#!/usr/bin/python3
# -*- coding: utf-8 -*-
r"""Pychemqt, Chemical Engineering Process simulator
Copyright (C) 2009-2025, Juan José Gómez Romera <jjgomera@gmail.com>
This program is free software: you can redistribute it and/or modify
it under the terms of the GNU General Public License as published by
the Free Software Foundation, either version 3 of the License, or
(at your option) any later version.
This program is distributed in the hope that it will be useful,
but WITHOUT ANY WARRANTY; without even the implied warranty of
MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE. See the
GNU General Public License for more details.
You should have received a copy of the GNU General Public License
along with this program. If not, see <http://www.gnu.org/licenses/>."""
from scipy.constants import R
from lib.EoS.Cubic.SRK import SRK
# Paramters from [4]_, Table 1
dat = {
2: (0.463100, 0.069800),
3: (0.555800, 0.120800),
4: (0.603800, 0.156300),
6: (0.660100, 0.178900),
5: (0.625100, 0.181800),
8: (0.709400, 0.210300),
7: (0.686000, 0.196000),
9: (0.588700, 0.221700),
10: (0.744600, 0.247600),
52: (0.721200, 0.236300),
53: (0.724500, 0.226900),
54: (0.664500, 0.215800),
55: (0.692300, 0.216200),
11: (0.784100, 0.282800),
79: (0.771000, 0.267500),
80: (0.766700, 0.261900),
436: (0.740500, 0.263500),
432: (0.722300, 0.246500),
433: (0.742100, 0.244700),
434: (0.733700, 0.258500),
435: (0.722800, 0.221400),
437: (0.695400, 0.218200),
12: (0.825300, 0.316400),
81: (0.814900, 0.298700),
590: (0.799200, 0.299500),
591: (0.799900, 0.300200),
598: (0.790900, 0.293400),
592: (0.759400, 0.285600),
593: (0.783500, 0.279800),
594: (0.768800, 0.285800),
595: (0.784700, 0.291100),
596: (0.763200, 0.261100),
597: (0.776100, 0.274800),
601: (0.765400, 0.271300),
602: (0.766500, 0.237300),
541: (0.731300, 0.253500),
82: (0.747700, 0.249800),
599: (0.747700, 0.233000),
600: (0.761000, 0.255800),
603: (0.551500, 0.313900),
13: (0.867500, 0.347200),
370: (0.758200, 0.311800),
369: (0.748600, 0.309100),
# 1720: (0.784300, 0.274400), # 2,4,4-trimethylhexane
371: (0.834300, 0.233400),
372: (0.671500, 0.274400),
373: (0.738100, 0.266600),
374: (0.740800, 0.270100),
375: (0.719300, 0.266000),
14: (0.890500, 0.386300),
15: (0.946700, 0.409100),
16: (0.960400, 0.447900),
17: (1.021200, 0.468600),
18: (1.080400, 0.483000),
19: (1.110400, 0.513200),
20: (1.127400, 0.550600),
21: (1.141400, 0.572800),
90: (1.099200, 0.629000),
91: (1.014100, 0.721300),
92: (1.068200, 0.793100),
611: (0.829000, 0.344600),
850: (0.825100, 0.335300), # 3-methyloctane
851: (0.836400, 0.327400), # 4-methyloctane
# 1451: (0.852000, 0.308800), # 3-ethylheptane
# : (0.870200, 0.295500), # 4-ethylheptane
612: (0.759600, 0.336800),
# : (0.816700, 0.305600), # 2,3-dimethylheptane
# : (0.775000, 0.342600), # 2,4-dimethylheptane
# : (0.773800, 0.340200), # 2,5-dimethylheptane
36: (0.633300, 0.190600),
37: (0.661100, 0.216800),
59: (0.711600, 0.233100),
93: (0.753100, 0.201200),
94: (0.723700, 0.220800),
95: (0.734000, 0.214100),
96: (0.800400, 0.186300),
97: (0.717100, 0.221100),
179: (0.650500, 0.300200),
583: (0.628500, 0.277500),
# 1716: (0.653000, 0.337600), # n-butylcyclopentane
398: (0.889000, 0.371400),
