Fluid Phase Equilibria 168 2000. 149163 www.elsevier.

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A compressed liquid density correlation

Kh. Nasrifar, Sh. Ayatollahi, M. Moshfeghian )
Department of Chemical Engineering, Shiraz Uniersity, Shiraz, Iran Received 26 August 1999; accepted 30 November 1999

Abstract A new correlation is developed for calculation of the compressed liquid density of pure compounds and mixtures. This correlation is used together with the HankinsonThomson COSTALD. correlation of saturated liquid density and the Riedel equation for the calculation of vapor pressures. The range of application of this correlation is quite wide; from freezing point temperature to critical point temperature and from saturation pressure to 500 MPa. The average of error for the prediction of the compressed liquid volume of 31 compounds consisting of 3324 experimental data points is 0.77% with y0.24% bias from the experimental data. For mixtures, the average of error for the prediction of the compressed liquid volume of 13 mixtures consisting of 2101 experimental data points is 1% with y0.22% bias from the experimental data. The comparison with other correlations shows that the new correlation is somewhat better and quite reliable to very high pressures. q 2000 Elsevier Science B.V. All rights reserved.
Keywords: Correlation; Liquid density; Compressed; Pure; Mixtures

1. Introduction The compressed liquid density of compounds is an important property for process simulation, pipeline design and liquid metering. Compressed liquid densities are usually calculated using correlations. A good compressed liquid density correlation must be simple and accurate, applicable to wide ranges of temperature and pressure for pure compounds and their liquid mixtures. It must also be predictive so that it can be used when experimental data are not available. Yen and Woods w1x developed a generalized compressed liquid density correlation, applicable to the whole liquid region. This correlation is also applicable to mixtures in addition to the pure compounds and is fairly accurate. Chueh and Prausnitz w2x introduced a generalized correlation for
)

Corresponding author. Tel.: q 98-71-30-3071; fax: q 98-71-67-2060. E-mail address: moshfeg@succ.shirazu.ac.ir M. Moshfeghian..

0378-3812r00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 9 9 . 0 0 3 3 6 - 2

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normal compressed liquids. This correlation is simple and applicable to nearly the whole liquid region and fairly accurate but it has not been extended to mixtures. The compressed liquid density correlation of Brelvi and OConnell w3,4x is quite accurate. This correlation needs a characteristic volume for each compound. In addition, an iterative and integration procedure is required to calculate the compressed liquid density. Thomson et al. w5x developed an excellent compressed liquid density correlation. This correlation was based on the Tait w6x equation. It is applicable to both pure compounds and mixtures. Although this correlation was optimized for pressures smaller than 68 MPa, it is quite predictive at very high pressures. The Thomson et al. w5x correlation is reliable and it is now widely used. However, this correlation has a discontinuity at reduced temperatures larger than 0.95 and after the discontinuity the quality of the correlation is not known. Lee and Liu w7x introduced an equation to calculate the compressed liquid densities of pure compounds. This model is a modification of the saturated liquid density equation of Spencer and Danner w8x. The model is accurate from low pressures to very high pressures; however, it requires an iterative procedure. In other words this model is implicit in volume. In addition, the Lee and Liu w7x model has not been extended to mixtures. Aalto et al. w9,10x modified the compressed liquid density correlation of Chang and Zhao w11x to improve the correlation for a wider range of temperature, from freezing point to critical point temperature. Although this modified correlation is quite accurate for a wide temperature range, the pressure range is small up to 20 MPa.. Also, the authors asserted that the accuracy of their model gets gradually worse as pressure increases. The objective of this work was to develop a new generalized compressed liquid density correlation with the least limitations. The correlation should be applicable to both pure compounds and their mixtures. The range of applications should be quite wide, from freezing point temperature to the critical point temperature and from saturation pressure to 500 MPa. The new correlation should be explicit in volume so it will not need an iterative procedure to obtain the liquid density. The correlation should be predictive. The ability of the correlation for prediction of the compressed liquid density is then compared with the other compressed liquid density correlations.

