Example 02.

06 Isobaric Heating of Ethylene Using a High Precision

Equation of State

Problem:
Ethylene from a pipeline (50 t/h, 70 bar, 5°C) passes a heat exchanger and is heated up to 45°C. The
pressure drop is negligible. As usual, in the data sheet of the heat exchanger the c P values at inlet and
outlet are given:
c P ( 5°C, 70 bar) = 3.984 J/g*K
c P (45°C, 70 bar) = 3.783 J/g*K
Calculate the heat to be exchanged
a) by estimation with an average c P
b) using a high-precision equation of state

Which solution shall be preferred?

Definitions and Constants:

5
J cm  0.01m kmol  1000mol kPa  1000Pa bar  10 Pa
R  8.31433
mol ˜ K 6
dm  0.1m g  0.001kg MPa  10 Pa h  3600s
6
MW  10 W

Theory

Like reference equations, state-of-the-art technical equations of state are formulated in terms of the
Helmholtz energy, which is split into an ideal gas part and a residual part. Instead of the specific
volume, the density is used as a variable:

a(T, U ) aid (T, U )  aR (T, U )

D id (W , G )  D R (W , G ) 2.104
RT RT
with W = Tc/T and G= U / Uc .

To calculate Did , an expression for the ideal gas heat capacity is required. In Appendix A parameters for
the following expressions are given:

c idP T
B  ( C  B )y 2 1  ( y  1)( D  Ey  Fy 2  Gy 3 ) , y
R AT 3.70
2 2
§ · § ·
id
c C /T E/T
P
A  B ¨¨ ¸¸  D ¨¨ ¸¸ 3.69
J /( kmol K ) © sinh( C / T ) ¹ © cosh( E / T ) ¹
The resulting expressions for Did can be derived using eq. 2.105 and the antiderivatives given in
Appendix C (F4 - Antiderivatives of cPid correlations):

a id (T , v) u id (T )  Ts id (T , v)
T T
dT v
³c dT  T ³ cvid 2.105
id
v  RT ln  a (T0 , v0 )
T0 T0
T v0
For eq. 3.70 the following antiderivatives are given:

³c RBT  R(C  B) *
id
P dT
AT
* [T  ( D  E  F  G  H  2) A ln
K
2
A
 (2 D  3E  4 F  5G  6 H  1)
AT
A3
 ( D  3E  6 F  10G  15 H )
2( A  T ) 2
A4
 ( E  4 F  10G  20 H ) C.197
3( A  T ) 3
A5
 ( F  5G  15 H )
4( A  T ) 4
A6
 (G  6 H )
5( A  T ) 5
A7
H ]  const.
6( A  T ) 6

cPid T
³ T dT RB ln
K
 R(C  B ) *

AT A
* [ln  (1  D  E  F  G  H )
K AT
§D 5 · A 2
3F
¨  E   2G  H ¸
©2 2 2 ¹ ( A  T )2
§E 10 · A3
 ¨  F  2G  H ¸
©3 3 ¹ ( A  T )3 C.198

§F 5 · A4
¨ G  H ¸
©4 2 ¹ ( A  T )4
§G · A
5
¨  H ¸
¹ (AT)
5
©5
H A6
 ]  const .
6 ( A  T )6
 For eq. 3.69 the antiderivatives are:

§C · §E· C.195
³c AT  BC coth ¨ ¸  DE tanh ¨ ¸  const .
id
P dT
©T ¹ ©T ¹
cPid T ªC §C · § C ·º
³ T dT A ln
K
 B « coth ¨ ¸  ln sinh ¨ ¸» 
¬T ©T ¹ © T ¹¼ C.196

ªE §E· § E ·º
 D « tanh ¨ ¸  ln cosh ¨ ¸»  const .
¬T ©T ¹ © T ¹¼

The constants cancel out when using the expressions in eq. 2.105, which also adds the value at a
reference point. Usually, href and s ref are set to be zero at the ideal gas state at Tref = 298.15 K and P ref
= 101325 Pa, even if this reference point is fictitious and the fluid regarded is in the liquid state.

