05 Chapter 11 (Compiled)

CHAPTER 11

Solution Thermodynamics
(Theory): Part 1

Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Topic Outcomes
Week Topic Topic Outcomes
8-9 Solution Thermodynamics: Theory It is expected that students are able to:
• Introduction to solution thermodynamics • Define and describe the important of

• The chemical potential and phase equilibria the thermodynamic terms such as partial
• Pure, partial, and solution properties and residual properties, fugacity and
• Ideal gas mixtures fugacity coefficient in chemical
• Ideal solution and Lewis Randall rule engineering.
• Fugacity and Fugacity Coefficient
• Pure species • Differentiate the difference between
• Solution fugacity and fugacity coefficient pure, partial, and solution properties.
• Fugacity coefficient and residual- property
relation • Estimate the fugacity and fugacity
• Fugacity coefficient from virial equation of coefficient for given pure (ideal or real),
states and mixture species at specified
• Generalized correlation for the fugacity conditions and approaches
coefficient
• Excess Properties
• Fundamental excess-property relation
• The excess Gibbs energy and activity
coefficient
• The nature of excess property

Scope of Lecture
Introduction to Solution Thermodynamics
Fundamental Property Relation
The Chemical Potential & Phase Equilibria
Partial Properties
Ideal Gas Mixtures

Introduction to Solution
Thermodynamics

Single Component System
Example: Steam Line
We know that for a single component system, the most common

thermodynamic variables are,
T and P
By now, we know how to determine Tsat, Psat, H (liquid and ideal/non-

ideal gas), V (liquid and ideal/non-ideal gas) and Hvap.

Mixture
We also learned about mixture before,
H   yiHi
We will see that this equation is only valid for ideal mixture
Consider the following systems,
A B
Both systems at the same T, P and n but with DIFFERENT
COMPOSITIONS.

Multicomponent System
Assuming an ideal mixture
 H A   yiAHi  H B   yiBHi
yiA  yiB
 H A   H B
So, we have new thermodynamic variables for multicomponent
system,
COMPOSITION
(x1, x2, x3) or (y1, y2, y3)
Example (Non-ideal Mixture)
Typical chemical processes involve a multicomponent system

whereby we CAN’T ASSUME IDEAL MIXTURE or IDEAL SOLUTION
BEHAVIOR
Consider mixing 1000 cm3 MeOH and 1000 cm3 H2O at 25 C
 2000cm3 solution
In fact
 1970cm3 solution
1000 cm3 1000 cm3
MeOH H2O

Main Objectives
Develop the theoretical foundation of thermodynamics to

gas mixtures and liquid solutions.
Introducing
• Chemical potential
• Partial Properties
• Fugacity
• Excess properties
• Ideal solution

Density of the Solution
Assume ideal solution
1 1
ρ 
V  xiVi
From above equation, the calculated solution molar density is
0.0396 mol/cm3.
The actual molar density is 0.0410 mol/cm3 that could be calculated

from
1 1
ρ 
V  xiVi Partial properties
We just introduced a new thermodynamic property for a

multicomponent system
PARTIAL PROPERTIES
Fundamental Property
Relation

Closed System
Basic relation connecting the Gibbs energy to the T & P in any

closed system
d nG   nV dP   nS dT
  nG    nG 
d nG    dP    dT
 P  T,n  T P,n
Applied to a single-phase fluid in a closed system wherein no

chemical reaction occur.

Open System
Consider the following system

• Open system & multicomponent
• Single phase at T & P
• Variable compositions (n1, n2, n2 etc)
So, Gibbs energy (G) could be written as a function T, P, n1,
n2, n3 etc.
nG g  P, T,n1 , n2 , ni ,

Chemical Potential
Apply partial differentiation and FPR
  nG    nG    nG 

d nG    dP   T  dT    dni
 P  T,n  P,n i   ni P,T,nj
  nG 
d nG   nV dP   nS dT    dni
i   ni P,T,nj
  nG 
μ 
Define, i  = Chemical potential of species i in the mixture
  ni P,T,nj
Note: FPR, fundamental property relations Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Fundamental Property Relation
Therefore
d nG   nV dP   nS dT μidni FPR for single-fluid systems of

i constant or variable composition
When n =1
dG VdP SdT μidxi G  G P, T, x1 , x2 , xi ,
i
  nG    nG 
V  S
 P  T,x  T  P, x
The Gibbs energy is expressed as

a function of its canonical
variables.
Note: FPR, fundamental property relations Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Q?
How do we determine the phase of multicomponent system ?
If it is two phases, how do we determine the composition of

each phase?
Before answering these, we need to establish THE CONCEPT

OF PHASE EQULIBRIA FOR MULTICOMPONENT SYSTEM.

The Chemical Potential
and Phase Equilibria

Chemical Potential
Consider the following system,

n
• Closed system & multicomponent
• Two phases in equilibrium n
• Mass transfer occurs if the equilibrium is disturbed
Each phases ( and ) is actually an open system

→ Free to transfer mass to the other, So
d nG   nV dP  nS dT μiαdniα

α α α
d nG   nV dP  nS dT μβidnβi

β β β
Note:  and , identify the phases Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Phase Equilibria
Add the 2 equations for a VL system ( →v and  → l)
d nG  d nG   nV dP  nV dP  nS dT  nS dT μivdniv  μlidnli
v l v l v l
i i
d nG   nV dP  nS dT μivdniv  μlidnli

i i
For equilibrium system
 nV dP  nS dT  nV dP  nS dT μivdniv  μlidnli
i i
So,
μ dn  μdn  0
i
v
i
v
i
i
l
i
l
i Also dnli  dniv
μ dn  μdn  μ  μ dn  0

i
v
i
v
i
i
l
i
v
i
i
v
i
l
i
v
i μiv  μli (i= 1, 2, ……, N)
Note: V, vapor; L, liquid Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Criteria
If apply to system with  phases (i.e., more than 2 phases)
μiv  μli  μβi  μiα   μiπ
This is criteria for the phase equilibrium for multicomponent system
Thus,
Multiple phase at the same T and P are in equilibrium when the

chemical potential (i) of each species is same in all phases
nα μiv
μiv  μli
nβ μli

