Example 02.

05 Density of Supercritical Ethylene Using a High Precision

Equation of State

Problem:
At 293.15 K, ethylene is already in a supercritical state (Tc = 282.35 K). How much ethylene is in a
pressurized bottle (50 dm3 ), if the pressure on the manometer is P = 20 MPa?

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

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
cid
§ 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
³ cv dT  T ³ cv
2.105
id id
 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 ¨ 18.867981 ¸
0.00021478776 ¨ ¸
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  »
id id º»
« 4 3 «  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 0.4 ˜ 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.

Solution:

3
Conditions: T  293.15K V  50dm P  20MPa

W ( T) 0.963

In the first step the molar volume of ethylene at the conditions inside the pressurized bottle has to be
calculated:
3
dm
v  vV_eos( T  P) v 0.017  0.145i (complex solution)
mol
3
dm
v  vL_eos( T  P) v 0.068
mol

Although in the supercritical state, the root function found only a complex and not 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.
Dividing the volume of the bottle by the molar volume yields the number of moles, that can be easily
converted to the mass of ethylene in the bottle:

V
n n 731.566 mol m  n ˜ mw m 20.523 kg
v

The pressurized bottle contains 20.523 kg of ethylene.

The following plot shows the dependence of the objective function of the root function on reduced
volume using the high precision equation of state for ethylene:

vr  0.40  0.41  1

3
P eos T  vr˜vc  P
P
2
0

1
0.4 0.5 0.6 0.7 0.8 0.9 1
vr