Fluid Phase Equilibria 153 1998.

231242

A saturated liquid density equation in conjunction with the Predictive-SoaveRedlichKwong equation of state for pure refrigerants and LNG multicomponent systems
Khashayar Nasrifar, Mahmood Moshfeghian
Received 5 June 1998; accepted 10 September 1998
)

Department of Chemical Engineering, School of Engineering, Shiraz Uniersity, P.O. Box 1133 Shiraz 71345, Iran

Abstract An equation and a set of mixing rules for the prediction of liquid density of pure refrigerants and liquified natural gas LNG. multicomponent systems have been developed. This equation uses the parameters of Mathias and Copeman wP.M. Mathias, T.W. Copeman, Fluid Phase Equilib. 13 1983. 91108x temperature dependentterm for the Predictive-SoaveRedlichKwong wT. Holderbaum, J. Gmehling, Fluid Phase Equilib. 70 1991. 251265x equation of state and hence it could be used together with this equation. The equation uses a characteristic parameter for each refrigerant; however, if it is not available, a value of zero is recommended. This model gives an average of absolute errors less than 0.42% for the prediction of liquid density of 28 pure refrigerants consisting of 2489 data points and 0.33% for 18 multicomponent LNG systems involving 132 data points. The model parameters were determined from pure component properties and reported. These parameters were then used without any adjustment to predict liquid density of multicomponent LNG mixtures and excellent results were obtained. The model was also compared with other available methods. q 1998 Elsevier Science B.V. All rights reserved.
Keywords: Liquid density equation; Equation of state; Refrigerant; LNG

1. Introduction Having known the hazardous effects of chloroflourocarbon CFC. refrigerants to the atmosphere, the development andror modification of available equations for accurately prediction of properties of alternative refrigerants are more pronounced. Two of these properties are vapor pressure and liquid density. Equations of states EOSs. are commonly used for calculation of vapor pressure. Using the
)

Corresponding author. Tel.: q98-71-30-3071; fax: q98-71-30-3071; e-mail: moshfeg@succ.shirazu.ac.ir

0378-3812r98r$ - see front matter q 1998 Elsevier Science B.V. All rights reserved. PII: S 0 3 7 8 - 3 8 1 2 9 8 . 0 0 4 2 2 - 1

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Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

given temperature dependent term by Mathias and Copeman w1x for attractive parameters in EOSs, equations like Predictive-SoaveRedlichKwong PSRK. w2x gives vapor pressures that deviate less than 0.5% from experimental data. This accuracy is enough for design purposes. There are also EOSs that predict accurately liquid density of pure components w3,4x or even their mixtures w5,6x. However, correlations are usually applied for design purposes. The EOSs, in spite of correlations, have narrower range of applicability specially at regions near critical point where deviations from experimental data become excessive. Nevertheless, they need the same number of parameters that are required for the calculation of other properties. Correlations are more accurate and reliable than EOSs, although they suffer from some shortcomings. Recently, Iglesias-Silva and Hall w7x have developed an excellent correlation for the prediction of liquid density of CFC and hydroflourocarbon HFC. refrigerants. This correlation requires two fitting parameters for each refrigerant in addition to the critical properties and as a result its accuracy is within the range of experimental data. However, they have not addressed the needed parameters for other widely used refrigerants such as light hydrocarbons or inorganic gases. Moreover, its extension to multicomponent systems has not been made. The corresponding state liquid density COSTALD. correlation w8x and the modified Rackett correlation by Spencer and Danner RSD. w9x are the two other widely used correlations for nearly all purposes including refrigeration. The former gives poor results for the calculation of liquid density of He and H 2 and the latter for multicomponent systems in addition to its inaccuracy for He and H 2 . In order to compensate the faults from correlations and EOSs, an equation for the calculation of saturated liquid density of refrigerants is developed. This equation can be used in conjunction with the PSRK EOS w2x.

2. The PSRK EOS For pure components, the PSRK EOS w2,10,11x is in essence the same as the SRK EOS w12x except that the Mathias and Copeman temperature dependent term w1x is used instead of the conventional temperature dependent term in the a-parameter of the SRK EOS. This substitution improves greatly the prediction of vapor pressures. The PSRK EOS is expressed by: Ps RT y yb qb. RTC PC
2 R 2 TC

1.

where b and a are given by: b s 0.08664

2.
f Tr .

a s 0.42748

PC

3.

where f Tr . is the Mathias and Copeman w1x temperature dependent term and Tr s TrTC . is reduced temperature. It is defined by: f Tr . s 1 q c1 1 y Tr q c 2 1 y Tr

( /

( /

q c 3 1 y Tr

( /

3 2

, Tr - 1

4.

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233

Table 1 Global constants in Eq. 7. d1 d2 d3 d4 1.1688 1.8177 y2.6581 2.1613

and f Tr . s 1 q c1 1 y Tr

( /

, Tr ) 1

5.

