Problems related to equation of state model

1. Van der Waals equation

Problem: Calculate the volume occupied by one mole of n-octane vapour at 427.85 K
where the saturation pressure is 0.215 MPa. Assume that n-octane follows the van der
Waals equation of state. The van der Waals constants a and b are 3.789 Pa (m3/mol)2
and 2.7310-4 m3/mol, respectively.

Solution: The van der Waals equation is cubic in volume. Calculation of P and T is
straight forward. However, calculation of volume, given P and T requires trial and
error method.
The equation can be rearranged as

+1 = +

( + 2 )

Where
vi= volume calculated in the ith iteration
vi+1= volume calculated from (i+1)th iteration
When i=0, v0 can be taken as equal to that predicted by the ideal gas law.
Calculation can be carried out till the convergence is obtained or the difference (vi+1-
vi) is less than a present value.
8.314 427.85
0 = = 6
= 16.55 103 3 /
0.215 10
8.314 427.85
1 =
+ = 3.789
= 15.78 103 3
( + 2 ) 6
{0.215 10 + (16.55103 )2 }

2 = 15.69 103 3
3 = 15.68 103 3
4 = 15.68 103 3
The convergence is achieved.
The volume of n-octane = 15.6810-3 m3/mol.

2. Redlich-kong equation of state

Problem: Calculate the molar volume of saturated vapour and saturated liquid of n-
octane at 0.215 MPa and 427.85 K assuming that the fluid follows the redlich-kong
equation of state. The critical constants of n-octane are Tc=569.4 K Pc=24.97 bar.
Solution: The parameter a and b of R K equation are
0.42748 2 2.5 0.42748 (8.314)2 (569.4)2.5
= 1 = 1
2 2.497 106 (427.85)2
= 4.4266 2
0.08664 0.08664 8.314 569.4
= = = 0.1643 103 3 /
2.497 106
Let us use cardans method to determine vg and vf
 4.426 0.215 106
= = = 0.0752
()2 (8.314 427.85)2
0.1643 103 0.215 106
= = = 9.9306 103
(8.314 427.85)
= 1
= = 0.0752 9.9306 103 (9.9306 103 )2
2

= = 0.0752 9.9306 103 = 7.4678 104

2 1
= = 0.0652 = 0.2681
3 3
3
2 2 0.0652
= + = 7.4678 104 = 0.0531
27 3 27 3
2 3 (0.0531)2 (0.2681)3
= + = = 8.8155 106
4 27 4 27
1
3 2 0.26813
= ( ) = = 0.0267
27 27
1
27 2 0.0531 1
= ( 3 ) = = 0.9944 = 6.07
2 2 0.0267
1 1 6.07
1 = 2 3 ( ) = 2(0.0267)3 ( ) = 0.09308
3 3
1 2 + 1 1
2 = 2 3 ( ) = 2(0.0267)3 (122.02) + = 0.0163
3 3 3
1 4 + 1 1
3 = 2 3 ( ) = 2(0.0267)3 (242.02) + = 0.0528
3 3 3
Z=0.9308 corresponds to saturated vapour and Z= 0.0163 corresponds to saturated
liquid.
0.9308 8.314 427.85
= = = 15.3999 103 3 /
0.215 106
0.0163 8.314 427.85
= = 0.2697 103 3 /
0.215 106

3. Soave-redlich-kwong equation of state

Problem: Calculate the molar volume of saturated liquid and saturated vapour for n-
octane at 427.85 K and 0.215MPa using soave-redlich-kwong equation of state. For n-
octane, Tc=569.4 K, Pc=24.97 bar and =0.398.
Solution: Using cardans method to calculate the molar volumes.
427.85 0.215 106
= = = 0.7514; = = = 0.0861
569.4 24.97
= 0.48 + 1.574 0.1762 = 0.48 + 1.574 0.398 0.176 (0.398)2
= 1.0786
2 2
= [1 + (1 )] = [1 + 1.0786(1 0.7514)] = 1.3079
0.42748 2 2 0.42748 (8.314)2 (569.4)2 1.3079
= = = 5.0180
2.497 106
 0.08664 0.08664 8.314 569.4
= = = 1.6426 104
2.497 105
5.0108 0.215 106
= = = 0.0853
()2 (8.314 427.85)2
0.1643 104 0.215 106
= = = 9.9282 103
(8.314 427.85)
= 1
= = 0.0853 9.9282 103 (9.9282 103 )2
2