Partial Properties

Partial Property of Individual Species
Based on the definition of i, let’s define a partial molar property as

follows,
  nM 
M i   M  V, U, H, S, G etc
This is a partial property of individual species as they exist in a

solution or mixture
This property is different from a pure species property primarily due to

molecular interaction of different species in the solution or mixture.

Partial Property of Gibbs Energy
Hence, the chemical potential of species i (i) is known also as

partial property of Gibbs energy for species i,
  nG  Compare   nM 

μi    Mi   
 ni P,T,nj  ni P,T,nj
  nG 
μi  Gi   

Relation of Molar – Partial Molar Properties
Let’s familiar with symbols in solution thermodynamics
Symbol Type of property Example
Mi Pure-species properties U i, H i, S i, G i
Mi Partial properties U i , Hi , S i , G i
M Solution or mixture properties U, H, S, G

Equations Relating Molar and Partial Molar
Properties (Homogenous Phase)
In general, for homogenous mixture
nM  Μ  T, P, n1, n 2 ,  , n i , 
  nM    nM    nM 

d nM    dP    dT    dni
 P  T,n  T P,n i  ni P,T,n
j
Could also be written as,
 nM   nM 
d nM    dP    dT   Midni
 P  T,x  T  P,x i
i.e. constant composition

Homogenous Phase (Cont.)
ni
Where, Also, xi  ni  xin
n
d nM  ndM Mdn dni  xidn  ndxi
Substitute into
 nM   nM 
d nM   dP   T  dT   Midni
 P  T,x P, x i
 nM   nM 
ndM Mdn    dP    dT   Mi  xidn ndxi 
 P  T,x  T  P, x i
Rearrange
  M   M    
 dM   
 P  T,x
dP   
 T P, x
dT   Midxi  n  M   Mi xi  dn  0
 
 i  i
1st bracket 2nd bracket

Summability Relations
This is equal to “0” if both terms in the brackets are zeros, so for
1st bracket,
 M   M 
dM    dP    dT   Midxi
  P  T,x   T P, x i
And the 2nd bracket,
M  xM
i
i i
Or
nM niM i
i
These equations show that the calculation of mixture properties of

constituent species from partial properties is by a simple
summability relation.

Gibbs/Duhem Equation
Further expanded
M   xiM i dM   xid M i   Midxi

i i i
Substitute into
 M   M 
dM    dP    dT   Midxi
  P  T,x   T P, x i
 M   M 
 x dM   M dx   P 
i
i i
i
i i dP    dT   Midxi
 T P, x i
T,x
 M   M 

  P
 dP  
 T,x   T
 dT 
 P, x
 x dMi
i i

Gibbs/Duhem Equation (Cont.)
 M   M 
  dP    dT   xidMi  0 Gibbs/Duhem Equation
 P  T,x  T P, x i
This equation must be satisfied for any changes in P, T, and M i in

a homogenous phase.
And shows that the partial properties of species making up a

solution are dependent on one another.
For const. T and P, it simplifies to,
 x dM  0
i
i i

Partial Property in Binary Solutions
Two-component system: i = 1, 2
Here, we will derive an equation for partial property of a species in

binary mixtures as in term of solution property (express a function of
composition at constant T and P)
From equation M   xM
i
i i
M  x 1M1  x 2 M 2 dM  x 1d M1  M1dx 1  x 2 d M 2  M 2 dx 2
x1  x2 1  dx1  dx2
dM  x 1d M1  M1dx 1  x 2 d M 2  M 2 dx 1

Binary Solutions (Cont.)
 M   M 

From equation P  dP    dT atconst. 0
xidMi T &P
  T,x   T P, x i
x 1d M1  x 2 d M 2  0
So,
dM
dM  M1dx 1  M 2 dx 1  M1  M 2
dx 1
Hence, we could show that,
dM dM
M1  M  x 2 M2  M  x1
dx 1 dx 1
M  x 1M1  x 2 M 2

Relations Among Partial Properties
d nG   nV dP   nS dT  Gidni

i
Maxwell relation (Chap. 6),
 V   S   Gi    nS   Gi    nV 

              
 T P,n  P T,n  T P,n  ni P,T,nj  T P,n  ni P,T,nj
 Gi   Gi 
   Si    Vi
 T P,x  T P,x
 d G i  V idP  S idT
H  U  PV Hi  U i  P V i

Parallel Relation
By application of definition of partial properties, we could

show that
Eqn. for const. composition Eqn. for partial properties
Similarly we can write
H  U  PV Hi  U i  P V i
dG  VdP  SdT d G i  VidP  S idT

Example 1
The need arises in a laboratory for 2,000 cm3 of an antifreeze solution

consisting of 30-mol-% MeOH in H2O. What volumes of pure methanol
and of pure water at 25˚C must be mixed to form the 2,000 cm3 of
antifreeze, also at 25˚C? Partial molar volumes for MeOH and H2O in a
30-mol-% MeOH solution and their pure-species molar volumes, both at
25˚C , are:
MeOH1 : V1  38.632cm3 mol-1 V1  40.727cm3 mol-1