The residual part is different for non-polar and polar fluids:

For non-polar fluids (methane, ethane, propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane,
argon, oxygen, nitrogen, ethylene, isobutane, cyclohexane, sulfur hexafluoride, carbon monoxide,
carbonyl sulfide, n-decane, hydrogen sulfide, isopentane, neopentane, isohexane, krypton, n-nonane,
toluene, xenon and R116):

D R (W , G ) n1GW 0.25  n 2GW 1.125  n3GW 1.5  n4G 2W 1..375  n5G 3W 0.25  n6G 7W 0.875
 n7G 2W 0.625e G  n8G 5W 1.75 e G  n9GW 3.625e G  n10G 4W 3.625e G
2 2

 n11G 3W 14.5 e G  n12G 4W 12 e G

3 3

For polar fluids (R11, R12, R22, R32, R113, R123, R125, R134a, R143a, R152a, carbon dioxide,
ammonia, acetone, nitrous oxide, sulfur dioxide, R141b, R142b, R218 and R245fa):

D R (W , G ) n1GW 0.25  n 2GW 1.25  n3GW 1.5  n 4G 3W 0.25  n5G 7W 0.875  n6GW 2.375e G
 n7G 2W 2 e G  n8G 5W 2.125e G  n9GW 3.5e G  n10GW 6.5e G
2 2

 n11G 4W 4.75e G  n12G 2W 12.5e G

2 3

References:
R. Span; W. Wagner; Int. J. Thermophys. 24(1), 41-109 (2003).
E. W. Lemmon; R. Span; J. Chem. Eng. Data 24(1), 41-109 (2006).
R. Span; W. Wagner; Int. J. Thermophys. 24(1), 111-162 (2003).
E. C. Ihmels; E. W. Lemmon; Fluid Phase Equilib. 207, 111-130 (2003).

Component Selection and Model Parameters:

Parameter vectors for the ideal gas heat capacity (c id ) and for the real part of the Helmholtz energy (c)
are stored in separate files and are imported as references. In the ideal heat capacity parameter vector,
the first element denotes the equation to be used (1 - 3.70, 2 - 3.69).
 Reference:H:\Th-Ex\02. PvT Behavior of Pure Components\Examples\02.EOS-ethylene.mcd(R)

name "ethylene" 0.9096223

ispolar  0 -2.4641015 § 1 ·
¨ ¸
0.56175311
¨ 100.6795534 ¸
-0.019688013 ¨ 3.466324 ¸
0.078831145 ¨ ¸
0.00021478776 ¨ 18.867981 ¸
c cid ¨ 1.584956 ¸
0.23151337
¨ 6.3700828 ¸
-0.037804454 ¨ ¸
-0.20122739 ¨ 0.0000544 ¸
-0.044960157 ¨ 0.0000307 ¸
¨ ¸
-0.02834296 © 0 ¹
0.012652824

3
cm g
Tc 282.35 K Pc 50.418 bar vc 130.947 mw 28.054
mol mol

Did and DR Functions, Auxiliary Functions

c P id function 3.70 and the two different integrals required for calculation of Did .
T
y370( T) 
cid ˜ K  T
2

cpid370( T)  R ˜ cid 

ǻ 3 ȼ
«  R ˜ c  c ˜ y370( T) 2 ˜ ª 1  º» »
id4 id3
« «  y370( T)  1 ˜ § cid  »
« « ¨ 5 ·¸ » »
« « ¨  cid6 ˜ y370( T)  ¸ » »
« « ¨ 2 ¸ » »
« « ¨  cid7 ˜ y370( T) ¸ » »
« « ¨ 3 ¸ » »
« « ¨  cid8 ˜ y370( T) ¸ » »
« « ¨ 4 ¸ » »
« « ¨  cid9 ˜ y370( T) ¸ » »
¬ ¬ © ¹ ¼ ¼
intcpdt370( T)  R ˜ cid ˜ T 
3

˜ª º
T
 R ˜ K ˜ cid  cid
4 3 « K  »
« ª § T ·º »
«  « cid5  cid6  cid7  cid8  cid9  2 ˜ cid2 ˜ ln¨ cid2  K ¸»  »
¬ © ¹¼
« 2 »
« cid
2
»
«   2 ˜ cid  3 ˜ cid  4 ˜ cid  5 ˜ cid  6 ˜ cid  1 ˜  »
5 6 7 8 9 T
« cid  »
« 2 K »
« cid
3 »
«  c  3 ˜ c  6 ˜ c  10 ˜ c  15 ˜ c ˜ 2 »

« id5 id
6
id
7
id
8
id
9 2 »
« §
2 ˜ ¨ cid  ¸
T· »
« © 2 K¹ »
« ª« cid
4 º» »
«  « c  4 ˜ c  10 ˜ c  20 ˜ c ˜ 2
»  »
« « id6 id id id
»
T· »
7 8 9 3
« « §
3 ˜ ¨ cid  ¸ » »
« ¬ © 2 K¹ ¼ »
« cid
5 »
«  c  5 ˜ c  15 ˜ c ˜ 2