401: (0.905100, 0.414400),
407: (0.963400, 0.442800),
410: (0.949500, 0.498000),
38: (0.605600, 0.228200),
39: (0.662000, 0.222400),
60: (0.579100, 0.296000),
87: (0.616300, 0.259500),
88: (0.583000, 0.285200),
577: (0.631700, 0.256300),
89: (0.604100, 0.274800),
84: (0.563000, 0.297300),
85: (0.571300, 0.290200),
86: (0.627100, 0.259000),
184: (0.518900, 0.354800),
190: (0.837400, 0.260300),
22: (0.520200, 0.130000),
23: (0.588300, 0.156700),
24: (0.634100, 0.184900),
25: (0.638300, 0.196600),
26: (0.714100, 0.161400),
27: (0.643500, 0.183300),
29: (0.693000, 0.201100),
30: (0.667900, 0.225400),
31: (0.673800, 0.218600),
32: (0.647800, 0.230800),
33: (0.709900, 0.178200),
34: (0.650100, 0.236800),
35: (0.731800, 0.235900),
552: (0.797500, 0.209600),
553: (0.743500, 0.239200),
554: (0.770400, 0.224300),
65: (0.655300, 0.167200),
66: (0.624500, 0.219200),
67: (0.187700, 0.346800),
151: (0.389800, 0.292800),
299: (0.404800, 0.331300),
# : (0.3909, 0.3174), # 2-pentyne
# 1349: (0.9930, 0.0104), # 3-hexyne
40: (0.604300, 0.228500),
41: (0.711700, 0.224200),
45: (0.745800, 0.251200),
42: (0.773700, 0.241500),
43: (0.801100, 0.242100),
44: (0.794100, 0.240000),
70: (0.792100, 0.271200),
71: (0.740200, 0.284000),
72: (0.744200, 0.308700),
73: (0.669600, 0.349100),
74: (0.764200, 0.300400),
75: (0.856900, 0.254200),
76: (0.868200, 0.260200),
77: (0.898700, 0.266300),
78: (0.846000, 0.295200),
377: (0.886600, 0.246900),
378: (0.835400, 0.270900),
379: (0.746500, 0.301200),
380: (0.881700, 0.261600),
381: (0.872500, 0.261300),
382: (0.835300, 0.277700),
194: (0.827400, 0.276200),
406: (0.981500, 0.302100),
185: (0.756600, 0.242700),
191: (1.016300, 0.220000),
200: (0.968500, 0.228400),
117: (1.301300, 0.200500),
134: (1.154500, 0.404700),
146: (0.691700, 0.695800),
145: (0.643400, 0.785400),
159: (0.345300, 0.898900),
161: (0.237400, 1.003500),
160: (0.415100, 0.850600),
450: (0.433700, 0.848300),
174: (0.837200, 0.356600),
177: (0.827600, 0.357000),
346: (0.726000, 0.454000),
347: (0.939100, 0.371700),
140: (0.795100, 0.220500),
153: (0.779300, 0.250700),
304: (0.784500, 0.279600),
165: (0.756400, 0.295000),
329: (0.829900, 0.288900),
133: (0.672000, 0.172700),
486: (0.955000, 0.033900),
162: (0.747300, 0.227900),
318: (0.830900, 0.230700),
337: (0.726600, 0.297300),
129: (0.673900, 0.171600),
131: (0.728000, 0.211900),
141: (0.617200, 0.308300),
157: (0.627800, 0.338000),
142: (0.741700, 0.277700),
155: (0.762300, 0.314200),
166: (0.767200, 0.345700),
156: (0.728300, 0.317400),
309: (0.772400, 0.343900),
118: (0.713100, 0.260200),
249: (0.582700, 0.350900),
147: (0.643700, 0.190900),
138: (0.702200, 0.269300),
294: (0.542500, 0.387700),
270: (0.534200, 0.369800),
# Used values in ref [5]_, see below
# 225: (0.644100, 0.172300),
# 643: (0.769900, 0.185300),
# 218: (0.671500, 0.149600),
# 247: (0.784700, 0.197400),
# 245: (0.590600, 0.276400),
# 243: (0.724900, 0.204100),
# 693: (0.662300, 0.391800),
# 321: (1.182200, 0.249900),
# 322: (0.751300, 0.188300),
# 642: (0.656000, 0.202100),
# 220: (0.665000, 0.201300),
# 216: (0.560500, 0.215600),
# 217: (0.630200, 0.183800),
# 234: (0.705800, 0.253700),
# 232: (0.638000, 0.261000),
# 231: (0.611400, 0.277200),
# 229: (0.742700, 0.199500),
# 215: (0.701200, 0.205600),
115: (0.620500, 0.150300),
