Calculations

using MS Excel
System: naphthalene + carbon dioxide at 35°C, 13 data points
Experimental data file: NFCD35SR.DA3
For α = 4.451; β = 5.79
Plots (Sample calculation in MathCad® in next pages):

EOS Plot

0.1
y2 [mole fraction]

0.01

Experimental
Peng-Robinson EoS
0.001
0 10 20 30 40
P, [MPa]

EOS Plot

1.0E-01

1.0E-02
y2 [mole fraction]

1.0E-03
Experimental
Peng-Robinson EoS
1.0E-04

1.0E-05
0 10 20 30 40
P, [MPa]

.
Peng/Robinson/Colpas EoS
Solubility of Naphthalene (2) in Carbon Dioxide (1) ‐ Peng/Robinson EoS
J
Data: T  35 °C P  12.2  MPa Ʀ  8.31446
mol  K

Tc1  304.25  K Pc1  7.38  MPa ω1  0.225

Tc2  748.1  K Pc2  4.05  MPa ω2  0.302 es mated values

3 3
cm 4 m
V2  110.3  1.103  10 y2.exp  0.0125
mol mol

Antoine equa on: Asub  13.583 Bsub  3733.9  K

 Bsub
Asub 13 t
P∞  Pa  10  3.828  10 Pa Ps ( t )  P∞  10

Peng/Robinson parameters: Ωa  0.457235529 Ωb  0.077796074

Assume that: y2  0 so that mixture proper es are similar to solvent proper es. y1  1

Colpas parameters: α  4.451 β  5.79

Pure solvent parameters:
2
κ1  0.37464  1.54226  ω1  0.26992  ω1  0.708

2 2 2
  T Ʀ  Tc1 2
α1  1  κ1   1 
J
 0.991 ac1  Ωa   0.396 
  Tc1  Pc1 2
 mol  Pa

J
2 Ʀ  Tc1 5 m
3
a1  ac1  α1  0.393  b1  Ωb   2.667  10
2 Pc1 mol
mol  Pa

P P
A1  a1   0.7302 B1  b1   0.12698
2 Ʀ T
Ʀ  T
 Calcula ons of compressibility factor of pure solvent: 

2
p1  B1  1  0.873 p2  A1  3B1  2B1  0.4279
Coefficients of generic
cubic equa on
p3  B1   B1  B1  A1   0.0745
2 3 2
f ( x)  x  p1  x  p2  x  p3
 

2 3
3  p2  p1 9  p1  p2  27  p3  2  p1 4
Q   0.05794 R   3.3878  10
9 54
 3 2 4
D  Q  R D  1.946  10

D > 0 (One real root, and two complex conjugate ones)

R  D  0.23877 R  D  0.24266
3 3
Š  Ť 

p1
x1  Š  Ť 
3
 0.28711  
f x1  0

ŠŤ p1 3
x2 
2

3

2
 ( Š  Ť )i  0.29296  0.41693i  
f x2  0

ŠŤ p1 3
x3 
2

3

2
 ( Š  Ť )i  0.29296  0.41693i  
f x3  0

D = 0 (Three real roots, at least two equal)

p1
x4  2  Š 
3
 0.769  
f x4  0.193
R
D < 0 (Three real, unequal roots) cosθ1   0.024i κ  2 Q  0.481i
3
Q

 θ1  p1 3

θ1  acos cosθ1  1.571  0.024i  x7  κ  cos 
 
3

3
 0.28906  0.41693i f  x7  1.355  10

θ1 3 p1 3
θ2 
3
 120  °  2.618  8.096i  10
x8  κ  cos θ2 
3
 
 0.28906  0.41693i  
f x8  1.355  10

θ1 3 p1 3
θ3 
3
 240  °  4.712  8.096i  10
x9  κ  cos θ3 
3
 0.2949    
f x9  1.355  10

Since D > 0: Z1  x1  0.287

 Calcula ons of fugacity: 
2
  T 
α2  1  κ2   1 
2
κ2  0.37464  1.54226  ω2  0.26992  ω2  0.816  1.67
  Tc2 

2 2
Ʀ  Tc2 J
2
J
2
ac2  Ωa   4.368  a2  ac2  α2  7.294 
Pc2 2 2
mol  Pa mol  Pa

lnϕ2   Z1  1  β  ln  Z1  B1   8.173

A1  Z1   1  2  B1
  ( 2  α  β)  ln  
2  2  B1  Z1   1  2  B1
 

4

ϕ2  exp lnϕ2  2.823  10 
 Calcula ons of solubility: 


Ps T  V2  P 
y2.calc  exp    0.01435
ϕ2  P
 Ʀ T  PF: Poyin ng factor


Ps T 6 1 3  V2  P 
y2.ideal   2.396  10  3.542  10 PF  exp    1.691
P ϕ2
 Ʀ T 
E: Enhancement factor
PF
E   5989 y2.Calc  y2.ideal E  0.01435
ϕ2

y2.calc  y2.exp
Error: Err   14.804  %
y2.exp