H2O  2 : V2  17.765cm3 mol-1 V2  18.068cm3 mol-1

Solution 1
Molar volume of the binary antifreeze solution
V  x1V1  x2 V2
=(0.3)(38.632) + (0.7)(17.765) = 24.025 cm3 mol-1
Since the required total volume of solution is Vt = 2,000 cm3, the total
number of moles required is:
Vt 2,000
n   83.246mol
V 24.025
Of this, 30% is methanol, and 70% is water:
nl = (0.3)(83.246) = 24.974 mol n2 = (0.7)(83.246) = 58.272 mol

Solution 1 (Cont.)
The volume of each pure

species is Vi t = ni Vi thus,
V1t = (24.974)(40.727) = 1,017 Tangent line

at x1=0.3
V2t = (58.272)(18.068) = 1,053 cm3
0.3

Ideal Gas Mixtures

Molar Volume of Ideal-Gas Mixture
Consider,
• System A contain species 1 at T, P V  ig

A 
RT
P
 V1ig
• System B contain species 2 at T, P V  ig

B 
RT
P
 V 2ig
• System C contain species 1 & 2 at T, P V  ig

C 
RT
P
 V ig

Partial Molar Volume of Species i
From definition of partial properties, the application of partial

to molar volume,
  RT  
  nV ig    n P   RT   n  RT
Vi ig
          
  n i  T, P, n j   ni  P   ni  P
 
T, P, n j
Thus,
RT
V Aig  V Big  V Cig   V ig  T, P   V iig  T, P   Viig  T, P 
P

Partial Pressure of Species i
The pressure that a species i would exert if it alone occupied

the molar volume of the mixture
p i V T, ig  n iRT
Divide by ideal gas for mixture, PV T, ig

 n T RT
pi n
 i  yi
P nT
y iRT
p i  y iP 
V ig
Note: VT, ig, total volume of ideal-gas mixture at T; pi, partial pressure of species i at T ; yi, Mole fraction of species i in the ideal-gas
mixture
Partial Molar Properties of Species i
Gibb’s Theorem
A partial molar property (other than volume) of a constituent

species in ideal-gas mixture is equal to corresponding molar
property of the species as a pure ideal-gas at the mixture but at a
pressure equal to its partial pressure in the mixture.
M i ig  V iig Miig  T,P   Mig

i  T, pi 

Partial Molar H, U, Cp of Species i
Apply Gibb’s theorem to enthalpy, internal energy and heat capacity
ig ig
, C ig
Since H , U and p
ig
C v independent of P
are
Hiig  T, P   Hig
i  T, pi   Hi  T, P 
ig
Hiig  Hig
i
Similarly Uiig  Uig

i
C piig  C ig
p, i C viig  C igv, i
So, for ideal-gas mixture
Hiig   yiHig
i Uiig   yiUig
i C piig   yiC ig
p, i (Chap. 4)

Property Change of Mixing (Hig,  Uig & Vig)
 Mig
mix  M final  Minitial  Mig
  y Mig
i i
But Mig   yiMig

i
So,  Mig
mix  0
for M = H, U, V Minitial Mfinal
Note: Both initial and final conditions (T, P) are the same.
E.g. Enthalpy change of mixing for ideal gas mixture,
 Hig
mix  0

Partial Molar Entropy of Species i
dT dP
i  C Pi
dSig R
ig
Sig is dependent of P, (Chap. 6)
T P
For isothermal mixing, dP

i  R
dS ig
P
dP 1
i  T,P   S i  T, pi   R
S ig  Rln
ig
Integrate from pi to P,
pi yi
i  T, pi   S i  T, P   Rlny i
S ig ig
From Gibb’s theorem
S iig  T, P   S ig
i  T, pi   S i  T, P   Rlny i
ig

Property Change of Mixing (Sig)
Hence, for ideal-gas mixture
S ig  T,P    yiS ig 
i  T, pi    yi S i  T, P   Rlnyi
ig

S ig  T, P    yiS ig
i  R  yilnyi
So, entropy change of mixing for ideal gas mixture
 S ig
mix  S ig
 T, P    y S
i i
ig
 R  yilnyi
1
mix  R  yiln
 S ig
yi

Partial Molar Gibbs Energy Species i
By parallel relation,
G ig  Hig  TS ig
Giig  Hiig  T S iig
So,
Giig  Hiig  T  S ig
i  Rlnyi   Hig
i  T  S i  Rlnyi 
ig
μig
i  Gi
ig
 G i  RTlny i
ig

Alternative Expression
In terms of variables (T, P) for Gibbs energy,
RT
i  Vi dP  S i dT 
dGig dP  RTdlnP
ig ig
(For const. T)
P
i  i  T   RTlnP
Integration, G ig
Integration const. at cons. T.
So,
i  Gi  G i  RT lnyi  i  T   RT lnP  RT lnyi

μig ig ig
i  i  T   RT lnyiP
μig

Property Change of Mixing (Gig)
Hence, for Gibbs energy of an Ideal-gas mixture
G ig
i   i i
y G ig
G ig
i   y i i  RT  yilnyi
G ig
mix  G   yi Gi  RT  yilnyi
 G ig ig ig
Alternative expression
i   yi Gi
G ig i   yii  T   RT
G ig  y lnyP
ig
i i