3. The proposed liquid density equation After examining a large number of correlations, the following equation is proposed. It has been formulated empirically in order to be satisfied at critical conditions. The equation is expressed by: rS 1r 3 s r 0 1 q d f Tr . y 1 . 6. rC and r 0 is defined by:
1r 3 2r 3 4r 3

r 0 s 1 q d1 1 y

Tr f Tr .

q d2 1 y

Tr f Tr .

q d3 1 y

Tr f Tr .

q d4 1 y

Tr f Tr .

7.

where r S and r C are respectively, saturated and critical molar liquid density, f Tr . is given by Eq. 4. , d is a characteristic parameter for each component and d1, d 2 , d 3 and d 4 are global constants independent of refrigerants which are given in Table 1. The procedure for determination of the global constants and characteristic parameter is explained in the following sections.

4. The proposed mixing rules In order to use Eq. 6. for predicting liquid density of mixtures, some mixture value for r C , d , f Tr . and TC must be specified. After evaluating several mixing rules for the prediction of liquid density of LNG mixtures, the following mixing rules have been proposed:
NC

TCm s X i TC i
i NC

8. 9. 10.

dm s X i d i
i NC NC

f m Tr . s
i

X i X j f i j Tr .
j

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Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

where f i j Tr . s f i Tr . f j Tr . and
NC
3r 4 y 3r 4 ry Cm s X i r C i

(
i

11.

12.

in Eqs. 8. 12. X is mole fraction. 5. Results and discussion The name of refrigerants, their formula, number, temperature ranges, number of points and sources for parameter estimation are given in Table 2. Before calculating the liquid densities, c1, c 2 and c 3
Table 2 Refrigerants experimental dataa used for fits Refrigerant no. 50 170 290 600 600a 1150 1270 702 704 720 728 732 744 740 717 11 12 13 13B1 14 22 23 113 114 142b 152a 123 134a
a

Name methane ethane propane n-butane i-butane ethylene propylene normal hydrogen helium neon nitrogen oxygen carbon dioxide argon ammonia trichlorofluoromethane dichlorodifluoromethane chlorotrifluoromethane bromotrifluoromethane carbon tetrafluoride chlorodifluoromethane trifluoromethane trifluorotrichloroethane dichlorotetrafluoroethane chlorodifluoroethane difluoroethane dichlorotrifluoroethane tetrafluoroethane

Chemical formula CH 4 C2H6 C 3H 8 n-C 4 H 10 i-C 4 H 10 C2H4 C 3H 6 H2 He Ne N2 O2 CO 2 A NH 3 CCl 3 F CCl 2 F2 CClF3 CBrF3 CF4 CHClF2 CHF3 CCl 2 FCClF2 CClF2 CClF2 CH 3 CClF2 CH 3 CHF2 CHCl 2 CF3 CH 2 FCF3

NPTS 64 56 48 52 47 61 45 65 33 67 60 55 67 65 60 60 60 67 67 68 65 63 60 61 64 61 63 53

T Range K. 92188 155300 190365 225420 215400 140276 185355 1530.8 2.54.6 24.642 64123 74150 217299 84147 218398 248463 203378 158297 178333 133218 198363 163291 267473 233408 218398 208363 283444 228364

The source is ASHRAE w13x except for R-123 and R-134a that is Dupont w14x.

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235

must be determined for each refrigerant. They have been determined such that the summation of absolute relative errors in calculating vapor pressures by the PSRK EOS and those from experimental data of Table 2 at the same temperature are minimized. Therefore, the objective function used for optimization of vapor pressures is:
NPTS

VP s

PCAL i P EXP i

y1 .

13.

The optimization has been performed by the use of a nonlinear regression package w15x. Using the above procedure, c1, c 2 and c 3 for 28 refrigerants have been determined. Table 3 shows the refrigerants, the relevant c1, c 2 , c 3 and the average of absolute percent deviation AAPD. for calculating the vapor pressures. As it is seen triflouromethane R-23. with an AAPD equal to 0.47 has the most error for the calculation of vapor pressures and carbon dioxide R-744. has the least with an
Table 3 The characteristic parameters, constants of Eq. 4. and the relevant AAPD a for the calculation of vapor pressure of pure refrigerants by the PSRK EOS Refrigerant CH 4 C2H6 C 3H 8 n-C 4 H 10 i-C 4 H 10 C2H4 C 3H 6 H2 He Ne N2 O2 CO 2 A NH 3 CCl 3 F CCl 2 F2 CClF3 CBrF3 CF4 CHClF2 CHF3 CCl 2 FCClF2 CClF2 CClF2 CH 3 CClF2 CH 3 CHF2 CHCl 2 CF3 CH 2 FCF3
a

NPTS 64 56 48 52 47 61 45 65 33 67 60 55 67 65 60 60 60 67 67 68 65 63 60 61 64 61 63 53 PCAL i P EXP i y1 .