»
« id7 id
8
id
9 4 »
« §
4 ˜ ¨ cid  ¸
T· »
« © 2 K¹ »
« ª« cid
6 º
» »
«  « c  6 ˜ c ˜ 2
»  »
« « id8 id
»
T· »
9 5
« « §
5 ˜ ¨ cid  ¸ » »
« ¬ © 2 K¹ ¼ »
« cid
7 »
« c ˜ 2 »
« id9 6 »
« §
6 ˜ ¨ cid  ¸
T· »
¬ © 2 K¹ ¼
intcp_Tdt370 ( T)  R ˜ cid ˜ ln§¨
T·
¸ 
3 © K¹
 R ˜ cid  cid ˜ ª ln§¨ cid 
T· º
« ¸  »
4 3 © 2 K¹
« cid »
«  1  cid  c  c  c  c ˜ 2
 »
id6 id7 id8 id9
« 5 T »
cid 
« 2 K »
« ª 2º »
« « § cid5 3 ˜ cid 5 ˜ cid · § cid
¨ ·¸ » »
«  « ¨ ¸˜
7 9 2
 cid   2 ˜ cid  » »
© 2 6 2 8 2 ¹ ¨ T ¸
« « ¨ cid2  K ¸ » »
« ¬ © ¹ ¼ »
« § cid 10 ˜ cid · § cid ·¸
3 »
« ¨ 6  c  2 ˜ c  9
¸ ˜
¨ 2
 »
¹ ¨c  T ¸
id7 id8
« © 3 3 »
« ¨ id2 K ¸ »
© ¹
« ª 4º »
« « § cid7 5 ˜ cid · § cid ·¸ » »
«  « ¨  cid 
9
¸˜¨ 2
»  »
2 ¹ ¨ T ¸
« «© 4
8
¨ cid2  K ¸ » »
« ¬ © ¹ ¼ »
« § cid · § cid2 ·¸
5 »
« ¨ 8  c ¸ ˜ ¨  »
¹ ¨c  T ¸
id
« © 5 9 »
« ¨ id2 K ¸ »
© ¹
« ª 5º »
« « cid9 §¨ cid2 ·¸ » »
«  « ˜
¨ ¸ » »
« « 6 ¨ cid  T ¸ » »
¬ ¬ © 2 K¹ ¼ ¼

c P id function 3.69 and the two different integrals required for calculation of Did .

ª 2 2º
« § cid ˜K
4
· § cid ˜K
6
· »
« ¨ ¸ ¨ ¸ »
cpid369( T)  « c id  cid ˜ ¨ ¸  cid ˜ ¨ ¸
T T J
»˜
3 ¨ § cid ˜ K · ¸ ¨ § cid ˜ K · ¸
« 2 5
» kmol ˜ K
« ¨ sinh¨ 4 ¸ ¸ ¨ cosh¨ 6 ¸ ¸ »
¬ © © T ¹¹ © © T ¹ ¹ ¼

ª§ § cid ˜ K · § cid ˜ K · · º
intcpdt369( T)  «¨ cid ˜ T  cid ˜ cid ˜ coth ¨ 4 ¸  cid ˜ cid ˜ coth ¨ 6 ¸ ¸ ˜ J »
¬© 2 K 3 4 © T ¹ 5 6 © T ¹ ¹ kmol¼
intcp_Tdt369 ( T)  ª c ˜ ln§ T ·  º J
« id2 ¨© K ¸¹ » ˜ kmol ˜ K
« § cid ˜ K § cid4 ˜ K · § § cid4 ˜ K · · · »
« c ˜ ¨ 4 ˜ coth ¨ ¸  ln¨ sinh¨ ¸ ¸ ¸  »
« id3 © T © T ¹ © © T ¹¹¹ »
« ª § cid ˜ K § cid6 ˜ K · § § cid ˜ K · · ·º »
«  «cid ˜ ¨ 6 ˜ coth ¨ ¸  ln¨ sinh¨ 6 ¸ ¸ ¸» »
¬ ¬ 5 © T © T ¹ © © T ¹ ¹ ¹¼ ¼