Summary: Partial Molar Properties of Species i
For those independent of P, e.g.
i  T, pi   Hi  T, P 
ig
Hiig   yiHig
i Uiig   yiUig
i
i  R dlnP (const. T)
For those dependent of P, e.g. dS ig
dP P 1
i  T, P   S i  T, pi   R
S ig  Rln  Rln
ig
pi yiP yi
Miig  T,P   Mig

i  T, pi 
Gibb’s theorem
i  T, pi   S i  T, P   Rlnyi
S ig ig
S ig  T, P    yiS ig
i  R  yilnyi
i  T, pi 
Giig  Hiig  T Siig Giig  Hig
i  TS i  RTlny i
ig
S ig
i  T, P   S  T, pi   Rlnyi
ig
i
i  Gi  G i  RT lnyi
μig ig ig
i  i  T   RT lnyi P
μig
i  i  T   RT lnyiP
G ig
RT
G   yii  T   RT From integration of, dGi  Vi dP  dP  RTlnP
ig ig
ig
i  y lnyPi i P
Summary: Property Change of Mixing
 Mig
mix  M final  Minitial  Mig
  i i
y Mig
 Hig
mix  0
 Uig
mix  0
 Vmix
ig
0
1
mix  R  yiln
 S ig
yi
mix  RT  yilnyi

 G ig

Example 2
What is the change entropy when 0.7 m3 of CO2 and 0.3 m3 of N2, each
at 1 bar and 25 C blend to form a gas mixture at the same conditions.
Assume ideal gas.
Example 3:
A stream of nitrogen flowing at the rate 2 kg s–1 and a stream of

hydrogen flowing at the rate of 0.5 kg s–1 mix adiabatically in a steady-
flow process. If the gases are assumed ideal, what is the rate of entropy
increase as a result of the process.

CHAPTER 11
Solution Thermodynamics
(Theory): Part 2
Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia

Scope of Lecture
Fugacity and Fugacity Coefficient: Pure Species
Generalized Correlation for the Fugacity Coefficient
Fugacity and Fugacity Coefficient: Species in Solution
Ideal Solution
Non-ideal Solution

Fugacity

Definition
A measure of a chemical potential in the form of 'adjusted pressure.'
It reflects the tendency of a substance to prefer one phase (solid, liquid

or gas) over another, and can be literally defined as “the tendency to
flee or escape”.
At a fixed T and P, a homogenous substance will have a different

fugacity for each phase.
The phase with the lowest fugacity will be the most favorable, and
will have the lowest Gibbs free energy.
Unit: same units as P (e.g., atm, psia, bars, etc.)

Introduction
Cubic equation of state
Pure species VLE for pure species
Pure liquid
Fundamental residual-
property relations
Species in solution
Fugacity (f) &
fugacity Virial equation of state
coefficient ()
Generalized
Extension to mixture
Correlations for 
Ideal solution model Lewis/Randall rule
Excess Gibbs energy &

activity coefficients
Excess properties
Nature of excess
properties
Fugacity and Fugacity
Coefficient: Pure Species

Fugacity of Pure Species
The concept of fugacity is introduced when we want to apply an

equation similar to G i  i  T   RTlnP
ig
(ideal gas) to a real fluid (liquid or
gas).
This is done by replacing P with a property specific to a particular

species called FUGACITY.
G i  i  T   RTln f i Fugacity of pure species i with unit

of P) i.e. i is a pseoudopressure.
Note: For a gas under an ideal gas condition, i = P

Residual G & Fugacity Coefficient
G i  i  T   RTln f i ― G ig
i  i  T   RTlnP
fi
G i  G ig
i  RTln f i  RTlnP  RTln
P
fi
G Ri  RTln
P
Define i as a fugacity coefficient for species i as follows,
fi
i  A dimensionless quantity
P
So for ideal gas, iis 1
Note: G, Gibbs energy Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Determination of Fugacity Coefficient, i
Fugacity coefficient of pure species from equation of state (EoS)
G Ri  RTln i
ln i 
G Ri GR

 Z  1 dP (Chap. 6)
RT RT P
Combine
G Ri dP
   Zi  1
P
RT 0 P
dP
 
P
lni  0 iZ  1
P
i from Virial Coefficient
The 2-term Virial equation for Zi:
B iiP
Zi  1 
RT
dP
 
P
lni  0 iZ  1
P
P  B iiP  dP B ii P B iiP
lni       dP 
0
 RT  P RT 0 RT
B P 
i  exp ii 
 RT 
Note: Bii = B

Alternative Equation
Alternatively for the 2-term Virial equation for Zi:
Zi  1 
BP BPC Pr

RT RT C Tr
P

 B 0  ωB1 r
Tr

 Zi  1  0  Zi  1 dPr
dP
P Pr
lni  
0 P Pr
lni  
P B 0
 ωB1  P
Pr  B 0  ωB1 r 
0 Tr Tr
For B0 and B1, see equation 3.65 and 3.66

P 
i  exp r B 0  ωB1   0.422 1 0.172
 Tr  B 0  0.083
Tr1.6
B  0.139
Tr4.2

i from Cubic EoS
Combine equation 11.33 with 6.66b (apply for species i)
G Ri
G Ri  RTln i  Zi  1 ln Zi  βi   qiIi
RT
We get,
lni  Zi  1 ln Zi  βi   qiIi
• Eq. 3.49 (vapor phase) Eq. 3.50 Eq. 3.51 • Case I: 
• Eq. 3.53 (liquid phase) • Case II: =
• Eq. 6.65b (Note: For van
der Waals, Ii = i/Zi

i from Generalized Correlations
Lee/Kesler correlation,
dP
 
P
lni  0 iZ  1
P
For P  PcPr  dP  Pc dPr
   Z0  ωZ1  1 r
Pc dPr dPr dP
 Zi  1    Zi  1
Pr Pr Pr
lni  
0 PcPr 0 Pr 0 Pr
lni  
0
Pr
 Z  1 P  ω0 Z1 dP
0 dPr Pr
Pr
r
lni  lni0  ωlni1 i    i

0
i 
1 ω
Values for i0 and i1 are found from Table E.13 – E.16.

