353

APPENDICES

Appendix A: Tables

Page Number

Properties of Pure Compounds

Properties of Single Carbon Number Groups
Universal Gas Constant
Binary Interaction Parameters
Conversion Factors

354
356
357
358
363

Appendix B: Critical Property Correlations in Field Units

364

Appendix C: Equation of State Expressions

368

Appendix D: Equilibrium Ratios

372

A. 1
A.2
A.3
A.4
A.5

Equilibrium Ratio Charts at 5000 psia (34.47 MPa) Convergence Pressure

GPA Copyright. Reproduced with permission from: "SI Engineering Data Book" (1980)

354

Appendix A

Table A. 1.

omEounds.
w

Name

Mw
kg/kgmol

Tb
K

m--*#,m-

Tc

P
_
a
_
_
1
-

pc
vc
MPa m3/kgmol

~~~

acentnc Rackett parachor

K
factor
Z,
- _ . I _ _ ~ - ~
~- ~
- **
16043 111 66 19056 4599 00986 02862 00115 028941 7405
Methane
30.070 184.55 305.32 4.872 0.1455 0.2793 0.0995 0.28128 112.91
Ethane
44.096 231.11 369.83 4.248 0.2000 0.2763 0.1523 0.27664 154.03
Propane
58.123 261.43 408.14 3.648 0.2627 0.2824 0.1770 0.27569 185.32
i-Butane
n-Butane
58.123 272.65 425.12 3.796 0.2550 0.2739 0.2002 0.27331 193.90
72.150 300.99 460.43 3.381 0.3058 0.2701 0.2275 0.2706* 229.37
i-Pentane
Neopentane
72.150 282.65 433.78 3.199 0.3036 0.2693 0.1964 0.27570 236.00
72.150 309.22 469.7 3.370 0.3130 0.2701 0.2515 0.26853 236.00
n-Pentane
2-Methylpentane 86.177 333.41 497.5 3.010 0.3664 0.2666 0.2781 0.2662* 269.15
0.2659 0.3013 0.26355 276.71
n-Hexane
86.177 341.88 507.6 3.025 0.371
0.261 1 0.3495 0.26074 318.44
n-Heptane
100.204 371.58 540.2 2.740 0.428
0.2559 0.3996 0.25678 359.33
n-Octane
114.231 398.83 568.7 2.490 0.486
n-Nonane
128.258 423.97 594.6 2.290 0.544
0.2520 0.4435 0.25456 399.57
142.285 447.3 617.7 2.110 0.600
0.2465 0.4923 0.25074 440.69
n-Decane
0.2419 0.5303 0.24990 482.00
1.949 0.659
n-Undecane
156.312 469.08 639
0.2382 0.5764 0.24692 522.26
170.338 489.47 658
1.820 0.716
n-Dodecane
0.2320 0.6174 0.24698 563.77
1.680 0.775
n-Tridecane
184.365 508.62 675
0.2262 0.6430 0.24322 606.05
1.570 0.830
n-Tetradecane
198.392 526.73 693
0.2235 0.6863 0.2303* 647.43
2 12.419 543.83 708
1.480 0.889
n-Pentadecane
0.2199 0.7174 0.2276* 688.50
1.400 0.944
n-Hexadecane
226.446 560.01 723
1.340 1.000 0.2190 0.7697 0.23431 730.05
n-Heptadecane
240.473 575.3 736
n-Octadecane
0.2168 0.8114 0.22917 77 1.95
1.270 1.060
254.500 589.86 747
n-Nonadecane
0.2150 0.8522 0.2158* 813.85
1.210 1.120
268.527 603.05 758
n-Eicosane
0.2126 0.9069 0.22811 853.67
1.160 1.170
282.553 616.93 768
n-Heneicosane
296.580 629.7 781.7 1.147 1.198 0.21 14 0.9220 0.2097* 897.64
n-Docosane
310.610 641.8 791.8 1,101 1.253
0.2095 0.95SO 0.2068* 939.55
n-Tncosane
324.630 653.4 801.3 1.059 1.307
0.2078 0.9890 0.2038* 981.4.3
n-Tetracosane
338.680 664.4 810.4 1.019 1.362
0.2061 1.0190 0.2011*_1023.40
* ZRAfrom L1.151 except those identified by * which are calculated from the Yamada-Gunn correlation,
E.(1.13).
** Parachor values are to be used only in Eq.(8.21).
Z,

Sp Gr

03000
0.3562
0.5070
0.5629
0.5840
0.6247
0.5974
