Solution Thermodynamics

ChE 307
Thermodynamics-II
Chapter 11
Instructor
Kaniz Fatema
Assistant Professor
ChE, BUET, Dhaka-1000
J a n u ary 2 0 2 2
1
Solution Thermodynamics -Theory
Introduction
• Property depends strongly on composition, P and T
• Multi-component gases or liquids undergo composition changes
• Purpose - to develop the theoretical foundation for application of
thermodynamics to gas mixture and liquid solution
• New property - chemical potential
• New class of thermodynamic properties - partial properties
• Gas mixtures – fugacity
• New class of solution properties - excess properties
2
Solution Thermodynamics-Theory
What is the most important property?
 Gibbs free energy, G and chemical potential, μ
 For pure component, G=G(P, T)
 For a homogeneous mixture, containing i components -
G=G(P, T, n1, n2...........ni)
3
Fundamental Property Relation
Gibbs energy to the temperature and pressure in any closed
system is expressed as,
where n is the total number of moles of the system.
An appropriate application is to a single-phase fluid in a closed

system wherein no chemical reactions occur.
4
Fundamental Property Relation
For open system-
The derivative in the final term is called the chemical potential

of species i in the mixture.
(11.1) [extensive property]
5
The Chemical potential
Consider a closed system containing of two phases in equilibrium.
Within this closed system, each individual phase is an open
system, free to transfer mass to the other.
for each phase:
d(nG)   (nV)  dP  (nS)  dT   μi dn i

d(nG)   (nV)  dP  (nS)  dT   μi dn i
Total system property :

nM  (nM)   (nM) 
d(nG)  (nV)dP  (nS)dT   μi dn i   μi dn i
6
The Chemical potential
 Phases  and .
 Free mass transfer between phases  and  
 Two phases are closed, and at equilibrium.

 At constant P and T, two phases are in equilibrium

when chemical potential of each species is the
same in both phases.
  provides a measure of the work a system is capable

of, when a change in mole numbers occurs e.g.,
chemical reaction or a transfer of mass
7
11.3 Partial properties
The partial molar property
- extensive property
- changes with ni
- at constant T, P and xj.
Partial property and molar property (except for

ideal solution).
M = solution properties, e.g., V, U, H, S, G

Mi = pure species properties, e.g., Vi , Ui , Hi , Si , Gi
Mi = partial properties, e.g., Vi , U i , H i , S i , G i
8
11.3 Partial properties contd…
The chemical potential and the partial molar

Gibbs energy are identical; i.e.,
9
Equation for solution property, M

The total differential of nM is:
 (nM)  (nM)
d(nM)    dP    dT   M i dni
 P T,n  T  P,n
Since ni = xin
  M   M    
 dM-   dP-   dT-  M i dx i  n   M   x i M i  dn  0
   P  T,x   T  P,x i   i 
10
n and dn are independent and arbitrary as a system can be chosen of any size.
  M   M    
 dM-   dP-   dT-  M i dx i  n   M   x i M i  dn  0
   P  T,x   T  P,x i   i 
dM   xi d Mi  Mi dxi
i i
11
Gibbs / Duhem equation: Change in thermodynamic property with T, P and x.
 M   M 
  dP    dT-  x i d M i  0 (11.13)
  P  T,x   T  P,x i
dM   xi d Mi  Mi dxi
i i
Special case:
constant T and P,
12
For a binary system
Derivation – CT q
For a binary system, the partial properties

are readily calculated from M and xi.
13
Partial Molar Properties in Binary Solutions
Example 11.3:
The need arise in a laboratory for 2000 cm3 of an antifreeze
solution consisting of 30 mol% methanol in water. What
volumes of pure methanol and of pure water at 25C must be
mixed to form the of antifreeze, also at 25C ? Partial molar
volumes and pure-species molar volumes, both at 25C , are:
V1  38 .632 cm 3 mol  1 V1  40.727 cm 3 mol  1

V 2  17 .765 cm 3 mol 1 V 2  1 8 .068 cm 3 mol 1
14
Partial Molar Properties in Binary Solutions
15
The line drawn tangent to

the V-x1 curve at x1=0.30,
illustrates the values of
= 38.632 cm3mol-1 and
= 17.76 cm3mol-1
16
Relations among Partial Properties
Counterpart thermodynamic equation for species in solution
Maxwell relation,
d(nG)  (nV)dP  (nS)dT   Gi dni ( 11.17 )
 V   S 
   -   ( 6 .16 )
  T  P,n   P  T,n
We have two additional equations:

  Gi   (nS)    Gi   (nV) 
   - and    
 T   n    n 
  P,n  i  P,T,n j  P  T,n  i  P,T,n j
17
Relations among Partial Properties
Every equation that provides a linear relation among thermodynamic properties

of a constant-composition solution, has a counterpart equation connecting the
corresponding partial properties of each species in the solution.
18
11.4 Ideal-Gas Mixtures
Dalton’s Law of partial pressure
ni
Pi  yi Pt where yi 
nt
Pt   Pi
i
Gibbs’s Theorem
n = ni + ∑ nj
=1+0
19
11.4 Ideal-Gas Mixtures contd…
Gibbs’s Theorem
Ideal gas
- Model gas
- Comprised of imaginary molecules
- Volume of a molecule is zero
- Molecules do not interact
Properties of each species is independent of

the presence of others Josiah Willard Gibbs
Basis for Gibbs’s theorem.
Mathematically:
20
Gibbs’s Theorem
Full description of ideal gas behavior, the equations
1. Enthalpy, independent of P
Analogous equation for Uig and other properties that are independent of P.
21
Gibbs’s Theorem
2. Entropy, dependent on P
Integration from Pi to P, Summability relation, Rearranging –
The left side is the entropy change of mixing for ideal gases.
22
Gibbs’s Theorem
3. Gibbs energy, G
Parallel relation –
dG = VdP – SdT
Elimination of Giig -
Integration - or,
Integration constant = = function of T only [at a constant T ]
23
Gibbs’s Theorem
Summability relation –
These equations are simple and provide a full description of ideal-gas behavior.
24
11.5 Fugacity and Fugacity Coefficient: Pure Species
For convenience, Gi and µi is expressed in terms of U and S.
µi approaches negative infinity when either P or yi approaches zero

[ ln(0) = undefined ]
‘Fugacity’ is introduced to replace µi
For a real fluid, an analogous equation from 11.27 is –
Here, fugacity of pure species i, fi replaces P
25
11.5 Fugacity and Fugacity Coefficient: Pure Species contd…
= residual Gibbs energy = GiR

fi/P = fugacity coefficient = φi
Complete definition of fi
The ideal-gas-state fugacity of i is equal to its pressure.
26
For the special case of an ideal gas,

GiR = 0
φi = 0
Φi can be expressed in terms of Z.
Φi and thus fi can be calculated from PVT data.
27
Fugacity from virial coefficient
Zi is given by:
Second virial coefficient, Bii is a function of T only

for a pure species.
28
Fugacity from cubic equations of state
- van der Waals,

- Redlich/Kwong,
- Soave/Redlich/Kwong,
- Peng/Robinson equations
29
Class Test 1
Chapter 10, 11 Theory based
Conceptual
Date # June 01, 2022
Explanation
Time # 8.30 am
Derivation
Room # OAB 254, 255, 256
Short math (example or similar)
30
11.5 Fugacity and Fugacity Coefficient: VLE for Pure Species
VLE in terms of fugacity
Saturated vapor - [eqn 6.66, 2 phases at

equilibrium]
Saturated liquid –
An alternative formula with fugacity coefficient -
31
11.5 Fugacity and Fugacity Coefficient: Fugacity of a Pure Liquid
Fugacity of pure liquid [subcooled/

compressed]
Fugacity in pure liquid is calculated in 2 steps.
1. Φi of sat’d vapor – eqn 11.34

fisat = Φi .Pisat
2. Fugacity change from the P increase

- Pisat to P [sat’d liq to compressed /
subcooled liq]
- Integrating from sat’d P to subcooled liq P:
- Another expression
32
11.5 Fugacity and Fugacity Coefficient: Fugacity of a Pure Liquid contd…
Poynting factor, fugacity with constant volm
- Vi, the liquid phase molar volume is a very weak

function of P at T, well below Tc
- Vi can be assumed constant for Vil
- Solving for fi –
- The exponential function is known as Poynting factor.
33
34
The lowest P in the steam table at 3000C= 1 kPa [ideal gas]

P* = fi* = 1 kPa
Now, apply eqn (A) at different P up to the sat’n P
Psat’n @3000C= 8592.7 kPa.
At P = 4000 kPa and 3000C
35
Selection of the reference condition
2
3
36
H and S from
steam table
--------------------
2
3
Sat’n P from
steam table
---------------
37
Similar calculation for other P to draw the plot.
38
At sat’n, values are unchanged.
fi and Φi for liquid > Poynting factor eqn
Molar volume, Vil = volm of sat’d liq water at

3000C.
39
11.5 Fugacity and Fugacity
Coefficient: Fugacity of a
Pure Liquid contd…
P, kPa fi, kPa ⲫi

4000 3611 0.90
8593 6739 0.78
40
11.6 Fugacity and Fugacity Coefficient
Species in solution
The eqn is analogous to that of in gas
The partial pressure is replaced by –
This is not a partial molar property, so a circumflex is

used rather than an overbar.
For phase eqm –
For VLE
41
11.6 Fugacity and Fugacity Coefficient: Species in Solution contd…
The eqn for a partial residual property
• The residual properties measure the departure from

ideal-gas values.
• Logical use is for gas.
• They can also be used for liquids.
For partial residual Gibbs energy –
For chemical potential -
42
11.6 Fugacity and Fugacity Coefficient: Species in Solution contd…
The eqn for a partial residual property

The combined eqn –
Where –
It is called the fugacity coefficient of species i in solution.
In case of liquid, yi is replaced by xi.
For an ideal gas, is zero.
43
11.6 Fugacity and Fugacity Coefficient: The Fundamental Residual-Property Relation
Extension of fundamental property relations to

residual properties
An alternative form of eqn 11.2 –
Introduction of fugacity coefficient –
Special case -
44
Fugacity Coefficients from the Virial Equation of State
can be calculated from eqn of state.
Second virial coefficient which is a function of T and yi.
B11, B22 = pure-species virial coefficient

B12 = cross coefficient, mixture property
Both are functions of T only.