VLE for Pure Species
From Chapter 6 we know that criteria for VLE for pure species is Gv
= Gl or Gv – Gl = 0
Let’s apply equation G i  i  T   RTln f i phase

for each
G iv  i  T   RTln f i v G li  i  T   RTln f i l
fi v fi v
By differences G  G  RTln l  0 ln l  0
v l
i i
fi fi
fi v
l
1 fi v  fi l  fi sat
fi
f i sat Another phase equilibrium

Also  i
sat
 sat iv  il  isat criteria for pure species
Pi
For a pure species coexisting liquid & vapor phases are in equilibrium
when they have the same T , P and  .
Note: VLE, Vapor/liquid equilibrium Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Fugacity of Pure Liquid
Fugacity of pure liquid at T and P calculated by the Poynting factor
equation ad derived below,
f i l Pisat  f i v Pisat  f i l  P  sat f i l  P  sat fil P 

f i  P   v sat
l
Pi  1 i  l sat Pi  i Pi
sat sat sat
f i Pi  Pisat f i l Pisat  f i Pi  f i l Pisat 
Also,
fil
G G l
i
l, sat
i  RTln f i  RTln f i
l l, sat
 RTln
f i l, sat
At const. T, dGi  V&idP

integrate from sat. liq. to compressed liq.,
P
G G   V dP
l l, sat l
i i i
Pisat

Fugacity of Pure Liquid (Cont.)
P
fil G G   V dP
l l, sat l
G li  G l,i sat  RTln f i l  RTln f i l, sat  RTln i i i
f i l, sat Pisat
Combine
fil
P Rearrange fi l 1
P
  V dP  exp  V dP
l l
RTln l, sat i l, sat i
fi Pisat
fi RT Pisat
f i l  P  sat
fi P   
l sat
Pi
f i Pi 
i l sat
Subs into
P
1 Vil
P
fi    V dP
l sat sat l
P exp fi    dP
l sat sat
i i i P exp
RT Pisat
i i
RT Pisat
Note: Vil is approximately const. & is evaluated at sat. liquid, therefore

The exp. Is known as
V P  P
l sat
 a Poynting factor Fugacity of
f i l  isatPisatexp i i
pure liquid i
RT
Example 4
For SO2 at 600 K and 300 bar, determine good estimates of the fugacity
and of GR/RT.
Tutorial 1:
Estimate the fugacity of isobutylene gas:

a) At 280 C and 20 bar.
b) At 280 C and 100 bar.
Tutorial 2:
Estimate the fugacity cyclopentane at 110 C and 275 bar. At 110 C the
vapor pressure of cyclopentane is 5.267 bar.

Fugacity and Fugacity
Coefficient: Species In Solution

Criteria for Phase Equilibrium
Revisit, for an ideal gas mixture
μig  i  i  T   RT ln yiP 

ig
i G
Parallel to the definition of fugacity for pure species, the introduction of

fugacity for species in solution,
i  Gi  i  T   RT lnf i
μig ig ˆ Replacing yiP with fugacity
Fugacity of species in i in a mixture or solution
At VLE μi  μi
v l
i  T   RT lnfî l  i  T   RT lnfî v
fî l  fî v Criteria of VLE for multicomponent system

Fugacity Coefficient
nGR  nG  nGig
   nGR      nG    nGig  

     
  ni  P,T,nj   ni  P,T,n j  ni  P,T,nj
ˆ fî
G  Gi  G   i    RT lnf i  RT ln yiP  RT ln
i
R
i
ig ig
i
yiP
GiR  RT lnî Fugacity coefficient of species i in solution,
Mostly applied to gas mixture

Fundamental Residual-Property Relation
 nG  1 nG
d  d nG  dT
 RT  RT RT 2
 nG 
d 
1
 nV dP   nS  dT   Gidni  n H  TS
   dT
 RT  RT RT 2
 nG  nVdP nSdT G dn nH nS
d    i i  2
dT  dT
 RT  RT RT RT RT RT
 nG  nVdP nH Gi
d
 RT

 RT

RT 2
dT   RT
dni
For ideal gas
 nGig  nVigdP nHig Giig Fundamental residual-

d    2
dT   dni
 RT  RT RT RT property relation

Alternative Form
 nG  nVdP nH G  nGig  nV igdP nHig Giig

d   dT   i dni ― d    2
dT   dni
 RT  RT RT 2
RT  RT  RT RT RT
GiR  RT lnî
 nGR  nVR dP nHR GiR

d    2
dT   dni
 RT  RT RT RT
 nGR  nVR nHR

d   dP  2
dT  lnîdni
 RT  RT RT
Thus,
ˆ  nGRi /RT 
lni    lnî is a partial property of GR/RT
 ni  P,T, nj

Calculation of Fugacity Coefficient
G R
 Z  1 dP   nG R
i /RT

 lnî   
RT P   n i  P,T, nj
ˆ    nZ  n 
P
dP
lni    
0
ni  P,T, n P
j
 nZ n 
P
dP
   
0
ni ni  P,T, n P
j
  nZ 
P
 n   dP

   
 ni   
0   ni  P,T, n  P
 P,T, n j j 
P
lnî   Z  1 dP
P
• Integration at cont. T & composition.
• Calculation from PVT data.
0

Using 2-Term Virial EoS
BP nBP
Z  1 nZ  n 
RT RT
   nZ  P    nB  
Z1     1   
  n1  P,T, n2 RT   n1  T,n2
Substitute into
P
lnˆ1   Z  1dP
P