2. Development of the new correlation 2.1. Saturated liquid density correlation Except for the correlation of Lee and Liu w7x, the calculation of compressed liquid density is a two-step procedure for the other previously cited correlations. Using these methods, in the first step the saturated liquid density is calculated and in the second step the effect of pressure on the saturated liquid density is evaluated. There are many accurate saturated liquid density correlations, e.g., the modified Rackett correlation of Spencer and Danner w8x, and the correlations of Hankinson and Thomson w12x, Iglesias-Silva and Hall w13x and Nasrifar and Moshfeghian w14x. Nasrifar and Moshfeghian w15x compared 18 methods for the calculation of the saturated liquid density of refrigerants and indicated that the Hankinson and Thomson w12x correlation is superior. However, in general, the Iglesias-Silva and Hall w13x correlation is better than the Hankinson and Thomson w12x correlation. The Iglesias-Silva and Hall w13x correlation is superior to the Hankinson and Thomson w12x correlation for polar compounds and non-hydrocarbons, although for hydrocarbons the Hankinson and Thomson w12x correlation is still superior.

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In this work, a two-step procedure is used too. For the calculation of the saturated liquid density, the Hankinson and Thomson w12x correlation is applied. This correlation is quite accurate for reduced temperatures smaller than 0.95, however, it works well up to the critical point w15x. It was selected because most of experimental data available in the literature are for hydrocarbons. In addition, in this correlation an excellent correlating parameter, the SoaveRedlichKwong acentric factor, v SRK , is used. The parameter v SRK will also be used in formulating of the compressed liquid density correlation. 2.2. The correlation of saturation pressure For developing the compressed liquid density correlation, the vapor pressure of compounds is needed. The generalized Riedel vapor pressure correlation w5,16x is used for this purpose. This correlation is expressed by: log Pr s Pr0. q v SRK Pr1. Pr0. s 5.8031817log Tr q 0.07608141 a Pr1. s 4.86601 b

1. 2. 3. 4. 5.

a s 35 y 36rTr y 96.736log Tr q Tr6 b s log Tr q 0.03721754a

where Tr is the reduced temperature and Pr the reduced pressure. 2.3. The new compressed liquid density correlation

For the development of a compressed liquid density correlation, the selection of variables plays an important role. Fig. 1 illustrates the variation of liquid specific volume of n-heptane as a function of PrX with temperature as a parameter. The variable PrX is defined by: PrX s Pr y Pr ,s

6.

where Pr,s is the reduced pressure at saturation PsrPc .. Therefore, the ordinate considers with the saturated specific volume of n-heptane at different temperatures. Fig. 1 also indicates that independent of the temperature and at high pressures the specific volumes approach an asymptote. This conclusion can also be obtained from any equation of state. In fact, equations of state indicate that at infinite pressure, the molar volume of a compound approaches the molar co-volume. Thus:

n` s lim n s b
P

7.

where b is molar co-volume and n` is molar volume at infinite pressure practically very high pressure.. So we can construct the following variable which is a function of PrX and temperature: n y ns s f PrX ,Tr . 8. n` y ns where ns is saturated molar volume which in this work is calculated using the Hankinson and Thomson w12x correlation. Eq. 8. has a value of 0 at saturation pressure or temperature. and a value

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Fig. 1. Specific volume of n-heptane as a function of excess reduced pressure with temperature as a parameter experimental data from Ref. w20x..

of 1 at very high pressure mathematically infinite pressure.. Therefore, we must look for an increasing function of pressure that behaves in this manner. Searching in mathematical handbooks indicates that a tangent hyperbolic function has the stated behavior. So we could have:

n y ns n` y ns

s C tanh C

9.

where C is a proportionality constant and C an increasing variable which is a function of PrX and Tr . To derive an expression for C , it is supposed that the same expression for C that is valid at low pressures remains valid at high pressures. In other words, having obtained an expression for C at low pressures, it will be used in Eq. 9.. At low pressures when C is small, tanh C can be approximated by C Appendix A. . Then Eq. 9. becomes:

n y ns n` y ns

s CC .

10.

However, we can approximate the molar volume of a liquid at any pressure from the saturated molar volume using Taylors series expansion:

n s ns q

/
E Pr

En

Pr y Pr ,s . q
s

1 2!

