Departure Function

Derive an expression for enthalpy change of a gas during an isothermal process assuming using
the following EOS:

Example 5.1
( ) P V b RT =

p
P
V
dH C dT V T dP
T
( | |
= +
| (
\ .

P (V-b) =RT
P
V R
T P
| |
=
|
\ .

dH =C
p
p
RT
V dP C dT bdP
P
| |
= +
|
\ .
dT +
2 1
( )
P
H C dT b P P = +

Derive an expression for enthalpy change of a gas during an isothermal process assuming
using the following EOS: Z =1 +AP
Example 5.2
r
/ T
2
0
r
r
P
R
r
r
c r r
P
dP H Z
T
RT T P
| |
=
|
\ .
r

2
2
0
r
P
R
r r
r r
c r r
AP dP H
T AP
RT T P
| |
= =
|
\ .

2 1
ig R R
H H H H = +
2 1
( )
ig
r r c
H A P P RT = +

Derive expressions for H
Example 5.3
R
, S
R
General expressions are:
from RK-EOS.
( ) 1
V
R
V V
P
H RT Z T P dV
T
=
( | |
= +
| (
\ .

..(1)
ln
V
R
V V
P R
S R Z dV
T V
=
( | |
= +
| (
\ .

..(2)

( ) ( )
RT a RT a
P
V b V V b V b V V b T
= =
+ +
..(3)
Where,
2 2.5
0.42748 0.08664
;
C
C
C C
R T
a b RT
P P
= =

3/2
'
2 ( )
V
P R a
T P T
T V b V V b T
( | |
= +
| (
+
\ .

-
1/2
'
( )
RT a
V b V V b T
(
(
+

=
1/2
3 '
2 ( )
a
V V b T +

( )
3 '
1
( ) 2
V
R
V
a dV
H RT Z
V V b T
=
= +
+

Putting / Z PV RT =
3
ln
2
R
a V b
H PV RT
b V
+ (
=
(

Replacing P we get:
( ) ( )
3
ln
2
R
bRT a a V b
H
V b V b b V
+ (
=
(
+

Similarly using (2) and (3) one may show:
( )
ln ln ln
2
R
PV
V b a V b
S R R
RT V bT V
+ | | | |
= +
| |
\ . \ .

Carbon dioxide at upstream conditions T
Example 5.4
1
=350 K and P
1
For CO
=80 bar is throttled to a
downstream pressure of 1.2 bar. Estimate the downstream temperature and S of the gas.
2
3 5
2
1.157
/ 5.457 1.045 10 10
ig
p
C R T
T
= +
:
T
1
=350K, P
1
=80 bar, T
C
=304.2K, P
C

= 73.8 bar and = 0.224
For the process H
2
H
1
Now H
=0 (Isenthalpic, from energy balance)
2
H
1
2 1
...........( )
R R ig
H H H A + =
Tr
1
=T
1
/T
c
=1.151, Pr
1
=P
1
/P
c

=1.084
If one assume that at 1.2 bar (at exit), the gas is ideal, then:
2
1

2 1
0; then
T
R ig ig R
p
T
H H C dT H = =
.. (B)
Use generalized correlations for residual properties, and read from relevant figures for
residual properties to find
1
R
H at given Tr
1
, & Pr
1
and then solve Equation (B) by trial &
error to get T
2
280K
Thus:
2 2
2 1 1
1 1
ln ln 31.5 /
R R ig R
p
T P
S S S S S C R J molK
T P
(
= + +
(

Estimate the final temperature and the work required when 1 mol of n-butane is compressed
isentropically in a steady-flow process from 1 bar and 50
Example 5.5
o
=0.2, T
C to 7.8 bar.
c
=425.1 K, P
c
T
=37.96 bar
1
=323 K, P
1
=1 bar, P
2
For the process,
=7.8 bar
0 S =
T
r2
=0.76017, P
r2
P
=0.2052,
r1
-3 -6 2
/ 1.9 36.9 1 For n-butane: 0 11.4 10
ig
p
C R T T = +
=0.02639; hence we assume that at state 1 the residual properties are zero as the gas is at
ideal state.

Using generalized correlations for state 2 and reading from relevant figures for residual
properties one finally obtains the following residual property values at 2:
From generalized correction at point 2
( )
0.5679
o
R
C
H
RT
= ,
( )
0.05210
o
R
C
S
RT
=
2
1
2
2 1
1
ln
T
R R
p
T
P dT
S C R S S
T P
= +

Assume T
2
S and solve iteratively with =0 to obtain the final value of T
2
Next use generalized correlation figures for residual enthalpies; whereby at point 2:
which is =381K.
0.30330
R
c
H
RT
=
W =
2 1
( )
ig R R
c
H H RT H H = +

2
1
2 1
( )
T
ig R R
p c
T
C dT RT H H = +

Finally, 5678 W = J /mol

Calculate the changes in enthalpy and entropy per mole when a mixture of 70 mole %
ethylene (1) and 30 mole% propylene (2) at 323K and 10 bar is taken to 60 bar and 600 K
using the generalized compressibility factor approach.
Example 5.6

3 6 2 9 3
1
4.196 154.565 10 81.076 10 16.813 10
ig
p
C x T x T x T

= + + ;

3 6 2 9 3
2
3.305 235.821 10 117.58 10 22.673 10
ig
p
C x T x T x T

= + +
Use pure species data to compute those of mixture.
Thus,
(1 =ethylene, 2 =Propylene)
Similarly

At state 1,
Now,
From Tables at given T
r,mix
and P
r,mix

At state 1
and
Thus,
Similarly on repeating the calculation for state 2, T =600K, P =60 bar, we obtain

Now,

Thus,
Where,
For component 1,

Similarly,

Similarly,
Hence,

Now,

Final answer on substitution of all parameters

A certain gas is compressed adiabatically from 293 K and 135 KPa to 550 KPa. What is the
work needed? What is the final T
Example 5.7
2
For the gas: C
? Assume ideal gas behavior. Compressor =0.8.
p
ig
=1.65 +8.9 x 10
-3
T 2.2 x 10
-6
T
For rev. process S =S
2

2
-S
1
Flow process thus lead to:
=0
(1) (2) S =

2
1
2
1
T
T
P
P
ig
p
P
dP
R
T
dT
C

s
W
2
T
293
(1.65 +8.9 x 10
-3
T 2.2 x 10
-6
T
2
T
dT
) =8.314 ln
550
135
| |
|
\ .

T
2
reversible

(by iteration) ~395 K
By first Law Q (=0) +W
s
W
=H
s
(isentropic, reversible) =H
2
H
1

2
1
T
T
ig
p
C = dT
395
reversible 3 6 2
S
293
W [1.65 8.9 x 10 T 2.2 x 10 T ) dT

= +
~3960 J /mol.
Thus actual work needed = W
rev
S

=3960/0.8 =4950 J /mol

= =
2
1
T
T
ig
p
rev
S
dT C H W
4950 =
2
3 6 2
293
[1.65 8.9 10 2.2 10 ]
irrev
T
x T x T dT

+

T
2
(actual) ~420
o
K 147
o

C

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Derive an expression for enthalpy change of a gas during an isothermal process assuming using

the following EOS:

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