0
P  dP P 1     nB  
ˆ  P    nB    dP
ln1   1    1   
 RT  n1 
0
 P RT   n1  T,n 
T,n2  0  2 
1    nB  P    nB  
P
lnˆ1  0 RT  n1  dP    How to evaluate?
T,n2
RT   n1  T,n2

Binary Mixture
For mixture Note,
B11  B1 B 22  B 2
B    yiy jB ij
i j
B12 
RT c12 0
Pc12

B  ω12B1 
ω1  ω2 Interaction (= 0 if
Consider a binary system (species 1 & 2) ω12  no data provided)
2
B  y1y1B11  y1y2B12  y2 y1B 21  y2 y2B 22 Tc12   Tc1Tc2  1 k12 

1/2
Zc12RT c12
Pc12 
B  y12B11  2y1y2B12  y22B 22 Vc12
3
 Vc1
1/3
 Vc2
1/3

B  y11 y2 B11  2y1y2B12  y2 1 y1 B 22 
Vc12   
 2 
Z  Zc2
Zc12  c1
2
Note: B11, B22, pure species coefficient; B12, cross coefficient Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
2nd Virial Coefficient
Rearrange further
B  y1B11  y1y2B11  2y1y2B12  y2B 22  y1y2B 22
 y1B11  y2B 22  2y1y2B12  y1y2B11  y1y2B 22
 y1B11  y2B 22  y1y2  2B12  B11  B 22 
B  y1B11  y2B 22  y1y2 12
Multiply by n (note: yi = ni/n)
n2
nB  n1B11  n2B 22  n1  12
n

2nd Virial Coefficient (Cont.)
Differentiate So,
   nB     n1 / n  P    nB  
   B 11  0  n  
2 12 
 lnˆ1   
 n1  T,n2  n1  RT  n1  T,n
2
u vu  uv
Note :  
v v2
 nn1  n1n 
 2   1 n n 
 B11  n2  n  12  B11  n2   21  12


n1 
  n n n1  lnˆ1 
P
RT

B11  y22 12 
 
n n n n   n 
 B11   2  22 1  12  B11   y2  y2 y1  12
 n n n1   n1  Similarly,
   nB 
   B11  1  y1  y2 12  B11  y22 12 lnˆ2 
P
RT

B 22  y12 12 
 n1  T,n2
Multicomponent Gas Mixtures
The general equation is,
P  
 B kk    yiy j  ik   ij  
1
lnˆk   
RT  2 i j 
Where,
 ik  2Bik  B ii  B kk and  ij  2Bij  B ii  B jj
 ii   jj  0 and  ik   ki
B ij 
RT cij
B 0
 ωijB1  ωij 
ωi  ω j
Tcij   TciTc2 
1/2
1 k ij
Pcij 2
3
ZcijRT cij V 1/3
V 1/3
 Zci  Zcj
Pcij  Vcij   ci cj


Zcij 
Vcij  2  2

Using Generic Cubic EoS
bi
ln i   Zi  1  ln Zi  βi   qiIi
ˆ
b
Refer to Chapter 14 if you interested in the details.
(Out of scope for this class)

Summary (1): Pure Species
Chemical potential: i  i  T   RTlnP
G ig
G i  i  T   RTln f i
  nG 
μi   
 ni P,T,nj
fi fi
G i  G ig
i  RTln G Ri  RTln
P P
• Provide fundamental criterion for fi
phase equilibrium i 
P
• However, the Gibbs energy, hence i is
defines in relation to the U and S – dP
 
P
(absolute value are unknown) EoS lni  0 iZ  1

P
Fugacity:  B iiP  P 1 
2-term Virial i  exp  i  exp r B  ωB  
0
 RT   Tr 
G i  i  T   RTln f i Cubic EoS lni  Zi  1 ln Zi  βi   qiIi
i  i0 i1 
• A quantity that take place of i Lee/Kesler ω
Note: U, internal energy; S, entropy Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Summary (2): Pure Species
VLE for pure species Fugacity of pure liquid
Sat. vap.: G iv  i  T   RTln f i v The  of pure species i as a compressed liq.:
fil
P
G  i  T   RTln f i
l l
Sat. liq.: G G
l l, sat
 RTln G G   V dP(isotherm)
l l, sat l
i i i i
i i
f i l, sat Pisat
P
v fil 1
f   V dP
l
ln
G  G  RTln i l
v
i
l
i fi l, sat
RT
i
fi Pisat
Since Vi is a weak function of P

VLE
fi v fil Vil P  Pisat 
G i  G i  RTln l  0
v l ln 
fi f i l, sat RT
f i sat  isatPisat
fi  
l sat sat 
Vil P  Pisat 
  
i
v
i
l
i
sat
fi  fi  fi
v l sat
i i P exp
RT

Summary (1): Species in Solution
Fugacity coefficient form the virial EoS
BP
The virial equation: Z  1
RT
• The mixture 2nd – virial coefficient B: B    yiy jB ij

i j
• For binary mixture: B  y1y1B11  y1y2B12  y2 y1B 21  y2 y2B 22
nBP
For n mol gas mixture: nZ  n 
RT
   nZ  P    nB  
Z1     1   
 n1  P,T, n2 RT  n1  T,n
2
1    nB  P    nB 
P
lnˆ1     dP   
0
RT   n1  T,n2
RT   n1  T,n2

Summary (2): Species in Solution
   nB  P    nB   RT cij
B 
P
1
lnˆ1   B ij   ωijB1
0
  dP   
0
RT  n1  T,n2 RT  n1  T,n
2
Pcij
B  y1y1B11  y1y2B12  y2y1B 21  y2y2B 22 ωi  ω j