0.631 1
0.6578
0.6638
0.6882
0.7070
0.7219
0.7342
0.7445
0.7527
0.7617
0.7633
0.7722
0.7772
0.7797
0.7820
0.7869
0.7924
0.7954
0.798 1
0.8004
. ...
0.8025

Tables

355

Table A. 1 (Cont.).

Mw

T,
T,
pc
"c
Z,
acentric Rackett parachor
K
K
MPa m3/kpmol
**
"
---__- factor Z,
Ethy 1ene
28.054 169.47 282.36 5.032 0.1291 0.2767 0.0852 0.28054 101.53
42.081 225.43 364.76 4.612 0.1810 0.2753 0.1424 0.27821 143.02
Propylene
1-Butene
56.107 266.9 419.59 4.020 0.2399 0.2765 0.1867 0.27351
56.107 276.87 435.58 4.206 0.2340 0.2717 0.2030 0.27044
cis-2-Butene
trans-2-Butene
56.107 274.03 428.63 4.103 0.2382 0.2742 0.2182 0.27212
40.065 238.65 393.15 5.470 0.1620 0.271 1 0.1596 0.27283
Propadiene
1 2-Butadiene
54.092
284
444
4.500 0.2190 0.2670 0.2509 0.2685*
1 3-Butadiene
54.092 268.74 425.37 4.330 0.2208 0.2704 0.1932 0.27130
1-Pentene
70.134 303.1 1 464.78 3.529 0.2960 0.2703 0.2329 0.27035
cis-2-Pentene
70. I34 310.08 475.93 3.654 0.3021 0.2790 0.2406 0.2694*
trans-2-Pentene
70.134 309.49 475.37 3.654 0.3021 0.2793 0.2373 0.2697*
2-Methyl- 1-Butene
70.134 304.3
465
3.400 0.2920 0.2568 0.2287 0.2705*
3-Methyl-1-Butene
70.134 293.21 450.37 3.516 0.3021 0.2837 0.2286 0.2705*
2-Methyl-2-Butene
70.134 311.71 471
3.400 0.2920 0.2535 0.2767 0.2663*
1-Hexene
84.161 336.63 504.03 3.140 0.3540 0.2653 0.2800 0.2660*
1-Heptene
98.188 366.79 537.29 2.830 0.4130 0.2616 0.3310 0.2615*
Cyclopentane
70.134 322.4 511.76 4.502 0.2583 0.2733 0.1943 0.26824 210.05
Methylc yclopentane
84.161 344.96 532.79 3.784 0.3189 0.2725 0.2302 0.2704*
Cyclohexane
84.161 353.87 553.54 4.075 0.3079 0.2726 0.2118 0.27286 247.89
Methylcyclohexane
98.188 374.08 572.19 3.471 0.3680 0.2685 0.2350 0.26986 289.00
Ethylcyclopentane
98.188 376.62 569.52 3.397 0.3745 0.2687 0.2715 0.2667*
Ethy lcyclohexane
112.215 404.95 609.15 3.040 0.4500 0.2701 0.2455 0.2690* 328.74
Benzene
78.114 353.24 562.16 4.898 0.2589 0.2714 0.2108 0.26967 210.96
Toluene
92.141 383.78 591.79 4.109 0.3158 0.2637 0.2641 0.2639* 252.33
Ethylbenzene
106.167 409.35 617.17 3.609 0.3738 0.2629 0.3036 0.26186 292.21
o-Xylene
106.167 417.58 630.37 3.734 0.3692 0.2630 0.3127 0.2620*
m-Xylene
106.167 412.27 617.05 3.541 0.3758 0.2594 0.3260 0.2620*
p-Xylene
106.167 411.51 616.26 3.511 0.3791 0.2598 0.3259 0.2870*
Nitrogen
28.014
77.35 126.1 3.394 0.0901 0.2917 0.0403 0.28971 61.12
Oxygen
3 1.999
90.17 154.58 5.043 0.0734 0.2880 0.0218 0.28962
Carbon Monoxide
28.010
81.7 132.92 3.499 0.093 1 0.2948 0.0663 0.28966
Carbon Dioxide
44.010 194.67 304.19 7.382 0.0940 0.2744 0.2276 0.27275 82.00
Hydrogen Sulphide
34.082 212.8 373.53 8.963 0.0985 0.2843 0.0827 0.28476 85.50
Sulpher Dioxide
64.065 263.13 430.75 7.884 0.1220 0.2686 0.2451 0.26729
Hydrogen
2.016
20.39 33.18 1.313 0.0642 0.3053 -0.2150 0.31997
Water
00560 02294 03449
18 015 373 15 647 2>1~~*~~
* Z,, from [l 151 except those identified by * which are calculated from the Yamada-Gunn correlation,
Eq(1 13)
** Parachor values are to be used only In Eq (8 21)
Name

