
• Fugacity for a pure liquid:

f i P  
l f v
P sat
f    
l
P sat
f i P 
l
sat

   
i i i i
Pi
Pi sat f i v Pi sat f i l Pi sat
f i sat A B C
 i
sat
 sat
Pi Pi sat
Bii P
ln  i
sat
   Z  1 P
i
v dP Z 1 
i
v

RT
0
Pi sat
 Bii P  dP Bii Pi sat
isat  exp 0

 RT  P
  exp
RT
5. Fugacity & Fugacity Coefficient: Pure Species
• Fugacity for a pure liquid:

f i P  
l f v
   
P sat
f l
P sat
f i P 
l
sat

   
i i i i
Pi
Pi sat f i v Pi sat f i l Pi sat
A B C

 
f i l Pi sat
1
 
v
f i Pi sat
5. Fugacity & Fugacity Coefficient: Pure Species
• Fugacity for a pure liquid:

f i P  
l f v
   
P sat
f l
P sat
f i P 
l
sat

   
i i i i
Pi
Pi sat f i v Pi sat f i l Pi sat
A B C
From
fi Gi  i T   RT ln f i
Gi  G sat
 RT ln
Gisat  i T   RT ln f i sat
i
f i sat
P
dG  VdP  SdT
Gi  Gisat   Vi l dP From

Pi sat (At constant t)

5. Fugacity & Fugacity Coefficient: Pure Species
• Ratio C becomes,
fi l  P  1
P Vi= molar volume of
 exp  V dP
l

f i  Pi 
l sat i saturated liquid at
RT Pi sat temperature of
interest
Vi l  P  Pi sat 
 exp
RT
• Substituting A, B, and C terms;

Vi l  P  Pi sat  The exponential is

f i l  isat Pi sat exp known as Poynting
RT Factor
Bii P sat
isat  exp
RT
6. Fugacity & Fugacity Coefficient: Species in Solution
Prof. Angel Darío González-Delgado
6. Fugacity & Fugacity Coefficient: Species in Solution

i  i T   RT ln fˆi Fugacity of species i in solution

fˆi  fˆi   ...  fˆi  Multiple phases at the

same T & P are in
equilibrium when the
fugacity of each constituent
species is the same in all
species
6. Fugacity & Fugacity Coefficient: Species in Solution
From definition of residual property: M R  M  M ig

• Multiplying by n: nM
R
 nM  nM ig

• Deriving respect to ni (T, P and nj constant):

   nM R      nM      nM ig
 
     
 ni  P ,T ,n  ni  P ,T ,n j  ni  P ,T ,n
j j
6. Fugacity & Fugacity Coefficient: Species in Solution
For a species i in a mixture of real gas or in a solution of liquids:

Partial residual
Gibbs energy Gi R  Gi  Gi ig

Gi R  RT ln ˆi
Fugacity of species
ˆ
f
i in solution
Mostly used for
ˆi  i gases, but can be
yi P
also used for
liquids
6. Fugacity & Fugacity Coefficient: Species in Solution

• Deriving 
nG 

 RT 
 nG  1 nG
d  d  nG   2 dT
 RT  RT RT

• Remember:
d  nG    nV  dP   nS  dT   i dni
i
6. Fugacity & Fugacity Coefficient: Species in Solution
• Substituting

 nG  1   nG
d         i i   2 dT
nV dP  nS dT   dn
 RT  RT  i  RT

 nG   nV   nS  1 nG
d 
 RT  RT
dP 
RT
dT  
RT i
i dni  2 dT
RT
6. Fugacity & Fugacity Coefficient: Species in Solution

• But, G  H  TS

 nG   nV   nS  1  nH TnS 
Then, d  
 RT  RT
dP 
RT
dT  
RT i
i dni   2  2  dT
 RT RT 

 nG   nV   nS  1 nH nS
d 
 RT  RT
dP 
RT
dT  
RT i
i dni  2 dT 
RT RT
dT
6. Fugacity & Fugacity Coefficient: Species in Solution
and Gi  i

 nG   nV  nH 1
Then, d  
 RT  RT
dP  2 dT 
RT

RT i
i dni

We can express G/RT as function of T,P and n

 nG   nV  nH Gi
d  dP  2 dT   dni
 RT  RT RT i RT
6. Fugacity & Fugacity Coefficient: Species in Solution
For particular case of an ideal gas:

  nV 
ig
 nG ig
nH ig
Gi ig
d   dP  2
dT   dni
 RT  RT RT i RT

For residual properties:

  nV 
R
 nG R
nH R Gi R
d  dP  2 dT   dni
 RT  RT RT i RT
6. Fugacity & Fugacity Coefficient: Species in Solution
Remember: Gi R  RT ln ˆi

  nV 
R
 nG R
nH R
Substituting: d   dP  2 dT   ln ˆi dni
 RT  RT RT i

This equation is usable in practice only in restricted forms.

