CHEN623: Fundamentals and Applications of

Thermodynamics to Chemical Engineers

Course Instructor: Professor Ioannis G. Economou

Chemical Engineering Program
Texas A&M University at Qatar
PO Box 23874, Doha, Qatar
e-mail: ioannis.economou@qatar.tamu.edu

Problem session 2
04 Sep 2022
Statistical Thermodynamics Advanced Chemical Engineering Fall 2022
Thermodynamics 1
 Problem 1
Obtain an expression for the fugacity of pure species that obeys van der Waals
equation of state. Use this equation to calculate the fugacity of Nitrogen gas at
150 oC and 5 bar and then compare the value obtained using the XSEOS
package.
For pure component:
f   P RT 
∞
RT ln   ∫V  ni − V dV − RT ln z + RT ( z − 1) (1)
 P pure i
= ( 3-54,pg46 )
In terms of molar volume, the equation above can be written as
f  ∞ RT 
RT ln   =∫  P − dυ − RT ln z + RT ( z − 1) ( 2)
 P pure i υ  υ 
RT a
vdW:
= P − 2 ( 3)
υ −b υ

Substitute (3) in (2)

f  ∞  RT a RT 
RT ln  = ∫υ  υ − b − υ − dυ − RT ln z + RT ( z − 1)
 P pure i
2
υ 
Integrate to obtain
∞
f   a 
RT ln  =   RT ln (υ − b ) + − RT ln υ  − RT ln z + RT ( z − 1)
 P pure i  υ υ

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 2
combine the terms with natural logarithm
∞
f   a 
RT ln  =   RT ln (υ − b ) + − RT ln υ  − RT ln z + RT ( z − 1)
 P pure i  υ υ

substituting the integration limits gives

f  υ −b a
RT ln   =− RT ln − − RT ln z + RT ( z − 1)
 P pure i υ υ
f  υ −b a
ln   = − ln − − ln z + ( z − 1)
 P pure i υ RTυ

RT a For Nitrogen
vdW:
= P − 2
υ −b υ Tc = 126.2 K
where Pc = 34 bar
2 2
27 R T RTc
a = b c

64 Pc 8Pc

bar ⋅ m3
−5
=R 8.314 ×10
mol ⋅ K

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 3
 Problem 2
Calculate the fugacity for each species for the following gases at 290 K and
800 bar:

a) Pure oxygen
b) Pure nitrogen
c) 30 mol% O2 and 70 mol% N2 using the Lewis-Randall rule
d) 30 mol% O2 and 70 mol% N2 using PREOS.

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 4
 Problem 3

Derive the expression for the isothermal-isobaric

partition function of a binary mixture then derive the
thermodynamic properties (S, V, μi) of this mixture.

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 5
L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022
Thermodynamics 6
 ∑ ∑e
∆ ( N , P, T ) =
V i = states
− β ( Ei + PVi )

Assuming that there is non-interacting molecules:=

Ei Ei , A + Ei , B
−β (E + Ei ,B + PVi )
∑ ∑ e i ,A
∆ ( N A , N B P, T ) =
V i = states

∑ ∑ e− βVi e
∆ ( N A , N B P, T ) =
− β Ei , A − β Ei ,B
e
V i = states

∑∑ e− βVi ∑
∆ ( N A , N B P, T ) = ∑
− β Ei , A − β E j ,B
e e
V
= i i states
= of A j states of B

∑ e − βV ∑ e
∆ ( N A , N B P, T ) = ∑
− β Ei , A − β Ei ,B
e
V
= i states
= of A j states of B

∑ e− PV kT ∑
∆ ( N A , N B P, T ) = ∑
− Ei , A kT − E j ,B kT
e e
V
= i states
= of A j states of B

∑ e− PV kT QA ( N A ,V , T ) QB ( N A ,V , T )
∆ ( N A , N B P, T ) =
V

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 7
 ∆ ( N , P, T )
−kT ln ∆
G=
 ∂G   ∂T   ∂P   ∂N 
− SdT + VdP + ∑ µi dN i
dG =   −S 
=  +V   + ∑ µi  i 
 ∂N i  N j≠i , P ,T  ∂N i  N j≠i , P ,T  ∂N i  N j≠i , P ,T  ∂N i  N j≠i , P ,T
 ∂G   ∂T   ∂P   ∂N i   ∂G 
  = −S   +V   + ∑ µi     = µi
 ∂T  N , P  ∂T  N , P  ∂T  N , P  ∂T  N , P
 ∂N i  N j≠i , P ,T
 ∂G 
  = −S  ∂ ln ∆ 
 ∂T  N , P µi = −kT  
 ∂G   ∂ ( −kT ln ∆ )   ∂N i  N j ≠i , P ,T
S=
−  = − 
 ∂T  N , P  ∂T N ,P U =G + TS − PV
 ∂ ln ∆    ∂ ln ∆   
S kT   + k ln ∆  ∂ ln ∆  
 ∂T  N , P U = − kT ln ∆ + T  kT   + k ln ∆  − P  −kT   
  ∂T  N , P    ∂P  N ,T 
 ∂ ln ∆   ∂ ln ∆ 
=U kT 2   + kTP  
 ∂G   ∂T   ∂P   ∂N i   ∂T  N , P  ∂P  N ,T
  = −S   +V   + ∑ µi  
 ∂P  N ,T  ∂P  N ,T  ∂P  N ,T  ∂P  N ,T
 ∂G 
  =V
 ∂P  N ,T
 ∂ ln ∆ 
V = −kT  
 ∂P  N ,T