Sp.Gr.

kg/kgmol

yL

0.5000
0.5210
0.6005
0.6286
0.61 12
0.5997
0.6576
0.6273
0.6458
0.6598
0.6524
0.6563
0.6322
0.6683
0.6769
0.7015
0.7603
0.7540
0.7835
0.7748
0.7712
0.7921
0.8829
0.8743
0.8744
0.8849
0.8694
0.8666
0.8094
1.1421
0.8180
0.8014
1.3946
10000

356

Appendix A

Table A.2.
SCN

MW

C6
c7
C8
c9
c10
c11
c12
C13
C14
C15
C16
C17
C18
C19
c20
c 21
c22
C23
C24
C25
C26
C27
C28
C29
C30
C3 1
C32
c33
c34
c35
C36
c37
C38
c39
C40
C4 1
C42
c43
c44
C45

84
96
107
121
134
147
161
175
I90
206
222
237
25 1
263
275
29 1
300
312
324
337
349
360
372
382
394
404
415
426
437
445
456
464
475
484
495
502
512
52 1
53 1
539

arbon num
-~~~
Sp.Gr

T,
K
337
366
390
416
439
461
482
501
520
539
557
573
586
598
612
624
637
648
659
67 1
68 1
69 1
701
709
719
728
737
745
753
760
768
774
782
788
796
801
807
813
82 1
826

rties.

"

*
1
1
1
_
1

T,

pc

"c

Z,

.K
L?E!!2&!L-0.690
0.727
0.749
0.768
0.782
0.793
0.804
0.815
0.826
0.836
0.843
0.851
0.856
0.861
0.866
0.871
0.876
0.881
0.885
0.888
0.892
0.896
0.899
0.902
0.905
0.909
0.912
0.9 15
0.917
0.920
0.922
0.925
0.927
0.929
0.93 1
0.933
0.934
0.936
0.938
0.940

510
547
574
603
627
649
670
689
708
727
743
758
770
78 1
79 3
804
815
825
834
844
853
862
870
877
885
893
90 1
907
914
920
926
932
938
943
950
954
959
964
970
914
_ ..

3.271
3.071
2.877
2.665
2.481
2.310
2.165
2.054
1.953
1.853
1.752
1.679
1.614
1.559
1.495
1.446
1.393
1.356
1.314
1.263
1.230
1.200
1.164
1.140
1.107
1.085
1.060
1.039
1.013
0.998
0.974
0.964
0.941
0.927
0.905
0.896
0.877
0.864
0.844
0.835

0.348
0.392
0.433
0.484
0.532
0.584
0.635
0.681
0.727
0.777
0.830
0.874
0.915
0.951
0.997
1.034
1.077
1.110
1.147
1.193
1.226
1.259
1.296
1.323
1.361
1.389
1.421
1.448
1.480
1.502
1.534
1.550
1.583
1.604
1.636
1.652
1.680
1.701
1.733

Tc, PC, and Vc: Calculated from Twu correlations, Eqs(6.23-25).

2,: Calculated from Pcvc=ZCRTc,
Acentric factor : Calculated from the Lee-Kesler correlation, Eq~(6.9-10).
ZRA:Calculated from the Yamada-Gunn correlation, Eq.(l.13).

0.268
0.265
0.261
0.257
0.253
0.250
0.247
0.244
0.241
0.238
0.235
0.233
0.23 1
0.229
0.226
0.224
0.221
0.220
0.217
0.215
0.213
0.211
0.209
0.207
0.205
0.203
0.201
0.199
0.197
0.196
0.194
0.193
0.191
0.190
0.188
0.187
0.185
0.184
0.181

9s.

e+#-

Acen Fact.

- -_
0.25 1
0.280
0.312
0.352
0.389
0.429
0.467
0.501
0.536
0.571
0.610
0.643
0.672
0.698
0.732
0.759
0.789
0.815
0.841
0.874
0.897
0.944
0.968
0.985
1.008
1.026
1.046
1.063
1.082
1.095
1.114
1.124
1.142
1.154
1.172
1.181
1.195
1.207
1.224

Rackett
0.269
0.266
0.263
0.260
0.256
0.253
0.250
0.247
0.244
0.240
0.237
0.234
0.232
0.229
0.226
0.224
0.221
0.219
0.217
0.214
0.212
0.200
0.198
0.196
0.194
0.193
0.191
0.189
0.188
0.187
0.185
0.184
0.182
0.181
0.180
0.179
0.178
0.177
0.175
0.174

__

357

Tables

Table A.2 (Cont.).

Generalised single carbon number group properties.
Ahmeds Correlation*:
O= A,+A,(C,)+ A3(C,)*+ A4(CJ3+A5/( C,)
where,

0 : Any physical property

C,: Carbon group number
with constants as follows:

M
T,, R
S
0

T,, R
P,, psia
v,,ft/lb

A,

- 131.11375
434.38878
0.86714949
- 0.50862704
915.53747
275.56275
5.223458 E-2

A,
24.96156
50.125279
3.4143408 E-3
8.700211 E-2
41.421337
- 12.522269
7.8709139 E-4

A?

- 0.34079022
- 0.9027283
- 2.839627 E-3

2.4941 184 E-3

7.0280657 E-3
2.4943308 E-8
1.4663890 E-5
- 1.8484814 E-5
- 0.7586859
5.8675351 E-3
- 2.8452129 E-3
0.29926384
1.7547264 E-7
- 1 9324432 E-5

A,
468.32575
- 601.85651
- 1.1627984
1.8518106
- 1.3028779E3
1.7117226 E3
4.4017952 E-2

The correlation gives the calculated critical properties by Whitson using the Riazi-Daubert
correlation, Eq.(6.14), and not those given in Table A.2.

* Ahmed, T: Hydrocarbon Phase Behaviour, Gulf Publishing Company, Houston (1989).

Table A.3.
Universal gas constant values.
P, Pressure
atm
bar
MPa

T, Temperature
K
K
K

v, Mol. Vol.
cm3/gmol
lit/gmol
m/kgmol

R
82.0567
0.083144
0.0083144

358

1
2
3
4

Appendix A

.oooo

N2
c02
c1
Ethylene
C2

,0600
,0280
,1000
,0610

.OOOO
,0760
.IO00
,1090

-.0030 .OOOO

.OOOO

6
7
8
9
10

Propylene
c3
iC4
nC4
iC5

,1000
,1240
,1200
,1690
,1600

,1300
,1370
,1300
,1300
.IO00

,0060
,0050
.O 190
,0230
,0230

.OOOO
.OOOO
.OOOO
.OOOO
,0100

,0020
,0010
,0040
,0090
,0380

.OOOO
.OOOO
,0005
,0006
,0010

11
12
13
14
15

Neopentane
nC5
nC6
Met Cyc Pent
Cyc Hex

,1600
,1870
,1900
,1900
,1900

.lo00
,1000
,1000
,1000
,1000

,0190
,0190
,0300
,0130
,0130

,0100 ,0350
,0100 ,0185
,0100 ,0380
,0100 ,0100
,0100 .0100

.0010

16
17
18
19
20

nC7
MetCycHex
Toluene
o-Xylene
nC8

,1900
,1900
,1900
,1900
,1900

.IO00
,1000
.IO00
,1000
,1000

,0130
,0200
,0200
,0270
,0150

,0100
,0100
,0100
.0100
,0100

,0100
,0100
,0100
,0200
,0100

.OOOO

.oooo .oooo

.OOOO
.OOOO
,0100
,0060

,000
.OOOO
.OOOO

.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO

,0004
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
,0300
.OOOO
.OOOO

.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
,0400
.OOOO

.OOOO
.OOOO
.OOOO
,0400
.OOOO

.OOOO
.OOOO
.OOOO
,0350
.OOOO

.OOOO
.OOOO
.OOOO
,0300
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
,0000

.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO

,0000

.OOOO
.OOOO
.OOOO

.OOOO ,0220 .OOOO

.OOOO .OOOO .OOOO
.OOOO .OOOO .OOOO .OOOO
.OOOO .OOOO ,0000 .OOOO
saw
From: Yarborough, L. : "Applications of a Generalized Equation of State to Petroleum Reservoir Fluids",
Equations of State in Engineering, Advances in Chemistry Series, Edited by K. C. Chao and Robinson, R. L.,
American Chemical Society, Washington, DC, 182, page 385-435(1979).
21
22
23
24

nC9
nC10-nC14
nC15-nC19
nC20-nC24

,1900
,1900
,1900
,1900
~~

,1000
,1000
,1000
,1000

,0150
,0100
,0100
.OOOO

.0100
,0060
,0080
.OOOO

,0100
,0080
.OOOO
.OOOO

Pd _ m u L

Tables

359

Table A.4.2.
No.

,0278
,0300
,0407

,1107
,1000
,1363

.OOOO

Component
N2
c02
c1
Ethylene
c2

6
7
8
9
10

Propylene
c3
iC4
nC4
iCj

,0800

.IO00
,1000
,1000
,1000
.IO00

,0289

,0763
,0944
,0700
,0867

,0241
,0056
,0078

,0200
,0220