6. Fugacity & Fugacity Coefficient: Species in Solution

 nG   
R
R nV nH R
d  dP  2 dT   ln ˆi dni
 RT  RT RT i

Dividing by dP at T and n constant (ni/n turns into xi):

V 
R
(G / RT ) 
R
 
RT  P T , x
6. Fugacity & Fugacity Coefficient: Species in Solution

 nG   
R
R nV nH R
d  dP  2 dT   ln ˆi dni
 RT  RT RT i

Dividing by dT at P and x constant:

HR  (G R / RT ) 
 T  
RT  T P, x
Is by the residual properties that experimental information enters to practical
application in thermodynamics.
6. Fugacity & Fugacity Coefficient: Species in Solution

  (nG R / RT ) 
ln ˆi   
 ni  P ,T ,n j
This equation shows that fugacity coefficient for a specie i in solution is a
partial property respect to G(residual)/RT, then we can obtain expressions
for partial properties:

Vi R   ln ˆi  H i R   ln ˆi 
   
RT  P T , x RT  T  P , x
2
6. Fugacity & Fugacity Coefficient: Species in Solution

Given that values of ln ˆi are partial properties in relation to G(residual)/RT,

summability relation takes the form:

 GR 
    yi ln ˆi
 RT  i
6. Fugacity & Fugacity Coefficient: Species in Solution
And values of ln ˆi must satisfy the equation of Gibbs/Duhem (as an special case):
 x d ln ˆ
i
i i 0

We must develop a general equation for calculating values of ln ˆi from data of
the compressibility factor:
P
GR dP
From previous slide:    Z  1
RT 0 P
P
nG R dP
   nZ  n 
Multiplying by n:
RT 0
P
6. Fugacity & Fugacity Coefficient: Species in Solution
By differentiation respect to ni at T, P and nj constant gives:
P
  ( nZ  n)  dP
ln ˆi    
0
ni T , P , n j P

 nZ   n 
  1
But:
   Zi
 ni   ni 
P
Replacing terms into equation we get: ln ˆi   Z i  1
dP
0 P
7. Generalized Correlation for Fugacity Coefficient
Prof. Angel Darío González-Delgado
7. Generalized Correlation for Fugacity Coefficient
• For pure gases, P  Pc Pr
dP  Pc dPr
w= Acentric factor, measures
the deviation in the vapor
P

• Hence, at P=Pr , ln i   Z i  1
dP pressure of a compound,
becomes, compared to noble gases for
0
P which the acentric factor
Pr

ln i   Z i  1
dPr takes the value zero
at constant Tr
0
Pr
Zo and Z1: Complex
• From Pitzer correlation, Z  Z   Z
0 1
functions of reduced
pressure and temperature
7. Generalized Correlation for Fugacity Coefficient
• Substitution of Zi becomes,
Pr

ln i  
 iZ 0
  Z i  1
1 dPr
Pr
0
Pr P

ln i    Zi  1
r
dPr 1 dPr
Or
0
   Zi
0
Pr 0
Pr

Where, ln i  ln i 0   ln i1
Pr Pr

ln i    Zi  1 r
dP dPr
0 0
ln    Z
i
1
i
1

0
Pr 0
Pr
7. Generalized Correlation for Fugacity Coefficient
ln   ln  0   ln  1 can also be written as:

    0

1 

Pr

ln i   Z i  1
dPr
can also be simplified by substituting:
0
Pr

Z 1 
Pr 
Tr
B  B1  Bo and B1: functions of reduced
temperature
7. Generalized Correlation for Fugacity Coefficient
Thus,