Eqns of B are called mixing rules.
45
Differentiation with respect to n1 -
46
11.6 Fugacity and Fugacity Coefficient: Fugacity Coefficients from the Virial Equation of State
contd…
47

Therefore -
Multi-component mixture -
48
11.7 Generalized Correlation for the Fugacity Coefficient
General eqn for Fugacity Coefficient of pure species
Residual H, S can be applied.
for simplicity –
The integrals can be evaluated for different Tr and Pr. Tables E.13-16
49
11.8 The Ideal Solution
General eqn for Fugacity Coefficient of pure species
• Real solution behavior is compared with an ideal solution.

• Excess properties are introduced.
For an ideal soln –
Similar eqns for thermodynamic properties –
Summability relation -
50
11.8 The Ideal Solution contd…
The Lewis/Randall Rule
For i in ideal soln –
After eliminating the integration constant –
• This eqn is known as the Lewis/Randall rule.

• It is for a species in an ideal soln at all T, P and xi.
For coefficient -
51
11.9 Excess Properties
Excess Properties
• Deviations of liquid solutions are measured from ideal

solution, not from ideal gas.
• Thus, excess properties, analogous to the residual properties

are introduced.
52
11.9 Excess Properties contd…
Solution of gases
• The ideal-gas mixture is a solution, soln of ideal gases.
• It can be expressed with eqns analogous to those of ideal soln.
• A general relation for difference –
53
Solution of gases
• In terms of residual and excess properties –
• The partial-property relation –
• The fundamental excess-property relation -
54
The Excess Gibbs Energy and the Activity Coefficient
G is of particular interest.
By difference –
Partial excess G –
Activity coefficient of i in soln –
And therefore,
55
The Excess Gibbs Energy and the Activity Coefficient
Excess G incorporating γi –
VE, HE, and γi are experimentally accessible.
56
The nature of excess

properties
1. All excess properties
become zero as either
species approaches
purity
2. GE is approx.
parabolic in shape, HE
and SE have
individualistic
dependencies
3. The maximum or
minimum ME often
occurs near the
equimolar
composition
57
58

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ChE 307

where n is the total number of moles of the system.

An appropriate application is to a single-phase fluid in a closed

The derivative in the final term is called the chemical potential

(11.1) [extensive property]

for each phase:

d(nG)   (nV)  dP  (nS)  dT   μi dn i

Total system property :

 At constant P and T, two phases are in equilibrium

  provides a measure of the work a system is capable

Partial property and molar property (except for

M = solution properties, e.g., V, U, H, S, G

Mi = partial properties, e.g., Vi , U i , H i , S i , G i

The chemical potential and the partial molar

Equation for solution property, M

Gibbs / Duhem equation: Change in thermodynamic property with T, P and x.

For a binary system

For a binary system, the partial properties

V1  38 .632 cm 3 mol  1 V1  40.727 cm 3 mol  1

The line drawn tangent to

= 38.632 cm3mol-1 and

Counterpart thermodynamic equation for species in solution

We have two additional equations:

Every equation that provides a linear relation among thermodynamic properties

Dalton’s Law of partial pressure

Properties of each species is independent of

Basis for Gibbs’s theorem.

Integration from Pi to P, Summability relation, Rearranging –

Integration constant = = function of T only [at a constant T ]

For convenience, Gi and µi is expressed in terms of U and S.

µi approaches negative infinity when either P or yi approaches zero

‘Fugacity’ is introduced to replace µi

For a real fluid, an analogous equation from 11.27 is –

Here, fugacity of pure species i, fi replaces P

= residual Gibbs energy = GiR

The ideal-gas-state fugacity of i is equal to its pressure.

For the special case of an ideal gas,

Φi can be expressed in terms of Z.

Φi and thus fi can be calculated from PVT data.

Fugacity from virial coefficient

Second virial coefficient, Bii is a function of T only

Fugacity from cubic equations of state

- van der Waals,

VLE in terms of fugacity

Saturated vapor - [eqn 6.66, 2 phases at

An alternative formula with fugacity coefficient -

Fugacity of pure liquid [subcooled/

Fugacity in pure liquid is calculated in 2 steps.

1. Φi of sat’d vapor – eqn 11.34

2. Fugacity change from the P increase

Poynting factor, fugacity with constant volm

- Vi, the liquid phase molar volume is a very weak

- Vi can be assumed constant for Vil

- The exponential function is known as Poynting factor.

The lowest P in the steam table at 3000C= 1 kPa [ideal gas]

Now, apply eqn (A) at different P up to the sat’n P

Psat’n @3000C= 8592.7 kPa.

At P = 4000 kPa and 3000C

Selection of the reference condition

Similar calculation for other P to draw the plot.