,0900 ,0010
,1000 ,0067
,0120 ,0050

11
12
13
14
15

Neopentane
nCj
nC6
Met CycPent
CycHex

,0870
.0878
,1400
,1400
,1400

,1000
,1000
,1000
,1000
.IO00

,0078
,0019
,0374
,0400
,0333

.0120
,0120
,0140
,0140
,0150

16
17
18
19
20

nC7
MetCycHex
Toluene
o-Xylene
nCg

,1422
,1450
,1500
,1500
,1500

.lo00 ,0307
,1000 ,0500
,1000 ,0978
,1000 ,1000
,1000 ,0448

,0411
,0230
.0300 ,0900
,0250 ,0500
,0200 ,0170

,0100
.0100

21
22
23
24

nCg
nC10-nC14
nCij-nC1g
nC20-nC24

,1500

,1000
,1000
.IO00
,1000

,0200 ,0170
,0300 ,0200
,0400 ,0350
.0450 ,0400

,0100
,0150
,0250
.0300

1
2
3
4

10-24

.oooo
.oooo .oooo

,1500
.1500

,1500

,0189
,0078

,0080

,0448
,0550
,0600
.0650

.OOOO

,0026 .OOOO
.OOOO
,0080

,0050
,0056
,0156
,0330
,0230

,0144

,0150

.OOOO

,0033
,0144
.OOOO
.OOOO
.OOOO

,0050
,0050
,0050
,0050

,0300
,0300
.0100

,0000
,010
.OOOO

,0078

.OOOO
.OOOO
.OOOO

.OOOO
.OOOO

.OOOO

.OOOO

,0300

,0204
,0111

.OOOO
.OOOO
.OOOO

.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

,0078
,0230
,0022
,0030
,0030

,0005

,0044
,0050
,0300
,0300
,0040

.0005
,0005
,0200
,0200
,0015

.OOOO
.OOOO

,0040
,0040
,0005

,0015
,0020
,0025
,0050

.OOOO
.0010

.0010

.OOOO
.OOOO

,0100
.0100
.OOOO

,0010
,0015

.OOOO

.OOOO
.OOOO
.OOOO
.OOOO

From: Knapp, H. and Doring, R. : Vapour-Liquid Equilibria for Mixtures of Low Boiling Substances,Berhens,
D. and Eckerman R., Eds(Dechema Chemistry Data Ser.), Part I- Binary System (1986).

Appendix A

360

Table A.4.3.
Binary interaction parameters for Peng-Robinson equation of state.
No.
1
2
3
4

,0311
,0500
,0515

,1070
,1200
,1322

,0215
,0026

.OOOO

Component
N2
c02
c1
Ethylene
c2

,0089

.OOOO

6
7
8
9
10

Propylene
c3
iC4
nC4
iC5

,0600 ,1300
,0852 ,1241
,1000 ,1400
.07 11 ,1333
,1000 ,1400

,0330
,0140
,0256
,0133
,0056

.OOOO

,0100
,0200
,0200
,0250

,0089
,0011
,0067
,0096

11
12
13
14
15

Neopentane
nC5
nC6
MetCycPent
CycHex

,1000
,1000
,1496
,1500
.1500

,1400
.I400
,1450
,1450
,1450

,0056
,0236
,0422
,0450
,0450

,0250 ,0080
,0250 ,0078
,0300 ,0140
,0310 ,0141
.03 10 ,0141

16
17
18
19
20

nC7
MetCycHex
Toluene
o-Xylene
nCg

,1441
,1700
,1500
,1500

,1450
,1450
,1800
,1400
,1400

,0352
,0450
,0600
,0470
,0470

,0300
,0300
,0400
,0300
,0300

21
22
23
24

nC9
nClo-nC14
nC15-nC19
nC20-nC24

,1550
,1550
,1550
,1550

,0145
,0145
,0145
,0145

,0474
,0500
,0600
,0700

10-24

.oooo
.oooo .oooo

,1500

.OOOO

.OOOO

,0100

.OOOO

,0080
,0080
,0080

,0078
,0033
,0111

,000
.OOOO

.OOOO

,004

,0170

.OOOO

,0080

.0100
,0110
,0120
,0120

,0111
.O 120
,0267
,0270
,0270

,0040
,0020
,0240
,0242
,0242

,0170
,0170
,0174
,0180
,0180

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

,0150
,0160
.0200
,0160
,0160

,0140
,0150
,0210
,0150
,0150

,0560
,0580
,0600
.0590
,0590

,0250
,0250
,0300
.0260
,0260

.0190
,0200
,0110
,0120
,0120

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

,0190
,0300
,0500 ,0400
,0600 ,0500

,0200
,0250
,0300
,0350

,0070
,0200
,0250
,0300

,0060

