Professional Documents
Culture Documents
11
JSCS – 3412 Note
NOTE
Acentric factor estimation from the corresponding states
principle
DU[AN K. GROZDANI]
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade,
Serbia and Montenegro (e-mail: dule@tmf.bg.ac.yu)
(Received 12 April, revised 3 June 2005)
Abstract: Acentric factor estimation from the corresponding states principle was
conducted. The reported values, or analytical expressions, of the functions f(0), f(1)
and f(2) are presented. The tabulated values of f(0), f(1) and f(2) by the Brandani rela-
tion of the Wagner type of vapor pressure equation are correlated. The estimation
procedures are tested on 44 nonpolar substances. The Ambrose and Walton expres-
sions have the best predictive characteristics.
Keywords: acentric factor, corresponding states principle, vapor pressure.
INTRODUCTION
Using the three-parameter corresponding states principle, the vapor pressure
of a pure nonpolar substance is given by the following relation:1
ln(prs) = f(0) (Tr) + wf(1) (Tr) (1)
or including a quadratic term w2 : 2
ln(prs) = f(0) (Tr) + wf(1) (Tr) + w2f(2) (Tr) (2)
where Tr = T/Tc is the reduced temperature and prs = ps/pc is the reduced vapor pressure.
Pitzer et al.1 (PLCHP), Chao et al.3 (CGOH), Carruth and Kobayashi4 (CK),
and His and Lu5 (HL) have reported their values of f(0) and f(1) (Table I). Lee and
Kesler6 (LK) have reported their analytical expressions of f(0) and f(1) in the form
of a Riedel type of vapor pressure equation
f(0) (Tr) = 5.92714 – 6.09648 / Tr – 1.28862ln(Tr) + 0.169347Tr6 (3)
doi: 10.2298/JSC0603213G
213
214 GROZDANI]
TABLE I. Continued
Tr f(0) f(1)
PLCHP CGOH CK HL PLCHP CGOH CK HL
0.540 – 4.525 – 4.564 – 5.457 – 5.234
0.550 – 4.398 – 4.352 – 5.158 – 5.162
0.560 – 4.223 – 4.186 – 4.198 – 4.789 – 4.881 – 4.746
0.570 – 4.023 – 4.651
0.580 – 3.887 – 3.868 – 3.866 – 4.329 – 4.393 – 4.299
0.590 – 3.707 – 4.168
0.600 – 3.574 – 3.555 – 3.553 – 3.914 – 3.937 – 3.887
0.610 – 3.419 – 3.749
0.620 – 3.283 – 3.279 – 3.270 – 3.546 – 3.557 – 3.495
0.630 – 3.150 – 3.369
0.640 – 3.012 – 3.012 – 3.009 – 3.201 – 3.201 – 3.092
0.650 – 2.878 – 3.039
0.660 – 2.758 – 2.758 – 2.761 – 2.878 – 2.878 – 2.777
0.670 – 2.636 – 2.729
0.680 – 2.524 – 2.524 – 2.531 – 2.579 – 2.579 – 2.482
0.690 – 2.411 – 2.441
0.700 – 2.303 – 2.303 – 2.303 – 2.303 – 2.303 – 2.303
0.720 – 2.093 – 2.091 – 2.061 – 2.026
0.740 – 1.895 – 1.895 – 1.842 – 1.817
0.760 – 1.709 – 1.704 – 1.623 – 1.633
0.780 – 1.531 – 1.529 – 1.428 – 1.428
0.800 – 1.363 – 1.361 – 1.255 – 1.248
0.820 – 1.202 – 1.094
0.840 – 1.048 – 0.933
0.860 – 0.900 – 0.794
0.880 – 0.760 – 0.656
0.900 – 0.622 – 0.530
0.920 – 0.488 – 0.414
0.940 – 0.359 – 0.306
0.950 – 0.297 – 0.251