/
E Pr2

E 2n

2 Pr y Pr ,s . q . . . s

11.

where subscript s indicates that the value must be evaluated at saturation. Eq. 11. is rearranged and rewritten as:

n y ns n` y ns

s K 1 Pr y Pr ,s . q K 2 Pr y Pr ,s . q . . .

12.

Kh. Nasrifar et al. r Fluid Phase Equilibria 168 (2000) 149163

153

where: 1 Kis i ! E Pri

E in

n` y ns .

i s 1,2,3, . . .

13 .

All the derivatives of volume with respect to Pr are functions of temperature inasmuch as they are at saturation. This is easily understood noting that at saturation the degree of freedom is one. In other words, K i is a function of temperature. Using Pades approximation w17x, the right-hand side of Eq. 12. can be approximated by a polynomial ratio. Consequently, we arrive at:

n y ns n` y ns

A q B Pr y Pr ,s . q D Pr y Pr ,s . q E Pr y Pr ,s . F q G Pr y Pr ,s . q H Pr y Pr ,s . q I Pr y Pr ,s .
2

14.

where A, B, D, E, F , G, H and I are some functions of K 1, K 2 , . . . . However, our evaluation during the optimization of the parameters showed that putting D s H s 0 has no effect on the quality of Eq. 14. and so we will have:

n y ns n` y ns

sC

J q L Pr y Pr ,s . q M Pr y Pr ,s . F q G Pr y Pr ,s . q I Pr y Pr ,s .
3

15.

where J s ArC, L s BrC and M s ErC. Comparing Eq. 15. with Eq. 10. results in:

Cs

J q L Pr y Pr ,s . q M Pr y Pr ,s . F q G Pr y Pr ,s . q I Pr y Pr ,s .
1r 3 2r 3

16 .

Eq. 16. is the final expression for C . We have also determined empirically that: J s j0 q ji 1 y Tr . F s f 0 1 y Tr . C s c 0 q c1 v SRK RTc Pc q j2 1 y Tr .

17. 18. 19. 20. 21.

n` s V

V s V 0 q V 1 v SRK

The parameters j0 , j1, j2 , L, M , f 0 , G, I, c 0 , c1, V 0 and V 1 are taken as global constants. Eq. 9. together with Eqs. 16. 21. are the working equations for calculation of the compressed liquid density of pure compounds. The final values of global constants are given in Table 1.

3. Extension to mixtures To extend the developed correlation to a mixture, some values of Tc , Pc and v SRK for the mixture are required. Because the proposed compressed liquid density correlation is coupled with the saturated liquid density correlation of Hankinson and Thomson w12x, the use of the mixing rules that are used

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Table 1 Global parameters of the new correlation j0 j1 j2 L M f0 G I c0 c1 V0 V1 1.3168=10y3 3.4448=10y 2 5.4131=10y 2 9.6840=10y 2 8.6761=10y6 48.8756 0.7185 3.4031=10y5 5.5526 y2.7659 7.9019=10y 2 y2.8431=10y 2

for the Hankinson and Thomson w12x correlation are plausible for the use with the developed compressed liquid density correlation. Moreover, as will be seen in the Section 4, the predictions of the compressed liquid density using the mixing rules of Hankinson and Thomson w12x are quite good. The mixing rules used are:
nc nc
) x i x j n i) j Tc , i jrnm

Tc ,m s
i

22. 23.
nc

j
1r 2

) ) n i) j Tc , i j s n i Tc , i n j Tc , j .

nc
) nm s 1r4

nc

x i n i) q 3
i nc

x i n i) 2r3
i

/
i

x i n i) 1r3

24. 25.

v SRK , m s x i v SRK , i
i

and:
) Pc ,m s 0.291 y 0.080 v SRK , m . RTc ,m rnm

26.

where n ) is characteristic volume and comes from the Hankinson and Thomson w12x saturated liquid density correlation. The parameters n ) and v SRK for a large number of compounds were given by Hankinson and Thomson w12x.

