CHBE 244: Chemical and Biological Engineering

Thermodynamics I
Lecture 31: Departure function - Entropy, density, pressure-dependent formulas
Apr 1, 2016

7.3 Entropy departure function

The entropy departure can be calculated using:
ig

ig

V ig

S S = (S S )T,V
V

S
V

ig
dV

(1)

Inserting the integral for the departure at fixed (T, V ) using a Maxwell relation,


ig #
ig
Z V ig 
Z V "
S
S
S
ig
dV
SS =

dV
V T
V T
V T
V



ig #
ig
Z V ig 
Z V "
P
P
P
dV
=

dV
T V
T V
T V
V

(2)

Since


P
T

ig
=
V

R
V

(3)

we may readily integrate the ideal gas integral eqn. (3) into eqn. (2) and becomes:


Z V 
P
R
V
ig
SS =

dV + R ln ig
(4)
T V
V
V

Recognizing the following eqn. (5) and (6), we can have eqn. (7) for the entropy
departure equation:
RT
V ig =
(5)
P

V
PV
=Z
=
V ig
RT


Z V 
1 P
1
S S ig
=

dV + ln Z
R
R T V
V

#


Z "
S S ig
Z
d

T
=
(Z 1)
+ ln Z
R
T

(6)

(7)

Note the ln(Z) term on the end of eqn. (7.) and it arises from the change in ideal gas
ig
ig
ST,P
ST,V
represented by the integral in eqn. (1).

7.4 Other departure functions

The departure functions of other functions (e.g. H = U + P V and A = U T S) may
be derived from the first two and the definitions of U and S.
U U ig P V RT
U U ig
H H ig
=
+
=
+Z 1
RT
RT
RT
RT

(8)

U U ig S S ig
A Aig
=

RT
RT
R

(9)

where we have used P V ig = RT for the ideal gas in the enthalpy departure. Using
H H ig just derived, the departure function of Gibbs energy can also be found:
H H ig S S ig
G Gig
=

RT
RT
R

(10)

7.5 Summary of density-dependent formulas

Forumlas for departures at fixed T,P are listed below.
They are useful for an equation of state as Z = f (T, ) such as cubic EOSs.
For internal energy (U ) departure function:


Z
(U U ig )
Z d
=
T
RT
T
0
For entropy (S) departure function:
#


Z "
(S S ig )
Z
d
=
T
(Z 1)
+ lnZ
R
T

0
2

(11)

(12)

 For enthalpy (H) departure function:

(H H ig )
=
RT

Z
0

Z
T
T

d
+Z 1

(13)

For Helmholtz energy (A) departure function:

(A Aig )
=
RT

Z
0

(Z 1)
d lnZ

(14)

For Gibbs energy (G) departure function:

(G Gig )
=
RT

Z
0

(Z 1)
d + (Z 1) lnZ

(15)

Some highlight useful forumlas for departures at fixed T,V are listed below.
For Helmholtz energy (A) departure function:
(A Aig )T,V
=
RT

Z
0

(Z 1)
d

(16)

For entropy (S) departure function:

(S S ig )T,V
=
R

Z
0

"

Z
T
T

#
(Z 1)

(17)

7.6 Pressure-dependent formulas

Sometimes it is difficult for the equation of state (EOS) to integrate to obtain departure
functions using the formulas in section 7.5.
It is because the EOS is more easily arranged and integrated in the form of Z = f (T, P )
such as the truncated virial EOS.
The following procedures are adapted for developing pressure-dependent formulas.
1. Write the derivative of the property with respect to pressure at constant temperature.
2. Convert to derivatives of measurable properties using methods from Chapter 5 of
the lecture notes (L26).
3

3. Write the difference between the derivative real fluid and the derivative ideal gas.
4. Insert integral over dP and limits from P = 0 (where the real fluid and the ideal
gas are the same) to the system pressure P .
5. Transform derivatives to derivatives of the compressibility factor (Z).
6. Evaluate the derivatives symbolically using the equation of state and integrate
analytically.
7. Rearrange in terms of density () and compressibility factor (Z) to make it more
compact.
The two most important departure functions at fixed temperature and pressure
(T,P) are:
For enthalpy (H):
(H H ig )
=
RT


T

Z
T


P

dP
P

(18)

For entropy (S):

(S S ig )
=
R


(Z 1) + T

Z
T

 
P

dP
P

(19)

Note the mathematical similarity between P in the pressure-dependent

formulas and in the density-dependent formulas!