 
Pr
Pr  1 dPr
ln i   B  B
T
0 r
Pr

ln i  
Pr 
B  B1   Pr  1 
Tr or  
i  exp B  B 
 Tr 
7.1 Fugacity Coefficient from the Virial Equation of State
• For a specie i in solution,
P
ln i   Z i  1
ˆ dP
0
P

• Virial equation of state:

BP
Z  1
RT
• For n mol of gas mixture:
the bimolecular
nBP
nZ  n  B   yi y j Bij interaction between
RT i j molecule i and j
Bij  B ji
7.1 Fugacity Coefficient from the Virial Equation of State
B   yi y j Bij
i j

• For binary mixture……

7.1 Fugacity Coefficient from the Virial Equation of State
B   yi y j Bij
i j
• For binary mixture:

B  y1 y1 B11  y1 y2 B12  y2 y1 B21  y2 y2 B22

B  y12 B11  2 y1 y2 B12  y22 B22

• B11 and B22 are virial coefficient of pure species, B12 and B21 are cross
coefficients.
• These equations, that relates mixture coefficients with pure specie
coefficients and interaction coefficients are called mixture rules.
7.1 Fugacity Coefficient from the Virial Equation of State
B  y1 y1 B11  y1 y2 B12  y2 y1 B21  y2 y2 B22
Can be written as:
B  y(1
1  y 2 )B11  2 y1 y2 B12  y(1
2  y 1 )B22
B  y1 B11  y1y 2 B11  2 y1 y2 B12  y2 B22  y 1 y2 B22

B  y1 B11  y2 B22  y1 y212

12  2 B12  B11  B22
7.1 Fugacity Coefficient from the Virial Equation of State
nBP
nZ  n 
RT
• For binary mixture: Differentiation with respect to n1:
 nZ  P  nB 
Z1     1  
 n1  RT  n1  T , n2

P
• Thus ln i   Z i  1
ˆ dP
becomes,
0
P
P
P  nB  dP P    nB  
ˆ
ln 1   ln ˆ1   
  RT  n1 T ,n
0
RT  n1  T , n2 P 2
7.1 Fugacity Coefficient from the Virial Equation of State
Multiplying B  y1 B11  y2 B22  y1 y212 by n,
nB  ny1 B11  ny2 B22  ny1 y212

Substituting yi  ni n,
n1n2
nB  n1 B11  n2 B22  12
n
Deriving respect to n1;

   nB    1 n1 
   B11    
 2 12
n  B  1  y  y   B  y 2  12
2

 n1 T ,n2
11 1 2 12 11
 n n2 
7.1 Fugacity Coefficient from the Virial Equation of State
   nB   P    nB  
Substituting    B11  y 2212 into ln ˆ1    ;
 n1  RT  n1 T ,n
T ,n2
2

ln ˆ 1 
P
RT

B11  y 2212 
Similarly;
ˆ
ln 2 
P
RT
B22  y2212 
7.1 Fugacity Coefficient from the Virial Equation of State
For multicomponent gas mixtures,
P  
 Bkk   yi y j 2 ik   ij 
ˆ 1
ln k 
RT  2 i j 

where
 ik  2 Bik  Bii  Bkk and  ij  2 Bij  Bii  B jj
with
 ii  0,  ki   ik
 kk  0,
7. Generalized Correlation for Fugacity Coefficient
P  
 Bkk   yi y j 2 ik   ij 
ˆ 1
ln k 
RT  2 i j 

Where,
Bˆ ij  B 0  ij B1 0.422
B  0.083  1.6
0
B1  0.139 
0.172
Tr Tr4.2
and
Bˆij RTcij
Bij 
Pcij
7. Generalized Correlation for Fugacity Coefficient
The calculation for ij , Tcij , Pcij (proposed by Prausnitz et al. ),

i   j
Tcij  TciTcj  1  kij 
1/ 2
ij 
2
Z ci  Z cj Z cij RTcij
Z cij  Pcij  Interaction
2 Vcij parameter
(specific to
3 i-j molecule
V 1/ 3
V 1/ 3
 pair)
Vcij   
ci cj
 2 
 
7. Generalized Correlation for Fugacity Coefficient
To do: solve the generalized correlation for fugacity coefficient for a
ternary mixture, and for a mixture of four cmponents:

P  
 Bkk   yi y j 2 ik   ij 
ˆ 1
ln k 
RT  2 i j 