4. Results To evaluate the developed correlation and the proposed mixing rules, the relevant global parameters of the correlation should be determined. For determining the global parameters of the compressed liquid density correlation, a data bank consisting of 799 experimental data points was built. The data

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bank contains only hydrocarbons with Tr less than 0.95 and pressures less than 500 MPa. Using a nonlinear regression package w18x and an objective function defined by:
nps

Fn s
i

ncal , i y nexp , i nexp, i

27.

the 12 global parameters of the correlation were determined. These parameters are reported in Table 1. The percent of average absolute deviation %AAD. for determining these parameters was 0.62. The distribution of errors around experimental data is shown in Fig. 2. The %Dev on the ordinate of Fig. 2 is defined by: ncal , i y nexp , i %Dev s 100. 28. nexp, i The maximum %Dev for this optimization was 3.2; however, most of the deviations are between y1 and 1. The ability of the proposed correlation to predict compressed liquid density is compared with several correlations. These correlations are Thomson et al. w5x TBH. , Yen and Woods w1x YW. , Chueh and Prausnitz w2x CP., Brelvi and OConnell w3,4x BO. , Chang and Zhao w11x CZ. , Lee and Liu w7x LL. , and the modified Chang and Zhao correlation by Aalto et al. w9,10x CZA. . Tables 2 and 3 illustrate these comparisons for 31 pure compounds composed of paraffins, olefins, halogenated paraffins, carbon dioxide, nitrogen and ammonia. These tables present the %AAD and %Bias of different correlations for the calculation of compressed liquid densities. The %Bias is defined by: 100 nps ncal , i y nexp , i %Bias s s . 29. nps nexp, i i Note that only a portion of hydrocarbon experimental data points cited in Tables 2 and 3 has been used in the optimization of the parameters of the new correlation and not all of them. Table 2

Fig. 2. Deviation plot of hydrocarbons used for optimization of the global parameters. The total number of experimental data points is 799 experimental data from Refs. w19,20,2225x..

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Table 2 Ability of different correlations in terms of %AAD a for prediction of the compressed liquid density of pure compounds Component Pressure range Ref. MPa. w23,30x w23x w20x w20x w20x w20x w20,35x w20x w20x w20x w20x w20,34x w20x w20x w35x w20x w20x w22x w24x w19x w25x w20x w23,33x w4x w20x w21x w26,27x w28x w29x w31x w32x nps 26 20. i 4 4. 150 116. 112 112. 149 132. 160 160. 207 207. 60 50. 152 133. 272 237. 66 56. 207 207. 70 70. 70 70. 27 27. 60 60. 50 50. i 198 170. 70 70. 85 65. 50 50. 306 269. 47 45. 16 16. 110 104. 224 219. 79 79. 6 6. 64 60. 212 196. 15 15. 3324 3075. This work 1.79 0.72. i 0.20 0.20. 1.10 0.84. 0.65 0.65. 0.57 0.38. 0.29 0.29. 0.95 0.95. 1.23 0.67. 0.36 0.25. 1.01 0.73. 1.34 0.79. 0.10 0.10. 0.87 0.87. 0.83 0.83. 0.75 0.75. 1.22 1.22. 1.62 1.62. i 1.28 0.77. 0.40 0.40. 1.66 0.80. 1.44 1.44. 0.61 0.34. 0.90 0.68. 3.07 3.07. 0.61 0.53. 0.32 0.30. 0.43 0.43. 0.34 0.34. 1.14 1.02. 0.58 0.26. 0.60 0.60. 0.77 0.59. YW b TBH c 2.05 0.04 1.12 0.48 0.37 0.96 2.80 4.43 1.94 0.72 4.24 0.36 4.78 4.34 3.66 4.49 4.74 1.27 0.31 1.11 7.19 0.43 1.24 1.85 0.37 0.25 0.74 0.41 0.49 0.49 0.38 1.40 0.67. b 0.04. 0.79. 0.68. 0.33. 0.12. 0.60. 1.05. 1.67. 0.63. 1.25. 0.51. 1.31. 2.10. 0.23. 1.98. 3.27. i 0.45. 0.12. 0.85. 0.73. 0.50. 0.14. 1.96. 0.16. 1.26. 0.45. 1.43. 2.73. 0.25. 2.64. 0.79. CP d 2.90 0.04 1.16 1.20 1.52 0.30 1.08 0.93 0.87 0.86 1.03 0.65 1.00 2.09 0.86 2.03 4.10 1.92 1.66 1.67 0.45 1.03 1.20 2.34 0.37 0.73 0.26 0.59 1.10 1.20 0.91 1.12 CZAe BO f 1.37 0.04 0.88 0.62 0.28 0.42 1.84 7.90 0.45 0.86 7.53 0.59 7.07 7.65 4.60 6.99 8.00 1.12 0.12 1.32 7.30 0.40 1.13 2.34 0.18 0.60 0.74 1.08 1.22 0.32 1.29 1.62 CZ g LLh