Set the correct functions for c P id and the two different integrals depending on the function used.
cpid ( T)  cpid370( T) if cid = 1
1

cpid369( T) if cid = 2
1

intcpdt( T)  intcpdt370( T) if cid = 1

1

intcpdt369( T) if cid = 2
1

intcp_Tdt( T)  intcp_Tdt370 ( T) if c id = 1
1

intcp_Tdt369 ( T) if c id = 2
1

vc ˜ 101.325kPa 1 § Tc · Tc § Tc ·
G0  187 intcpdt¨ ¸  ˜ intcp_Tdt¨ ¸
R ˜ 298.15 K G0 D id W  G 
©W¹ W © W ¹  ln§¨ G0 ·¸
Tc ©G¹
R˜
W
0.25 1.125 1.5 2 1.375 3 0.25
DRnp W  G  c ˜ G ˜ W  c ˜G˜W  c ˜G˜W  c ˜G ˜W  c ˜G ˜W 
1 2 3 4 5
2
7 0.875 2 0.625 G 5 1.75 ( G) 3.625 G
c ˜G ˜W  c ˜G ˜W ˜e  c ˜G ˜W ˜e  c ˜G˜W ˜e 
6 7 8 9
2 3 3
4 3.625 G 3 14.5 G 4 12 G
c ˜G ˜W ˜e c ˜G ˜W ˜e c ˜G ˜W ˜e
10 11 12
0.25 1.25 1.5 3 0.25 7 0.875
DRp W  G  c ˜ G ˜ W  c ˜G˜W  c ˜G˜W  c ˜G ˜W  c ˜G ˜W 
1 2 3 4 5
2
2.375 G 2 2 G 5 2.125 G 3.5 G
c ˜ G˜ W ˜e  c ˜G ˜W ˜e  c ˜G ˜W ˜e  c ˜G˜W ˜e 
6 7 8 9
2 2 3
6.5 G 4 4.75 G 2 12.5 G
c ˜G˜W ˜e c ˜G ˜W ˜e c ˜G ˜W ˜e
10 11 12

DR W  G  DRnp W  G

DRp W  G if ispolar = 1 Auxiliary functions:

Tc vc
D W  G  D id W  G  D R W  G W ( T)  G ( v) 
T v
 Different Thermodynamic Functions of T and v:

§ d D W ( T)  G ( v) ·
Peos( T  v)  R ˜ T ˜ ¨
pressure ¸
© dv ¹

R˜T
v as function of P (vapor) vV_eos( T  P)  vm
P
ª Peos( T  v)  P º
root«  v»
¬ P ¼

v as function of P (liquid) vL_eos( T  P)  v m 0.38 ˜ vc

ª Peos( T  v)  P º
root«  v»
¬ P ¼

A starting value close above the hardcore volume is usually possible and ensures finding the liquid root.
As P(v) covers several orders of magnitude, the objective of the root function should be the relative
deviation in pressure.

ª § d D W ( T)  G ( v) ·  v ˜ § d D W ( T)  G ( v) ·  1º
h eos( T  v)  R ˜ T ˜ «T ˜ ¨
h as function of T and v ¸ ¨ ¸ »
¬ © dT ¹ © dv ¹ ¼

Solution:

Conditions: Tin  5  273.15 K W Tin 1.015

Tout  45  273.15 K W Tout 0.887

kg
P  70bar mflow  50000
h
a) In the first step the mean heat capacity in the temperature range between 5 and 45°C is
calculated:
3.984  3.783 J J
cP_av  cP_av 3.883
2 g˜ K g˜ K

The heat stream to be supplied by the heat exchanger can then be calculated via:

Qflow  mflow ˜ Tout  Tin ˜ cP_av Qflow 2.157 MW

b) In the first step the molar volume of ethylene at the conditions has to be calculated:

3
dm 5 J
vin  vL_eos Tin  P vin 0.077 h eos Tin  vin 5.355 u 10
mol mol
3
dm 5 J
vout  vL_eos Tout  P vout 0.223 h eos Tout  vout 5.285 u 10
mol mol

Although in the supercritical state, the root function does not succeed to find a real solution when
starting from the ideal gas volume. The second function usually used to find the liquid volume starts at
a very low liquid volume and converges to the correct solution.

In the next step the molar and total enthalphy difference between inlet and outlet stream is calculated:

J
'h  h eos Tout  vout  h eos Tin  vin 'h 6960.506
mol

mflow kmol
n flow  n flow 1782.277
mw h

Qflow  'h ˜ n flow Qflow 3.446 MW

There is a large difference between the two results. Although the c P values are correct, approach a)
does not yield a reasonable result. The problem is that c P has a sharp maximum in the area in the
vicinity of the critical point, as the following plot illustrates:

T  278.15K  279.15K  318.15K

h eos T  0.05K  vL_eos T  0.05K  P  h eos T  0.05K  vL_eos T  0.05K  P

c P ( T)  
0.1K ˜ mw

12

10

cP ( T) 8
J
g˜ K 6

2
275 280 285 290 295 300 305 310 315 320
T
K