,0100
,0010

.OOOO
.OOOO
.OOOO
.OOOO

,0400

,0450

,0080

.0100

,0150
,0200

.0010

.0015

From: Knapp, H. and Doring, R. : "Vapor-Liquid Equilibria for Mixtures of Low Boiling Substances", Berhens,
D. and Eckerman R., Eds(Dechema Chemistry Data Ser.), Part I- Binary System (1986).

Tables

36 1

Table A.4.4.
Binary interaction parameters for Patel-Teja equation of state.
No.

Component

1
2

N2
c02

3
4
5

c1

10-24

.oooo
,0600

.OOOO

Ethylene
c2

,0320
,0400
,0600

,0930
,1100
,1280

,0050

.OOOO
,0010

.OOOO

6
7
8
9
10

Propylene
c3
iC4
nC4
iC5

,0800
,0740
,0540
.03 10
,0110

.1300
,1280
,1270
.1150
,1250

,0090
,0040
,0020
,0020
,0100

,0200
,0300
,0300
,0300
,0300

,0002
,0010
,0010
,0010

11
12
13
14
15

Neopentane
nC5
nC6
MetCycPent
CycHex

,0110
.OOOO
.O 100
,0120
.0140

,1000
,1350
,1400
.1400
,1400

,0100
,0100
,0360
,0370
,0370

,0400
,0400
,0400
,0400
,0400

16
17
18
19
20

nC7
MetCycHex
Toluene
o-Xylene
nCg

,0160
.0180
,0300
,0600
,0400

,1400
,1400
.1500
,1600
.1400

,0370
.0380
,0620
,0620
,0600

,0400
,0400
,0400

21
22
23
24

nCg
nC10-nC14
nC1ynCig
nC20-nC24

,0450

,0500
,0550

,1400
,1500
.1800
,2000

.0400
,0430
,0800
,1280

,0600

.OOOO
.0080

,0050

.OOOO
.OOOO

,0006
,0010

.OOOO
.OOOO
,0100
,0060

,000
.OOOO
.OOOO

,0010
.OOOO
.OOOO
.OOOO
.OOOO

.0010
.OOOO
.OOOO
.OOOO
.OOOO

,0004
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO

.OOOO
.OOOO
.OOOO
,0400
.OOOO

.OOOO
.OOOO
.OOOO
,0400
.OOOO

.OOOO

,0400

.OOOO
.OOOO
.OOOO
,0450
.OOOO

.OOOO
.OOOO
.OOOO
,0300
.OOOO

,0400
,0600
,0800
,1000

.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO

,0500

,0005

.OOOO
.OOOO
,0350
.OOOO

.OOOO
.OOOO

.OOOO
.OOOO

.WOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO

.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO
.OOOO
.OOOO

.OOOO
.OOOO
.OOOO

.OOOO

From: Willman, B. T. and Teja, A. S. : "Continuous Thermodynamics of Phase Equilibria Using a Multivarate
Distribution Function and an Equation of State", AIChE J, 32(12), 2067-2078 (1986).

Appendix A

362

Table A.4.5.
Interaction parameters of C 0 2 , N2 and H2S binaries for
tion of state
Valderrama-Patel-T
-*-

-_xide

Methane
Ethane
Propane
I-Butane
n-Butane
n-Pentane
n-Hexane
n-Heptane
arbon Dioxide

0 092
0 134
0 128
0 126
0 138
0 141
0 118
0 110
-

NJtropn
0 035
0 038
0 070
0 134
0 114
0 088
0 150
0 142
-0 036

- Hjdr

Sulfide

0 080
0 095
0 088
0 050
0 050
0 047
0 047
0 047
0 088

All hydrocarbon-hydrocarbonBIP=O

Table A.4.6
Interaction parameters and coefficients of methanol and water binanes for Valderrama-PatelTeja equation of state with non-random mixing $e, Eqs.(4 8 6 2 )
Methanol
Component (1)
Methane
Ethane
Propane
i-Butane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
Carbon dioxide
Nitrogen
Hydrogen sulfide
Methanol
Water

k,,
02538
00137

$1

07319
00519
0 0779
03209
02917
07908
05607
04592
05331
0 0700
10440
0 I 133
00000

0 1233
0 1465
02528
02245
0 1461
0 1403
0 05 10
02484
0 0694
00000

**

e
-