CH 4 0.0533.5 C2H6 0.02 C 3H 8 0.0120 n-C 4 H 10 220 i-C 4 H 10 220 n-C 5 H 12 120 n-C 6 H 14 0.1503 n-C 7 H 16 5500 n-C 8 H 18 220 i-C 8 H 18 0.150 n-C 9 H 20 5500 n-C 10 H 22 220 n-C 11 H 24 5500 n-C 13 H 28 5500 n-C 16 H 34 0.1450 n-C 17 H 36 5500 n-C 20 H 42 5500 C2H4 0.836.2 C 3H 6 1.49.7 1-C 4 H 8 1.469 C6H6 64300 CO 2 160 N2 0.431.7 NH 3 0.2141.8 CCl 2 FCClF2 0.53.5 CH 3 CHF2 0.76.5 CCl 2 FCH 3 0.568 CClF2 CH 3 12 CH 2 F2 0.320 CHClF2 16.22 CHF2 CHF2 0.59.3 Overall
a b

0.87 1.35 1.16 0.04 0.04 0.55 0.69 1.26 1.53 0.77 0.75 1.04 0.61 0.61 0.98 0.33 0.31 0.19 0.76 1.32 1.69 1.03 4.42 10.59 0.75 0.53 0.42 0.65 0.96 0.83 0.79 5.06 11.22 0.57 0.15 0.39 1.01 5.37 8.93 1.21 6.84 8.61 1.38 4.65 1.78 2.00 7.98 8.66 2.32 11.55 8.69 1.50 1.06 1.74 0.33 0.42 0.77 1.51 1.40 1.16 0.68 1.68 3.67 2.65 0.42 0.95 1.52 0.57 1.65 0.66 1.67 2.35 0.21 0.24 0.97 0.74 0.57 4.60 0.36 0.40 0.43 0.96 1.07 1.43 1.06 0.56 1.21 0.36 0.62 0.97 0.55 2.39 1.21 0.97 1.43 2.24

%AAD s 100rnps. S inps < ncal, i y nexp, i <rnexp, i . Yen and Woods w1x. c Thomson et al. w5x. d Chueh and Prausnitz w2x. e Modified ChangZhao by Aalto et al. w9x. f Brelvi and OConnell w3,4x. g Chang and Zhao w11x. h Lee and Liu w7x. i The numbers in the parentheses indicate the case in which Tr - 0.95.

indicates that the new correlation and the correlations of TBH and BO are better than the other correlations with overall %AAD equal to 0.77, 0.79 and 0.97, respectively. The respected overall %Bias presented in Table 3 are y0.24, 0.41 and 0.04, respectively. Note that except for the TBH

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157

Table 3 Ability of different correlations in terms of %Biasa for prediction of the compressed liquid density of pure compounds Component Pressure range Ref. MPa. CH 4 C2H6 C 3H 8 n-C 4 H 10 i-C 4 H 10 n-C 5 H 12 n-C 6 H 14 n-C 7 H 16 n-C 8 H 18 i-C 8 H 18 n-C 9 H 20 n-C 10 H 22 n-C 11 H 24 n-C 13 H 28 n-C 16 H 34 n-C 17 H 36 n-C 20 H 42 C2H4 C 3H 6 1yC 4 H 8 C6H6 CO 2 N2 NH 3 CCl 2 FCClF2 CH 3 CHF2 CCl 2 FCH 3 CClF2 CH 3 CH 2 F2 CHClF2 CHF2 CHF2 Overall
a b

nps 26 20. i 4 4. 150 116. 112 112. 149 132. 160 160. 207 207. 60 50. 152 133. 272 237. 66 56. 207 207. 70 70. 70 70. 27 27. 60 60. 50 50. i 198 170. 70 70. 85 65. 50 50. 306 269. 47 45. 16 16. 110 104. 224 219. 79 79. 6 6. 64 60. 212 196. 15 15. 3324 3075.