0.960 – 0.235 – 0.198
0.970 – 0.175 – 0.147
0.980 – 0.115 – 0.097
0.990 – 0.058 – 0.048
1.000 0.000 0.000
TABLE II. Correlation results
Model
PLCHP CGOH CK HL
f(0) f(1) f(0) f(1) f(0) f(1) f(0) f(1)
A – 5.7664 ´ 100 – 4.9727 ´ 100 – 2.1117 ´ 100 5.7745´ 101 – 5.5080 ´ 100 – 1.2577 ´ 101 – 4.9078 ´ 100 – 9.7824 ´ 100
B 4.4335 ´ 10-1 1.2509 ´ 100 – 1.0260 ´ 101 – 1.6518 ´ 102 – 6.3391 ´ 10-1 2.5055 ´ 101 – 1.9991 ´ 100 1.5711 ´ 101
C 1.4580 ´ 100 – 6.7016 ´ 100 1.4536 ´ 101 1.8019 ´ 102 3.1917 ´ 100 – 4.1098 ´ 101 4.3672 ´ 100 – 2.6509 ´ 101
D –1.0839´ 101 –7.6151´ 10-1 –1.9255´ 101 – 1.9331´ 102 – 8.7988´ 100 4.4772´ 101 –1.1093´ 101 3.2449´ 101
E 1.2703´ 102 5.9709´ 101 2.8799´ 101 3.9425´ 102 2.2373´ 101 –1.1824´ 102 5.0205´ 101 –2.4422´ 102
s[1] 0.00113 0.00455 0.0135 0.0654 0.0164 0.177 0.00422 0.0301
pav[%] 0.16 0.39 0.09 0.41 0.22 1.26 0.11 0.81
pmax[%] 1.15 2.15 0.23 1.00 0.52 2.72 0.29 1.84
218 GROZDANI]
From the values for Tbr from Table III it follows that the Chao et al.3 expressions
(Table II) are not applicable to any of the substances from this Table, while the Carruth
220 GROZDANI]
and Kobayashi4 expressions (Table II) are not applicable to some of the substances.
From the results presented in Table IV, it can be concluded that the Ambrose and
Walton7 expressions (Eqs. 5–7) have the best predictive characteristics.
TABLE IV. Comparison of the predicted and literature values of w
Expressions pav/% Expressions pav/% Expressions pav/%
PLCHP 1.96 LK 1.59 BI 1.14
CGOH – AW 0.42 BII 0.80
CK 1.41 SP 1.39 TCC 0.88
HL 2.02
NOTATION
n Number of data points
m Number of parameters
T Temperature, K
p Pressure, bar
ps Vapor pressure, bar
pav Percentage average error, %
pmax Maximum percent error, %
Greek letters
w Acentric factor
s Standard deviation
Subscripts
b Boiling property
c Critical property
r Reduced property
exp Experimental value
cal Calculated value
IZVOD
REFERENCES
1. K. S. Pitzer, D. Z. Lippmann, R. F. Curl, C. M. Huggins, D. E. Petersen, J. Am. Chem. Soc. 77
(1955) 3433
2. G. Z. A. Wu, L. I. Stiel, AIChE J. 31 (1985) 1632
3. K. C. Chao, R. A. Greenkorn, O. Olabisi, B. H. Hensel, AIChE J. 17 (1971) 353
4. G. F. Carruth, R. Kobayashi, Ind. Eng. Chem. Fundam. 11 (1972) 509
5. C. Hsi, B. C.-Y. Lu, AIChE J. 20 (1974) 109
6. B. I. Lee, M. G. Kesler, AIChE J. 21 (1975) 510
7. D. Ambrose, J. Walton, Pure & Appl. Chem. 61 (1989) 1395
8. D. R. Schreiber, K. S. Pitzer, Fluid Phase Equilib. 46 (1989) 113
9. S. Brandani, Ind. Eng. Chem. Res. 32 (1993) 756
10. C. H. Twu, J. E. Coon, J. R. Cunningham, Fluid Phase Equilib. 96 (1994) 19
11. B. E. Poling, J. M. Prausnitz, J. P. O’Connell, The Properties of Gases and Liquids, McGraw-Hill,
New York, 2001.