~~~~~

Water

1); E-4

I;,

6 88
2170
0 00
1760
0 00
5828
1754
27 17
3691
1 I 56
7 22
0 00
0 00
0 00

05028
04974
05465
05863
05800
05525
04577
04165
0 3901
0 1965
04792
0 1382

18180
14870
16070
17863
16885
I6188
15730
I5201
I5200
07232
2 6575
03809
0 0000
00000

**
00000
~~~~~~~

*klJ of propane-methanol is temperature dependent kpm=O 0278+0 0009 1 1(T-273)

**k,, of water-methanol IS temperature dependent kmw=-O 100+0 000185(T-273)

1bIE-4
49 00
45 40
39 30
37 40
33 57
23 72
31 41
35 21
35 31
23 74
64 46
13 24
0 00
0 00

363

Tables

Table A S .

= Pa
E + OS
= Pa
1.o*
E + 05
= m3
1.589 873
E - 01
X
=
m3/s
1.840
131
E
06
X
E + 00
= kJ
1.055 056
X
=K
"C +273.15
1.0*
E + 00
= mPa.s
X
1
.o*
E
+
00
= mm2/s
X
= m2
9.869 233
E - 13
X
1.0*
E
02
= mN
X
E + 00
1 .o*
= mN/m
X
=m
3.048*
E-01
X
= m2
9.290 304*
E - 02
X
= mm2/s
9.290 304*
E + 04
X
= m'
2.831 685
ft'
E - 02
X
= m'/m'
1.781 076
E - 01
ft'/bbl
X
6.242
796
E
02
ft'/lbm
= m3/kg
X
= "C
(OF - 32)/1.8
"F
=K
"F
( O F + 459.67)/1.8
= m3
E - 03
3.785 412
gal (US)
X
2.54*
in.
E - 02
=m
X
= m'
6.451 6"
E - 04
in.'
X
= m'
1.638 706
in.'
E - 05
X
4.448 222
E + 00
=N
Ibf
X
=
Pa.s
E
+
03
6.894
1bf d m '
I57
X
E - 01
= kg
Ibm
4.535 924
X
= kg/m3
E+01
1.601 846
Ibm/ft'
X
= m3
1.0*
E
06
mL
X
1.333 224
E - 02
= MPa
mmHg=torr
X
E
03
= MPa
6.894
757
psi
X
=K
1/1.8*
"R
X
E-04
= m2/s
10"
St (stoke)
+
06
SI Unit Prefix~-h(rmlli)=E - 03 k(lulo)=E + 03 M(mega)=E
* Conversion factor is exact
atm(std)
bar
bbl (US)
bbl/D
Btu
"C
cp (centi poise)
cSt (cent] Stoke)
d (darcy)
dyne
dyne/cm
ft
ft2
ft%

x_x x

Ixv----**-*

_I

Appendix B

364

CORRELATIONS FOR ESTIMATING CRITICAL PROPERTIES

IN FIELD UNITS

The units of temperature, pressure and volume are Rankine, psia, and fts/lbmol, respectively,
in all the following equations. The specific gravity, S, is defined relative to water at 60 O F .
The correlations in SI unit are given in Section 6.2.

Lee-Kesler Correlations
T, = 341.7+811S+(0.4244+0.1174S)Tb+(0.4669-3.2623S)X10s/Tb
lnP, = 8.3634-0.0566/S-(0.24244+2.2898/S+0.11857/S2)~lO~3Tb

+(1.4685+3.648/S+0.47227/S2)x lO-T; - (0.42019+ 1.6977/S2)x10-oT:

0 =(hPb, -5.92714+6.09648/Tbr

+ 1.28862 hTb, -0.169347Tir)/

(15.2518- 1.5.6875/Tbr -13.4721 hTb, +0.4357T,6,) fOrTbr 2 0.8

w = -7.904 + O.1352Kw- 0.007465K: + 8.359Tb,

+(1.408 - 0.01063K,)/Tb,
for Tbr>0.8
where Pbr=Pb/Pc, Tb,=Tflc; Pb is the pressure at which Tb is measured, e.g., the normal
boiling point at 14.69 psia, and K, is the Watson characterisation factor, Eq.(6.2).

Cavett Correlations
T, = 768.071 +1.7134 (Tb-459.67)-0.10834~lO-~(T~
-459.67)2+0.3889~10-6(Tb-459.67)3
-0.89213~
1O-(Tb -459.67)API+0.53095 x 10-5(Tb-459.67)API+0.32712 x 10-7(Tb-459.67)API
IogP, = 2.829+0.9412~10-3(Tb-459.67)-0.30475~lO-~(T~
-459.67)*
-459.67)API
+O.15184x10-*(Tb -459.67)3 -0.20876x104(Tb -459.67)API+0.11048x10-7(Tb
-0.4827 x 10-7(Tb-459.67)API +0.1395 x 10-(Tb -459.67)API
where API = (141.5/S) - 131.5.

Critical Properties Correlations

365

Riazi-Daubert Correlations

Twu Correlations
The method initially correlates the properties of normal paraffins as the reference. The
calculated values are then adjusted for petroleum fractions using the difference between the
specific gravity of the hydrocarbon fraction and that of the normal paraffin with the same
boiling point as the correlating parameter.

Normal Paraffins:
The properties of normal paraffins are correlated with the normal boiling point temperature,
Tcp= Tb[0.533272+0.191017~10-3Tb
+0.779681~1O-'T,2
-0.284376 x lO-''T:

+0.959468 x lo2 / ( T b /100)"]'

Pcp= (3.83354 + 1.19629$

+ 3 4 . 8 8 8 8 ~+ 3 6 . 1 9 5 2 ~+~1 0 4 . 1 9 3 ~ ~ ) ~

v,, = [l- (0.419869 - 0 . 5 0 5 8 3 9 ~- 1.56436~'- 9481.70~'~))1-~

S, = 0.843593 - 0 . 1 2 8 6 2 4 ~- 3 . 3 6 1 5 9 ~-~1 3 7 4 9 . 5 ~ ' ~

where the subscript p refers to properties of normal paraffins and,

~y

1- Tb/ Tcp

Appendix B

366
The molecular weight of paraffins is given by the following implicit relation,

Tb = exp (5.71419+2.71579 lnM, -0.286590(1nMp)2 -39.8544/(1nM,)-0.122488/(1nM,)*]

-24.7522 lnM,

+ 35.3155(1nMp)*

which can be solved iteratively using the following initial guess,

M , = T , / ( 1 0 . 4 4 -0.0052 T b )
Petroleum Fractions:

The properties of any petroleum fraction are estimated by adjusting the calculated properties of
the normal paraffin with the same boiling point as,
Critical Temperature:
T, = Tc,[(l + 2fT)/(l- 2fT)]

0.0398285-0.9481251

AS,=exp[5(SP-S)] - 1
Critical Volume:
v, =v,,[(1+2f,)/(l-2f,)]

f , = AS10.466590 / T i + ( - 0 . 1 8 2 4 2 1

AS^ = exp[4(~;- sz)]- 1

Critical Pressure:
2

pc = Pcp(Tc /Tcp)(Vcp Ivcj[(l+2fp)1(l-2fp)]

+ 3.01721/T!)ASv]

367

Critical Properties Correlations

1

2.53262-46.1955/T2-0.00127885Tb
1

-1 1.4277+252.140/T~+O.O0230535T~

AS = exp [O. 5 ( S - S)] - 1

Molecular Weight:
1nM = (lnMp)[(l+ 2fM)/(l- 2 f ~ ) ] 2

f,,, = AS,[IY

+ (-0.0175691 + 0.193168/Ti)AS,]

Y = 0.0123420- 0.328086/T,f

AS,= exp[5(Sp - S)]

-1

368

EQUATION OF STATE EXPRESSIONS

The general cubic equation of state, Eq.(4.12),

p=-- RT
v-b

a
V ~ + U V - W ~

takes the following dimensionless form:

Z3- ( l + B - U)Z2 + ( A - BU - U - W2)Z- (AB-BW2

- W 2 )= 0

where
A=-

aP
(RT)*

bP
BE--

RT

UP
RT

WP
WE-,
RT

Ue-

and

ZI-

VP
RT

The above equation results in the following expression for the fugacity coefficient of a pure
compound:

In $ = (Z - 1) - ln(Z - B) -

Jm

22+u +
In 2 2 + u - JFZ?

Jm

The expression for fugacity of a component in a mixture is:

ln$l

2 ( 2 z + u ) w ; w 2+(UZ-2W2)U,U
A[
( 2 2 + uz - W2)(U2 + 4W2)

where, the dimensionless derivatives of EOS parameters are defined as,

with the total number of moles, n, defined as,

369

Equation of State Expressions

Implementing the random mixing rules for the mixture EOS parameters (Section 4.3. l),
a = x x x i x j a i j , b = c x i b , , u = c x i u i , and w = c x i w i
i

we obtain.
B(bi /b)
In(+ = -ln(Z - B) + Z-B

[ 2 z x j a i j / a - (Ui/U)U2+4(Wi/W)W2
j
u2+ 4 w 2

Jm

2 z + u - m X ] - A [2(2Z+U)(w,/w)W2+(UZ-2W2)(Ui/u)U
(Z2 + uz - W2)(U2 + 4W2)
2z+u+JoZiF

Solution of Cubic Equation

z~+~,z*+~,z+~,=o
Let,
J = (gala, - 27a3 - 2a:)/54

Q = (3a, - a:)/9

D = Q 3 + J2

If D>O, the equation has only one real root:

Z, = (J + & ) I 3

+ (J - - , 6 ) 1 1 3

-a, / 3

If D<O, the equation has three real roots:

Z, = 2 J ? j c o s ( e / 3 ) - a , / 3
Z, = 2 m c o S ( e / 3+ 120) - al / 3

Z, = 2J?jcos(8/3+24O0)-a,/3
where,

If D=O, the equation has three real roots, at least two of them are equal:
Z I -- 2 J 3 - a , / 3

Z, =Z, =-J13-a,/3

Appendix C

370
THERMODYNAMIC PROPERTIES USING PENG-ROBINSON EOS (PR)
P = RT/(v - b) - aca/[v(v + b) + b(v - b)]

(4.27)

a = [ 1 + m (1 - TF.5)]2

(4.23)
(4.31)

Molar Enthalpy
The total enthalpy is calculated from the following thermodynamic relation,

where the last term is the total internal energy at low pressure and prevailing temperature, and it
is determined by summing the internal energy of individual pure components.
Applying the Peng-Robinson equation of state to calculate

, using the random mixing

rules, Eqs(4.74) and (4.78), and dividing the obtained expres'sion by the total number of
moles, n, result in,
- 'Ib

h = --In(a'

2&b

v+(a+l)b

+ Pv +

c
N

xiiii,o

where,
N

a'= c c x i x j ( l- kij)ai'*a~~*[m,T~'*
+CX~'']
When using the volume shift concept to correct the predicted molar volume by PR, Eq.(4.3 l),
the corrected molar enthalpy is given by,
-

h""' = 6 - c p

Partial Molar Enthalpy

Multiplying the molar enthalpy, E, derived above, by n and differentiating the obtained
expression of the total enthalpy, we obtain,

Equation of Stare Expressions

37 1

where vi is the partial molar volume.

When using the volume shift, the corrected partial molar enthalpy is given by,
hP, = h, - c,P

Partial Molar Volume

VI=[%)

T,P.n,,,

Converting the molar volume in PR to total volume, by multiplying it with n, and

differentiating it, we obtain,

(RT + b,P)(v'

+ 2bv - b2)+

v. =

P(v'

2biRT - 2 x x j a i j- 2biP(v - b) (v - b) + bia

J

+ 2bv - b') + 2P(v - b)(v + b) - 2RT(v + b) + a

372
Equilibrium Ratio

?
c
0

e
e
0

*0

x
s

-3

2
LL

M
.-

x
w

373

Pressure, kPa
Figure D.2. Equilibrium ratio at 34.47 MPa (5000 psia) convergence pressure

Next Page
374

PRESSURE, PSlA

Equilibrium Ratio

K I

...

Pressure, kPa
Figure D.3. Equilibrium ratio at 34.47 MPa (5000 psia) convergence pressure.

ETHANE