This work y0.94 0.12. i y0.20 y0.20. 0.26 0.84. 0.28 0.28. y0.11 0.13. y0.29 y0.29. y0.95 y0.95. 0.51 0.03. 0.08 0.23. y0.84 y0.68. 0.32 y0.22. 0.03 0.03. 0.19 0.19. 0.23 0.23. y0.66 y0.66. 0.07 0.07. 1.01 1.01. i y0.83 y0.25. y0.39 y0.39. y1.66 y0.80. 1.44 1.44. y0.40 y0.10. y0.36 y0.10. 3.07 3.07. y0.61 y0.53. 0.18 0.18. y0.20 y0.20. 0.33 0.33. 0.56 0.66. y0.58 y0.26. 0.17 0.17. y0.24 y0.08.

YW b TBH c 1.98 y0.02 1.12 0.07 0.31 y0.94 y0.68 3.49 y1.87 0.14 2.30 y0.23 3.14 2.79 3.57 2.00 2.43 0.69 0.05 y0.06 7.19 0.02 1.21 1.85 y0.13 0.07 0.06 0.41 y0.44 y0.24 y0.08 0.40 0.58. i y0.01. 0.79. 0.53. 0.30. 0.01. y0.56. y0.45. 1.67. y0.03. y0.49. 0.51. 0.15. 1.71. 0.07. 1.55. 3.26. b y0.27. y0.11. y0.85. y0.73. 0.48. 0.09. 1.96. 0.15. 1.25. y0.39. 1.43. 2.71. 0.24. 1.60. 0.41.

CP d y1.63 y0.01 y0.68 y0.53 y1.32 y0.08 y1.08 0.80 0.46 0.58 0.57 0.65 0.79 2.09 0.81 1.94 4.10 y1.33 y1.66 y1.43 0.45 y0.55 y0.92 2.34 y0.13 y0.12 y0.08 0.56 y0.21 y1.06 0.53 y0.17

CZAe BO f 1.30 y0.01 0.86 0.36 0.23 y0.20 0.62 7.87 0.29 0.71 7.24 0.59 6.77 7.56 4.56 6.72 7.94 0.47 y0.01 y0.08 7.30 0.25 1.10 2.34 0.06 0.59 0.53 1.08 1.10 y0.11 1.29 1.35 y0.66 y0.01 y0.02 0.09 0.39 y0.12 y0.61 0.56 0.04 y0.35 y0.55 0.57 y0.97 y1.00 y1.38 y2.00 y2.32 y1.38 0.30 y1.46 0.67 2.65 y1.51 0.52 y0.02 0.73 y0.23 0.96 0.90 y0.05 0.03 0.04

CZ g 1.23 y0.01 1.15 0.55 0.29 y0.23 y0.32 4.22 0.51 0.59 4.59 0.12 5.08 6.83 4.61 7.88 11.55 0.31 0.41 y1.26 1.68 0.12 0.21 1.67 0.24 0.56 y0.24 1.07 0.39 0.24 2.39 1.03

LLh y0.92 0.55 1.02 0.42 0.40 y0.17 y1.68 y10.57 y0.36 0.18 y11.22 y0.39 y8.36 y8.47 y1.73 y8.66 y8.64 0.14 y0.25 y1.09 y1.77 0.32 1.33 2.35 y0.80 y4.60 0.25 1.43 y0.32 y0.78 y0.97 y1.52

0.0533.5 0.02 0.0120 220 220 120 0.1503 5500 220 0.150 5500 220 5500 5500 0.1450 5500 5500 0.836.2 1.49.7 1.469 64300 160 0.431.7 0.2141.8 0.53.5 0.76.5 0.568 12 0.320 16.22 0.59.3

w23,30x w23x w20x w20x w20x w20x w20,35x w20x w20x w20x w20x w20,34x w20x w20x w35x w20x w20x w22x w24x w19x w25x w20x w23,33x w4x w20x w21x w26,27x w28x w29x w31x w32x