ωij 
2
 12  2B12  B11  B 22 yi  ni /n
Tcij   TciTc2 
1/2
1 k 
P
  P
 
ij
lnˆ1  B11  y22 12 lnˆ2  B 22  y12 12
RT RT
ZcijRT cij
Pcij 
Vcij
For multicomponent gas mixture, the general form:
3
 
 B kk    yiy j  ik   ij  
P 1  Vci1/3  Vcj1/3 
lnˆk    Vcij   
RT  2 i j   2 
 
 ik  2Bik  B ii  B kk  il  2Bij  Bii  B jj
Zci  Zcj
Zcij 
 ii   jj  0  ik   ki 2

Example 5
Estimate ˆ1 and ˆ2 for an equimolar mixture of methyl ethyl

ketone(1)/toluene(2) at 50 C and 25 kPa. Set all kij = 0.
Tutorial 3:
For the system ethylene(1)/propylene(2) as a gas, estimate fˆ1, fˆ,2 &ˆ1

ˆ2 at 150 C, P = 30 bar, and y1 = 0.35.
Tutorial 4:
For the system methane(1)/ethane(2)/propane(3) as a gas, estimate f,ˆ1

fˆ2 fˆ3 ˆ1 ,ˆ2 , ˆ2 , , at 100 C, P = 35 bar, y1 = 0.21 and y2 =
0.43.

The Ideal Solution

Ideal Solution
We know for ideal-gas mixture
i  Gi  G i  RT lnyi
μig ig ig
No molecular forces/interaction and negligible particle volume

(compare to molar volume).
For an ideal solution, we define
i  Gi  G i  T, P   RT lnxi
μid id id
There exist intermolecular interaction but the various molecules

have similar size, structure and intermolecular forces.
Applicable for real gas mixture and liquid solution (application is

most often to liquid solution).
Thus, for an ideal solution G   xi Gi   xiG i  RT  xi lnxi

id id

Entropy
Substitute into
μi  Gi dG VdP SdT μidxi dG VdP SdT  Gidxi
i i
Apply criterion of exactness,
   nS     Gi 
Si       
 xi  P,T, x  T  P, x
For ideal solution,
  Giid 
S  
id
   

i  T, P   RT lnxi
  G id 


i
  T  P, x   T  P, x
S   
id i  T, P 
  G id   
 RlnxiT 
 
i  Siid  S i  Rlnxi
 T  P, x   T  P, x
S id   xi  S i  Rlnxi    xiS i  R  xilnxi

Enthalpy & Molar Volume
Enthalpy Molar Volume
dG VdP SdT  Gidxi

Hiid  Giid  T S iid i
Apply criterion of exactness,
Hiid  G i  RT lnxi  T  S i  RT lnxi    Gi   V 

    i   Vi
  P  x
 T,x  i  P,T, x
 G i  TS i
For ideal solution,
Hi  Hi
id   Giid 
V  
id   G id
   

i  T, P   RT lnxi



i
  P  T,x   P  T,x
For ideal solution,  G id
V   i
id  T, P  
i  Viid  Vi
 P  T,x
Hid   xiHi
V id   xi Vi

Non-Ideal Solution

Excess Property
Previous: The real solution is evaluated with reference to ideal gas

mixture by using the definition of residual property.
Hence the following equation is generally and easily apply for a gas
mixture.
Real liquid solution is, however, much more convenient to be

evaluated with reference to its departure from an ideal solution
(not ideal-gas) behavior.

Definition
Hence, we define an excess property as,

→ The difference between actual property of a solution and the
property of an ideal solution at the same T, P and xi
ME  M  Mid M  ME  Mid (M = V, U, H, S, G etc)
Example:
H  HE  Hid
Now, let’s apply this definition to Gibb’s energy

Excess Gibbs Energy
G E  G  G id nGE  nG  nGid
  nGE      nG     nGid  
G  Gi  G
i
E
i
id
     
  ni  P,T, nj   ni  P,T, n j   ni  P,T, nj
Gi  i  T   RT lnfî Giid  G i  RT lnxi  i  T   RT lnf i  RT lnxi
GiE  i  T   RT lnfî   i  T   RT lnf i  RT lnxi 
GiE  RT lnfî  RT lnf i  RT lnxi
 fî 
G  RT ln
i
E


 xi f i 
Activity Coefficient
The previous equation could be written as,
GiE  RT ln i
Where, fî
i  An activity coefficient for species i
xi f i
fî   i xi f i For a liquid solution

Ideal Solution (Lewis/Randall Rule)
For ideal solution,
 fî id 
G 0
E
RT ln   RT ln  i   0
i 
 xi f i 
So,
fî id
i  1 fî id  xi f i Lewis/Randall rule
xi f i
Also divide by Pxi
fî id xi f i
 îid  i
Px i Px i

Fundamental Excess-Property Relation
 nG  1 nG
d  d nG  dT
 RT  RT RT 2
 nG 
d 
1
 nV dP   nS  dT   Gidni  n H  TS
   dT
 RT  RT RT 2
 nG  nVdP nSdT G dn nH nS
d    i i  2
dT  dT
 RT  RT RT RT RT RT
 nG  nVdP nH Gi
d
 RT

 RT

RT 2
dT   RT
dni
For ideal solution
 nGid  nViddP nHid Giid

d    2
dT   dni
 RT  RT RT RT

Fundamental Excess-Property Relation
 nG  nVdP nH G  nGid  nV iddP nHid Giid

d   dT   i dni ― d    2
dT   dni
 RT  RT RT 2
RT  RT  RT RT RT
 nGE  nVE dP nHE GiE

d    2
dT   dni
 RT  RT RT RT
 nGE  nVE nHE

d   dP  2
dT  ln idni
 RT  RT RT
Thus,
 nGEi /RT 
ln i    ln i is a partial property of GE/RT
 ni  P,T, n j