222: (0.718300, 0.150100),
112: (0.681600, 0.188300),
100: (0.609200, 0.202600),
132: (0.651800, 0.174300),
126: (0.740400, 0.177900),
127: (0.876700, 0.144400),
479: (0.609400, 0.219600),
122: (0.485900, 0.201200),
658: (0.604900, 0.197300),
659: (0.715600, 0.157400),
119: (0.625200, 0.249800),
172: (0.671700, 0.231800),
224: (0.310400, 0.250100),
171: (0.690600, 0.219600),
116: (0.372900, 0.235700),
136: (0.618000, 0.194700),
269: (0.563800, 0.259900),
290: (0.760300, 0.227200),
# : (0.5777, 0.2713), # methyl propyl sulfide
# : (0.6667, 0.2416), # methyl isopropyl sulfide
227: (0.591200, 0.164300),
137: (0.608600, 0.198400),
# 1296: (0.6738, 0.2497), # 2-methyl-2-propylthiol
743: (0.745100, 0.264900),
113: (1.349800, -0.040600),
226: (0.993800, 0.129600),
46: (0.446800, 0.109300),
47: (0.487100, 0.071700),
105: (0.459700, 0.154300),
994: (0.4304, 0.0834), # xenon
1: (0.256300, -0.074200),
62: (0.949900, 0.163300),
49: (0.580900, 0.272700),
110: (0.058700, 0.497100),
51: (0.635800, 0.261400),
50: (0.459400, 0.179000),
102: (0.621100, 0.091000),
104: (0.628800, 0.112400),
63: (0.783800, 0.160400),
630: (0.707600, 0.429200),
951: (0.6878, 0.0952), # nitrogen trifluoride
# : (0.7958, 0.1473), # boron tribromide
219: (0.536800, 0.138700),
# Aditional parameters for CFCs from [5]_, Table 2
239: (0.7381, 0.0553),
242: (0.5176, 0.2169),
215: (0.6176, 0.1737),
218: (0.6635, 0.1515),
216: (0.6129, 0.1848),
217: (0.6336, 0.1819),
225: (0.7056, 0.1372),
642: (0.6310, 0.2083),
247: (0.7054, 0.1775),
654: (0.6449, 0.2152),
220: (0.666, 0.2001),
# r113a: (0.674, 0.2018),
# r151: (0.6628, 0.2163),
235: (0.6867, 0.207),
652: (0.6747, 0.2165),
241: (0.71165, 0.1866),
322: (0.7393, 0.1941),
# r1112: (0.6902, 0.2164),
243: (0.6964, 0.2136),
230: (0.7008, 0.2167),
229: (0.7076, 0.2137),
232: (0.7076, 0.2167),
231: (0.7074, 0.2168),
245: (0.7484, 0.1952),
236: (0.7372, 0.1977),
643: (0.7962, 0.1723),
# r132b: (0.7868, 0.1869),
# 1242: (0.7584, 0.2043),
645: (0.8503, 0.1498),
# 1870: (0.7692, 0.2072),
# r124a: (0.7998, 0.1938),
234: (0.859, 0.2122),
# chloropentafluoroacetone: (0.7018, 0.3309),
692: (0.7198, 0.3375),
693: (0.8271, 0.2845),
319: (0.8516, 0.3009),
# perfluropentane: (0.6569, 0.4611),
320: (1.1143, 0.1635),
340: (1.2063, 0.1657),
321: (0.8998, 0.3877),
326: (0.9354, 0.4432)}
# Procedure to calculate parameters from vapor pressure experimental data
# Soave, G.
# Rigorous and Simplified Procedures for Determining the Pure-Component
# Parameters in the Redlich-Kwong-Soave Equation of State.
# Chem. Eng. Sci. 35(8) (1980) 1725-1729
# 10.1016/0009-2509(80)85007-x
[docs]
class MSRK(SRK):
r"""Modified SRK two parameters cubic equation of state as explain in [1]_
.. math::
\begin{array}[t]{l}
P = \frac{RT}{V-b}-\frac{a}{V\left(V+b\right)}\\
a = 0.42747\frac{R^2T_c^2}{P_c}\alpha\\
b = 0.08664\frac{RT_c}{P_c}\\
\alpha = 1 + m\left(1-Tr\right) + n\left(\frac{1}{T_R}-1\right)\\
\end{array}
m and n are compound specific parameters, compiled from [4]_ and [5]_, in
case compound with no available parameters use the generalized correlation
give in [6]_.