Example 8.2 Real entropy in a combustion engine

A properly operating internal combustion engine requires a spark plug. The cycle involves
adiabatically compressing the fuel-air mixture and then introducing the spark. Assume the
fuel-air mixture in an engine enters the cylinder at 0.08 M P a and 20o C and is adiabatically
and reversibly compressed in the closed cylinder until its volume is 1/7 the initial volume.
Assuming that no ignition has occurred at this point, determine the final T and P , as well
as the work needed to compress each mole of air-fuel mixture. You may assume that CVig for
the mixture is 32 J/mole K (independent of T ), and that the gas obeys the equation of
state,
P V = RT + aP
(20)
where a is a constant with value a = 187 cm3 /mole. Do not assume CV is independent of
. Solve using density integrals.
Solution:
System: Closed system of the gas within the piston/cylinder
Assumptions: (1.) No flow; (2.) Adiabatic and reversible Isentropic
The entropy balance of the system also shows the process is isentropic by including all
assumptions:
0
0
7

0
0

*

X
X
Q
*

dS
>

out
out
in in


S
m

+
S

=
+
=
0
(21)
S
m

gen

dt
T

 sys
out
in


Recall the departure function approach from Figure 1,

Figure 1: Illustration of calculation of state changes for a generic property M using departure
functions where M is U, H, S, G, or A. Reference to Figure 8.2 of Liras textbook
Use the initial state (T1 , P1 ) to find the initial entropy (S1 ) and molar volume (V1 ).
5

 Then, use the final entropy (S2 ) and molar volume (V2 ) to find the final state (T2 , P2 ).
In this problem, we are asked to use density integrals to evaluate the EOS.
First, we need to rearrange the EOS in terms of Z = f (T, ).
This can be done by dividing all terms of the EOS (eqn. (20)) by RT which yields,
PV
aP
=1+
RT
RT

(22)

Note that V = 1, and multiply the last term by V , Z = 1 + aZ rearranges to

Z=

1
1 a

(23)

We also find the density at the two states using the EOS (eqn.(22)):
=

P
RT + aP

(24)

For the molar density of the fuel-air mixture at the initial state (T1 = 20o C and
P1 = 0.08 M P a),
1 =

P1
=
RT1 + aP1
8.314

cm3 M P a
moleK

(0.08 M P a)
(20 + 273 K) + (187

cm3
)(0.08
mole

1 = 3.257 105

M P a)
mol
cm3

(25)

As we know the fuel-air mixture is compressed by 7 times of the initial volume, therefore
the molar density of the fuel-air mixture at the final state increased by 7 times.


mol
5 mol
2 = 7 1 = (7) 3.257 10
= 2.280 104
3
cm
cm3
Two pathways can be chosen to determine the departure function.
Method I: fixed temperature and volume (T,V )
Method II: fixed temperature and pressure (T,P)

(26)

 Method I:
In terms of fixed T and V , this is an easier approach and we know:


Z
T


=0

(27)

1
1 a
a

=
1 a 1 a
1 a

(28)

For the term of Z 1,

Z 1=

For the departure function of entropy at constant temperature and volume,

#


Z "
Z
(S S ig )T,V
Z
d
d
(Z 1)
=
T
= a
R
T

0
0 1 a

(29)

ig

(S S )T,V
= ln(1 a)
R

For the entropy change between initial state and final state,
S2 S1 = (S S ig )T,V,2 + (S2ig S1ig ) (S S ig )T,V,1
 
 

 

 
T2
cm3
CV
V2
4 mole
ln
= R ln 1 187
2.28 10
+
+
ln
mole
cm3
R
T1
V1
 

 

3
cm
5 mole
R ln 1 187
3.257 10
mole
cm3


32
T2
S
= 0 = 0.04357 +
ln

ln(7) + 0.00611 = 0
R
8.314
293.15
T2 = 490.8 K
(30)
Method II:
In terms of fixed T and P ,
#


Z "
d
(S S ig )
Z
=
T
(Z 1)
+ lnZ
R
T

0


Z
d
1
= a
+ lnZ = ln(1 a) + ln
1 a
0 1 a

(S S ig )
=0
R

(31)

 Since the departure is zero, it drops out of the calculations.

The final volume (V2 ) is given, and we need to calculate the final pressure (P2 ).
For the entropy change of ideal gas,
ig

S = S2 S1 =

S2ig

S1ig


= CP ln

T2
T1


Rln

P2
P1


(32)

For the entropy change of real gas, the pressure ratio must be inserted in the last
term.
 


T2
RT2
RT1
S = CP ln
Rln
/
T1
V2 a V1 a
 


(33)
T2
V1 a
= (CP R)ln
Rln
T1
V2 a
Rearranging,

 


V2
1 a2
T2
+ Rln
+ Rln
S = CV ln
T1
V1
1 a1
 
 
V2
T2
+ Rln
Rln(1 a1 )
= Rln(1 a2 ) + CV ln
T1
V1


(34)

This answer is the same as method I that results in T2 = 490.8 K

For the final pressure (P2 ),

P2 =


3 M P a
(490.8 K)
8.314 cm
moleK

RT2

= 0.972 M P a
=
cm3
V2 a
(1/2.28 104 mole
) 187 mole
cm3

(35)

For the work required to compress each mole of air-fuel mixture (W ),

W = U = (U U ig )2 + CV T (U U ig )1 = 0 + CV T 0 = 6325

J
mole
(36)