%Bias s 100rnps. S inps ncal, i y nexp, i .rnexp, i . Yen and Woods w1x. c Thomson et al. w5x. d Chueh and Prausnitz w2x. e Modified ChangZhao by Aalto et al. w9x. f Brelvi and OConnell w3,4x. g Chang and Zhao w11x. h Lee and Liu w7x. i The numbers in the parentheses indicate the case in which Tr - 0.95.

correlation, the comparisons are from low temperature to near the critical point and the total number of experimental data points is 3324. However, due to limitation of the TBH correlation the discontinuity at Tr ) 0.95., the total number of experimental data points used for the TBH correlation

158

Table 4 Ability of different correlations for prediction of the compressed liquid density of mixtures System CF3 CHF2 qCH 2 FCF3 CH 2 F2 qCH 2 FCF3 CH 2 F2 qCF3 CHF2 qCH 2 FCF3 CH 4 q n-C 10 H 22 C 2 H 6 qC 3 H 6 n-C 10 H 22 q n-C 14 H 30 n-C 12 H 24 q n-C 16 H 34 n-C 10 H 22 q n-C 14 H 30 q n-C 16 H 34 n-C 16 H 34 q n-C 6 H 14 C 3 H 8 qC 6 H 6 C 3 H 8 q1-C 4 H 8 C 3 H 6 qC 3 H 8 N2 qCH 4 Overall
a b

Pressure range MPa. 0.430 0.53 0.73.2 3.431 1.468.9 0.1430 0.1331.3 0.1359 0.1450 0.668.9 0.768.94 0.668.9 1.335.2

Temperature range K. 280349 250330 280340 294394 261311 298358 298358 298358 298373 311444 278344 261344 92152

nps 144 36 53 174 170 104 84 91 113 394 415 190 133 2101

Ref. w36x w36x w36x w34x w37x w38x w38x w38x w35x w39x w40x w41x w42x

This work %AAD c 0.62 1.67 2.02 1.47 0.39 0.61 0.71 0.51 0.74 0.80 1.73 0.51 1.06 1.00 %Biasd y0.62 y1.67 y2.02 y1.47 y0.30 0.15 0.51 0.27 y0.14 y0.75 1.29 y0.40 y1.04 y0.22

TBH a %AAD 0.48 0.92 1.12 1.17 0.53 1.11 0.57 1.05 1.46 0.79 1.72 0.41 1.32 1.03 %Bias 0.41 y0.92 y1.12 y1.13 y0.51 y0.91 y0.57 y1.04 y1.45 y0.74 1.29 y0.41 y1.32 y0.35

CZAb %AAD 0.18 1.28 1.53 1.01 0.68 2.98 2.68 3.56 4.95 0.79 2.35 0.70 0.91 1.62 %Bias 0.00 y1.28 y1.53 y1.00 0.36 2.90 2.66 3.55 4.93 y0.03 1.92 0.47 y0.33 0.95

Kh. Nasrifar et al. r Fluid Phase Equilibria 168 (2000) 149163

Thomson et al. w5x. Modified ChangZhao by Aalto et al. w10x. c %AAD s 100rnps. S inps < ncal, i y nexp, i <rnexp, i . d %Bias s 100rnps. S inps ncal, i y nexp, i .rnexp, i .

Kh. Nasrifar et al. r Fluid Phase Equilibria 168 (2000) 149163

159

Fig. 3. Deviation plot for n-undecane: Specific volume percent deviation as a function of pressure experimental data from Ref. w20x..

was 3075 and the temperature range was for Tr smaller than 0.95. For the same conditions and the same number of experimental data points as used for the TBH correlation, the new correlation gives a %AAD of 0.59 and a %Bias of y0.08. However, the larger errors for the CZA, CZ and the LL correlations are due to the limitations of the correlations. They should not be used for the whole range, although they are quite accurate for their range of applications. The predictions with our correlation presented in Table 2 show that the maximum error occurs for NH 3 with a %AAD of 3.07. It can be explained noting that NH 3 is a polar liquid and is not suitable

Fig. 4. Deviation plot of N2 qCH 4 binary mixture as a function of temperature experimental data from Ref. w42x..