.. math::
\begin{array}[t]{l}
m = 0.4745 + 2.7349\omega Z_c + 6.0984\left(\omega Z_c\right)^2\\
m = 0.0674 + 2.1031\omega Z_c + 3.9512\left(\omega Z_c\right)^2\\
\end{array}
Examples
--------
Example 4.3 from [2]_, Propane saturated at 300K
>>> from lib.mezcla import Mezcla
>>> mix = Mezcla(5, ids=[4], caudalMolar=1, fraccionMolar=[1])
>>> eq = MSRK(300, 9.9742e5, mix)
>>> '%0.1f' % ( eq.Vl.ccmol)
'98.2'
>>> eq = MSRK(300, 42.477e5, mix)
>>> '%0.1f' % (eq.Vg.ccmol)
'94.9'
"""
__title__ = "M-SRK (1979)"
__status__ = "MSRK"
__doi__ = (
{"autor": "Soave, G.",
"title": "Application of a Cubic Equation of State to Vapor-Liquid "
"Equilibria of Systems Containing Polar Compounds",
"ref": "Inst. Chem. Eng. Symp. Ser. 56 (1979) 1.2/1-1.2/16",
"doi": ""},
{"autor": "Soave, G.",
"title": "Improvement of the van der Waals Equation of State",
"ref": "Chem. Eng. Sci. 39(2) (1984) 357-369",
"doi": "10.1016/0009-2509(84)80034-2"},
{"autor": "Poling, B.E, Prausnitz, J.M, O'Connell, J.P",
"title": "The Properties of Gases and Liquids 5th Edition",
"ref": "McGraw-Hill, New York, 2001",
"doi": ""},
{"autor": "Sandarusi, J.A., Kidnay, A.J., Yesavage, V.F.",
"title": "Compilation of Parameters for a Polar Fluid Soave-Redlich-"
"Kwong Equation of State",
"ref": "Ind. Eng. Chem. Process Des. Dev. 25(4) (1986) 957-963",
"doi": "10.1021/i200035a020"},
{"autor": "Kadhem, Q.M.A, Al-Sahhaf, T.A., Hamam, S.E.M.",
"title": "Parameters of the Modified Soave-Redlich-Kwong Equation of "
"State for Some Chlorofluorocarbons, Hydrofluorocarbons and"
"Fluorocarbons",
"ref": "J. Fluorine Chem. 43(1) (1989) 87-104",
"doi": "10.1016/s0022-1139(00)81638-3"},
{"autor": "Valderrama, J.O., De la Puente, H., Ibrahim, A.A.",
"title": "Generalization of a Polar-Fluid Soave-Redlich-Kwong "
"Equation of State",
"ref": "Fluid Phase Equilibria 93 (1994) 377-383",
"doi": "10.1016/0378-3812(94)87021-7"})
[docs]
def _alfa(self, cmp, T):
"""Special alpha function for this modified version, if the compound
specified parameters are not available in database use the standard
SRK alpha expresion"""
if cmp.id in dat:
m, n = dat[cmp.id]
else:
# Generalized correlation from Valderrama et al., [6]_
Zc = cmp.Pc.kPa*cmp.Vc*cmp.M/R/cmp.Tc
x = cmp.f_acent*Zc
m = 0.4745 + 2.7349*x + 6.0984*x**2 # Eq 4
n = 0.0674 + 2.1031*x + 3.9512*x**2 # Eq 5
alfa = 1 + m*(1-T/cmp.Tc) + n*(cmp.Tc/T-1) # Eq 7
return alfa
if __name__ == "__main__":
from lib.mezcla import Mezcla
mix = Mezcla(5, ids=[4], caudalMolar=1, fraccionMolar=[1])
eq = MSRK(300, 9.9742e5, mix)
print('%0.0f %0.1f' % (eq.Vg.ccmol, eq.Vl.ccmol))
eq = MSRK(300, 42.477e5, mix)
print('%0.1f' % (eq.Vl.ccmol))