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 8
 ∑
∆ ( N A , N B P, T ) = ∑ ∑
− PV kT − Ei , A kT − E j ,B kT
e e e
V
= i states
= of A j states of B

 ∂ ln ∆ 
=S kT   + k ln ∆
 ∂ T N ,P
∂   G
ln  ∑ e − PV kT ∑ ∑
− Ei , A kT − E j ,B kT
S kT e − e
∂T N , P=  V i states
= of A j states of B  T
− E j ,B kT  PV + Ei , A + E j , B 
∑e ∑of A ∑
− PV kT − Ei , A kT
e e  
V
= i states
= j states of B  kT 2  G
S = kT −
∑e ∑ ∑
− Ei , A kT − E j ,B kT
− PV kT
e e T
V i = states of A j = states of B

Recall that

P V E G G H
S= + − =− +
T T T T T

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 9
  ∂ ln ∆ 
V = −kT  
 ∂P  N ,T

∂  
ln  ∑ e − PV kT ∑ ∑
− Ei , A kT − E j ,B kT
V = −kT e e 
∂P N ,T=  V i states
= of A j states of B 
kT  V 
∑e ∑ ∑
− PV kT −E kT −E
e i ,A e j ,B  − 
= V i states
= of A j states of B  kT 
V=
− kT V
=
∑ e− PV kT ∑ e i ,A ∑ e j ,B
−E kT −E kT

V
= i states
= of A j states of B

 ∂ ln ∆ 
µ A = −kT  
 ∂N A  N B , P ,T

∂  
ln  ∑ e − PV kT ∑ ∑
− Ei , A kT − E j ,B kT
µ A = −kT e e 
∂N A N B , P ,T=  V i states
= of A j states of B 
 1  ∂Ei , A  
∑ e− PV ∑ ∑
− Ei , A kT − E j ,B kT
kT
e e − 
 kT  ∂N A  N , P ,T 
V
= i states
µ A = −kT
= of A j states of B
 B 
∑e ∑ ∑ e
− PV kT − Ei , A kT − E j ,B kT
e
V
= i states
= of A j states of B

 1  ∂Ei , B  
∑ e− PV ∑ ∑
− Ei , A kT − E j ,B kT
kT
e e − 
 kT  ∂N B  N , P ,T 
V
= i states
µ B = −kT
= of A j states of B
 A 
∑e ∑ ∑ e
− PV kT − Ei , A kT − E j ,B kT
e
V
= i states
= of A j states of B

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 10
 Problem 4

A flat graphite surface is in contact with reservoir of

gas molecules at fixed chemical potential. There are M
sites on the graphite surface on which gas molecules
can adsorb, each site can adsorb only a single
molecule, and the absorbed molecules do not interact
with each other. Starting from the grand canonical
partition function, develop an expression for the
coverage – that is, the fraction of the adsorption sites
that are occupied (contain an adsorbed gas molecule)
as a function of the chemical potential of the gas
molecules in the reservoir.

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 11
L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022
Thermodynamics 12
The number of ways of placing N indistinguishable molecules on M
distinguishable (since they are fixed in space) lattice sites is M!/N!(M-
N)! and let qADS represent the partition function for a single adsorbed
molecule. Then
M!
Ξ ∑=
e N µ / kT Q ( N ,V ,T )
N
∑N e N µ / kT
=
N ! ( M − N )!
N
qAD

M! M!
∑N=
N ! ( M − N )!
( qAD e )
µ / kT N
(
∑N N ! ( M − N ) ! AD
q e )
µ / kT N
(1)
M −N

Where the term (1)M-N has been introduced in order to

use a binomial expansion to simplify the expression to:

(q + 1)
µ / kT M
M! e
Ξ ∑=
N ! ( M − N ) !
( qAD e )
µ / kT N
()
1
M −N AD

M!
N

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 13
 ( qADeµ / kT + 1)
M
 ∂ ln Ξ  ∂
N kT
=   kT ln
 ∂µ V ,T ∂µ V ,T M!
1 M µ / kT 1
( )
µ / kT M −1
N kT q e + 1 q e
( qADe + 1)
M AD AD
µ / kT M ! kT
M!
( qADeµ / kT + 1)
M −1

qAD e µ / kT
N =
( M − 1) ! qAD e µ / kT M
( AD )
M µ / kT
q e µ / kT
+ 1 qAD e +1
M!
Therefore

N qAD e µ / kT
θ =
=
M qAD e µ / kT + 1

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 14
 P
µ (T ,P ) µ0 (T ,P0 ) + kT ln
=
P0
so that
P µ0 / kTµ / kT µ0 / kT −ln P0 + ln P
=e e= e
P0
P µ / kT
qADS e
N P0 λ −1 P P P0 e − µ0 / kT
θ =
= = −1 = λ
where=
P µ / kT
M q
ADS e +1 λ P +1 P + λ qAD
P0

L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022

Thermodynamics 15
L8 – Statistical Thermodynamics Advanced Chemical Engineering Fall 2022
Thermodynamics 16