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to be correlated using the acentric factor. In this case, the correlation of Brelvi and OConnell w3,4x or Huang and OConnell w43x is suitable. Fig. 3 demonstrates a deviation plot for n-undecane. It shows the %Dev of n-undecane as a function of pressure at different temperatures. Except for the temperature 573 K, the deviations from experimental data points are small from saturation pressure to 500 MPa. Even at the temperature 573 K the agreement is quite good for pressures less than 50 MPa. This means that for temperatures near the critical point the error increases at high pressures. The ability of our correlation to predict the compressed liquid density of mixtures is shown in Table 4. The correlation is also compared with the TBH and CZA correlations. The total number of points used for the comparison is 2101 and the maximum pressure is 450 MPa. Table 4 indicates that the overall %AAD and %Bias for our correlation are 1.00 and y0.22, for the TBH correlation 1.03 and y0.35 and for the CZA correlation 1.62 and 0.95, respectively. Fig. 4 shows a deviation plot for the mixture of N2 and CH 4 as a function of temperature. The pressure range of this system is from 1.28 to 35.2 MPa, the temperature range from 92 to 152 K and the composition range from 28.36% to 70.60% N2 . The maximum %Bias is y4.90 and occurs at the temperature 152 K; however, the most of deviations are between y2.8 and 0.20.

5. Conclusion A generalized compressed liquid density correlation Eq. 9. together with Eqs. 16. 21.. for both pure compounds and mixtures have been developed, The temperature and pressure range are quite wide; from freezing point to the critical point and from saturation pressure to 500 MPa. The developed correlation contains 12 global parameters. These parameters have been obtained from a portion of hydrocarbon experimental liquid density data; however, the comparisons show that the correlation is quite predictive for other compounds. Using the new correlation, the average of %AAD for predicting the compressed liquid density 3324 experimental data points of 31 compounds is 0.77. For the mixtures, the average of %AAD is 1.00 for 2101 experimental data points of 13 mixtures. The comparisons with other correlations show that the developed correlation is superior. It should be emphasized that no adjustable or fitting parameters were used to predict the compressed liquid density of mixtures. Only the global parameters determined from a few pure compound density data that are reported in Table 1 were used.

6. Nomenclature

b
A, B c 0 , c1 C D, E f0

molar co-volume m3rkmol. individual constants global constants of Eq. 19. a linear function of v SRK as given by Eq. 19. individual constants global constant of Eq. 18.

Kh. Nasrifar et al. r Fluid Phase Equilibria 168 (2000) 149163

161

F G H I j0 , j1, j2 J Ki L, M nc nps P PrX R T n nU n` x Greek letters a b F v SRK V 0, V1 V Subscript c cal exp i, j m r s

a function given by Eq. 18. global constant of Eq. 16. a constant global constant of Eq. 16. global constants of Eq. 17. a function of temperature as defined by Eq. 17. functions defined by Eq. 13. global constants of Eq. 16. number of compounds number of points pressure MPa. reduced pressure minus reduced pressure at saturation gas constant 8314 m3 Parkmol K. Temperature K. volume m3rkmol. characteristic volume m3rkmol. molar volume at infinite pressure m3rkmol. molar fraction a function given by Eq. 4. a function given by Eq. 5. objective function acentric factor based on SoaveRedlichKwong equation of state global constants of Eq. 21. a function of v SRK as defined by Eq. 21.

critical calculated value experimental value dummy indexes mixture reduced saturated

Appendix A Tangent hyperbolic function is expressed by: tanh C s eC y eyC eC q ey C

A-1.

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Kh. Nasrifar et al. r Fluid Phase Equilibria 168 (2000) 149163

and the exponential functions eC and eyC are expressed by series: eC s 1 q C q 1 2!

C 2q
1

1 3!

C 3q...
1

A-2. A-3.

eyC s 1 y C q

2!

C 2y

3!

C 3qy . . .

For small values of C , the right-hand sides of Eqs. A-2. and A-3. reduce to the two first terms. So: eC f 1 q C eyC f 1 y C . Substituting Eqs. A-4. and A-5. into A-1. gives approximately: tanh C f C

A-4. A-5. A-6.

For small values of C . .

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