= 9.9282 103
= = 0.0853 9.9282 103 = 8.4688 104
2 1
= = 7.5371 102 = 0.2580
3 3
3
2 2 7.5371 102
= + = 8.4688 104
27 3 27 3
= 4.9797 102
2 3 (4.9797 102 )2 (0.2580)3
= + = = 1.6121 105
4 27 4 27
1
3 2 0.25803
= ( ) = = 2.5220 102
27 27
1
27 2 4.9797 102
= ( 3 ) = = 0.9873 = 9.14
2 2.5220 102
1 1 9.14 1
1 = 2 3 ( ) = 2(2.5220 102 )3 ( ) + = 0.9191
3 3 3 3
1 2 + 1 1
2 = 2 3 ( ) = 2(2.5220 102 )3 (123.05) +
3 3 3
2
= 1.3393 10
1 4 + 1 1
3 = 2 3 ( ) = 2(2.5220 102 )3 (243.05) +
3 3 3
= 6.7452 102
Z=0.9191 corresponds to saturated vapour and Z= 1.3393 102 corresponds to
saturated liquid.
0.9191 8.314 427.85
= = = 15.206 103 3 /
0.215 106
1.3393 102 8.314 427.85
= = 0.216 103 3 /
0.215 106

4. Peng-robinson equation of state

Problem: Calculate the molar volume of saturated liquid and saturated vapour for n-
octane at 427.85 K and 0.215MPa using Peng-robinson equation of state. For
n-octane, Tc=569.4 K, Pc=24.97 bar and =0.398. Use cardans method to
determine vf and vg.
Solution: Using Cardans method to find molar volumes.
 427.85 0.215 106
= = = 0.7514; = = = 0.0861
569.4 24.97
= 0.37464 + 1.54226 0.2692
= 0.37464 + 1.54226 0.398 0.269 0.3982 = 9.4570 101
2 2
= [1 + (1 )] = [1 + 9.4570 101 (1 0.7514)] = 1.2677
0.457242 0.45724 (8.314)2 (569.4)2 1.2677
= = = 5.2024
2.497 106
0.07780 0.07780 8.314 569.4
= = = 1.4750 104
2.497 105
5.2024 0.215 106
= = = 8.8398 102
()2 (8.314 427.85)2
01.4750 104 0.215 106
= = = 8.9151 103
(8.314 427.85)
= 1 + = 1 + 8.9151 103 = 0.9911
= 2 3 2
= 8.8398 102 2 8.9151 103 3
(8.9151 103 )2 = 7.0329 102
= + 2 + 3
= 8.8398 102 8.9151 103 + (8.9151 103 )2
+ (8.9151 103 )3 = 7.0789 104
2 (0.9911)2
= = 7.0329 102 = 0.2571
3 3
23
= +
27 3
2 (0.9911)3 0.9911 7.0329 102
= + 7.0789
27 3
104 = 4.9584 102
2 3 (4.9584 102 )2 (0.2571)3
= + = = 1.4677 105
4 27 4 27
1
3 2 0.25713
= ( ) = = 2.5088 102
27 27
1
27 2 4.9584 102
= ( 3 ) = = 0.9882
2 2 2.5088 102
= 0.1533
1 1 0.9911
1 = 2 3 ( ) = 2(2.5088 102 )3 (0.0511) +
3 3 3
= 0.9151
1 2 + 1 0.9911
2 = 2 3 ( ) = 2(2.5088 102 )3 (2.144) +
3 3 3
= 1.2106 102
 1 4 + 1 0.9911
3 = 2 3 ( ) = 2(2.5088 102 )3 (4.237) +
3 3 3
2
= 6.3904 10
Z=0.9151 corresponds to saturated vapour and Z= 1.2106 102 corresponds to
saturated liquid.
0.9151 8.314 427.85
= = = 15.14 103 3 /
0.215 106
1.2106 102 8.314 427.85
= 6
= 0.2003 103 3 /
0.215 10