GE/RT
GE
  xiln i
RT i
 x dln
i
i i 0 (Const T, P)
These equations find important in phase-equilibrium

thermodynamicas

Gibbs Energy & Related Properties

VLE
Consider a multicomponent system in VLE, the fugacity of species i

for each phase
For vapor mixture fî v  îv yiP
For liquid solution fî l   i xiP
VLE criteria
fî v  fî l îv yiP   i xiP
This is the VLE relation that relates the composition of vapor phase
and that of liquid phase.
See Chap. 10 for application of this relation and Chap. 12 for i

The Nature of Excess Properties
Chloroform(1)/n-heptane(2) Acetone(1)/Methanol(2) Acetone(1)/Chloroform(2)
500 500 1000

J mol–1
Ethanol(1)/n-heptane(2) Ethanol(1)/Chloroform(2) Ethanol(1)/Water(2)
1000 500
500
–500 –500 –1000

0 1 0 1 0 1
x1 x1 x1

6 Binary Systems (Previous Figure)
Excess properties are often strong function of T, but at normal T are

not strongly influenced by P.
Excess properties for six binary liquid mixture at 50 C (atm. P)

→Common behavior,
1. Excess properties become “0” as either species 1 (approaches

purity)
2. GE is approximately parabolic shape; HE and TSE exhibit individual

composition dependence.
3. The extreme value of ME often occurs near the equimolar

composition.

Summary (1): Ideal Solution
G  G  T,P   RT lnxi
id id G id   xiG i  RT  xi lnxi
i i
i  T,P   RT lnyi
cf. Giig  G ig
  Giid   G id 
S          RT lnxi Siid  S i  Rlnxi S   xiS i  R  xilnxi
id i id
i
  T  P, x   T P
  Giid  G i 
V  
i
id
    Viid  Vi V id   xi Vi
  P  T, x   P T
Hiid  Giid  T Siid  G i  RT lnxi  T  S i  RT lnxi  Hiid  Hi H   xiHi

Summary (2): Non-ideal Solution
The GE is of particular interest  nG  nVdP nH G
d   2
dT   i dni
 RT  RT RT RT
G E  G  G id
 nGid  nViddP nHid Giid
Gi  i  T   RT lnfî d    2
dT   dni
 RT  RT RT RT
Giid  i  T   RT lnxi f i

nV E   G E /RT
 
 
RT P 
 fî    T, x
Gi  RT ln
E


 xi f i  HE    G E /RT  
Exp. accessible values:
  T   Activity coefficient from
RT   T  P, x
fî The activity
VLE data, VE & HE values
i  come from mixing exp.
xi f i coefficient of species  nGEi /RT 
i in solution ln i   
 ni  P,T,nj
GiE  RT ln i
cf. GiE  RT lnî GE

  xiln i Important applications in
RT phase-equilibrium
For ideal solution, GiE  0,  i  1 thermodynamics
x i dln i  0 (Cont. T, P)

Example 6
2 kmol h–1 of liquid n-octane (species 1) are continuously mixed with 4

kmol h–1 of liquid iso-octane (species 2). The mixing process occurs at
constant T and P; mechanical power requirements are negligible.
a) Use an energy balance to determine the rate of heat transfer.

b) Use an entropy balance to determine the rate of entropy
generation (W K–1)

Homework
Chapter 11 : 11.1, 11.17, 11.18, 11.23, 11.28,

Tutorial 2, 4
Dateline : Apr 30, 2018 (Mon)

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CHAPTER 11

Mohd Asmadi Bin Mohammed Yussuf

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

• Introduction to solution thermodynamics • Define and describe the important of

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Introduction to Solution Thermodynamics

Fundamental Property Relation

The Chemical Potential & Phase Equilibria

Ideal Gas Mixtures

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Example: Steam Line

We know that for a single component system, the most common

By now, we know how to determine Tsat, Psat, H (liquid and ideal/non-

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Consider the following systems,

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Typical chemical processes involve a multicomponent system

Consider mixing 1000 cm3 MeOH and 1000 cm3 H2O at 25 C

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Develop the theoretical foundation of thermodynamics to

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

The actual molar density is 0.0410 mol/cm3 that could be calculated

We just introduced a new thermodynamic property for a

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Basic relation connecting the Gibbs energy to the T & P in any

d nG   nV dP   nS dT

Applied to a single-phase fluid in a closed system wherein no

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Consider the following system

So, Gibbs energy (G) could be written as a function T, P, n1,

nG g  P, T,n1 , n2 , ni ,

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Apply partial differentiation and FPR

  nG    nG    nG 

d nG   nV dP   nS dT μidni FPR for single-fluid systems of

The Gibbs energy is expressed as

How do we determine the phase of multicomponent system ?

If it is two phases, how do we determine the composition of

Before answering these, we need to establish THE CONCEPT

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Consider the following system,

Each phases ( and ) is actually an open system

d nG   nV dP  nS dT μiαdniα

d nG   nV dP  nS dT μβidnβi

d nG   nV dP  nS dT μivdniv  μlidnli

μ dn  μdn  μ  μ dn  0

μiv  μli  μβi  μiα   μiπ

This is criteria for the phase equilibrium for multicomponent system

Multiple phase at the same T and P are in equilibrium when the

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Based on the definition of i, let’s define a partial molar property as

This is a partial property of individual species as they exist in a

This property is different from a pure species property primarily due to

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

Hence, the chemical potential of species i (i) is known also as

  nG  Compare   nM 