d =10 2
y2.20 1.26 y0.38 0.00 3.87 y4.05 4.98 y22.38 30.11 y5.59 y3.08 0.95 0.98 y3.59 5.88 0.55 1.24 y0.16 2.24 y1.53 0.45 6.90 y0.28 y3.15 4.54 6.07 1.07 0.96

c1 0.5857 0.7178 0.7863 0.8787 0.8288 0.7172 0.7647 0.2053 y0.0590 0.6208 0.5867 0.5914 0.8679 0.5391 0.9618 0.8611 0.8143 0.7956 0.8032 0.8099 0.8867 1.0145 0.9803 0.9217 0.8742 0.9231 1.0041 1.0708

c2 y0.7206 y0.7644 y0.7459 y0.9399 y0.8285 y0.8757 y0.6111 y0.4241 y0.6527 y1.5052 y0.4459 y0.7127 y0.7135 y0.5686 y0.9524 y0.9711 y0.6838 y0.6096 y0.6106 y0.6134 y0.7232 y1.2356 y1.0880 y0.5981 y0.0861 y0.1238 y1.0020 y0.9536

c3 1.2899 1.6396 1.8454 2.2666 2.3201 1.8771 1.3958 y0.1032 0.4271 2.7912 0.8926 1.4829 2.6563 1.1338 2.1480 2.4291 1.7469 1.6819 1.5152 1.6465 1.8186 2.8585 2.6255 1.5593 y0.7367 y0.8003 2.7005 2.3776

AAPD a 0.29 0.26 0.21 0.43 0.43 0.41 0.26 0.09 0.07 0.32 0.12 0.37 0.04 0.14 0.38 0.37 0.22 0.35 0.25 0.21 0.28 0.47 0.40 0.23 0.35 0.34 0.22 0.22

100 AAPD s NPTS NPTS i

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Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

Table 4 Ability of different methods for the calculation of liquid density of pure refrigerants Refrigerant NPTS T Range K. 92190 95300 90365 140420 115400 110276 90360 1432 2.25.1 24.644 64125 55154 217301 84150 198403 200463 150378 91301 170333 100223 120368 150294 240483 190410 200400 170371 200455 200370 Source AAPD a This work with d s 0 w13,16x 1.12 w13,16x 0.74 w13,16x 0.26 w13,16x 0.19 w13,16x 2.29 w13,16x 2.13 w13,16x 3.13 w13,16x 7.51 w13,16x 12.36 w13,16x 2.86 w13,16x 1.54 w13,16x 0.55 w13,16x 0.56 w13,16x 1.69 w13,16x 3.76 w13,16x 0.49 w13,16,17x 0.82 w13,16x 0.20 w13,16x 1.34 w13,16x 0.84 w13,1618x 0.48 w13,16x 4.27 w13,16x 0.26 w13,16x 1.76 w13,16,19x 3.07 w13,16,20x 3.81 w14,21x 0.53 w14,21,22x 0.47 2.00 This work with d b 0.25 0.36 0.21 0.19 0.70 0.72 0.46 1.28 0.96 0.25 0.22 0.51 0.19 0.27 0.47 0.18 0.19 0.19 0.33 0.12 0.22 0.77 0.15 1.53 0.70 0.27 0.24 0.20 0.42 COSTALD 0.14 0.09 0.16 0.12 0.20 0.45 0.58 1.24 3.66 0.33 0.27 0.24 0.43 0.13 1.36 0.45 0.40 0.12 0.15 0.04 0.27 0.63 0.23 1.78 0.67 0.53 0.36 0.27 0.52 RSD 0.29 0.23 0.41 0.19 0.31 0.63 0.71 0.81 2.92 0.52 0.39 0.45 0.45 0.50 0.40 0.55 0.75 0.27 0.18 0.17 0.20 0.60 0.19 1.66 1.08 0.43 0.33 0.27 0.54 ISH 0.10 0.24 0.41 0.15 0.39 0.33 0.40 0.63 0.57 0.20 0.19 0.27 0.17 0.20 0.12 0.08 0.22 0.24 0.14 0.10 0.19 0.33 0.26 0.88 0.49 0.32 0.22 0.16 0.28

CH 4 C2H6 C 3H 8 n-C 4 H 10 i-C 4 H 10 C2H4 C 3H 6 H2 He Ne N2 O2 CO 2 A NH 3 CCl 3 F CCl 2 F2 CClF3 CBrF3 CF4 CHClF2 CHF3 CCl 2 FCClF2 CClF2 CClF2 CH 3 CClF2 CH 3 CHF2 CHCl 2 CF3 CH 2 FCF3 Average
a

84 90 96 81 89 79 87 87 69 77 77 87 83 80 87 88 114 92 85 91 125 78 93 84 92 118 86 90

y1 . r EXP i b Values of d are given in Table 3.

100 AAPD s NPTS NPTS i

r CAL i

AAPD of 0.04. Consequently, the PSRK EOS calculates the vapor pressures of the 28 refrigerants within 0.47% of experimental data. In order to calculate the liquid density of the refrigerants using Eq. 6. , the global constants and characteristic parameter for each of the refrigerants must be determined. The global constants d1, d 2 , d 3 and d 4 and the characteristic parameters, d , have been optimized in a two step procedure. The objective function applied for the optimization is:
NPTS

Vps

r CAL i r EXP i

y1

14.

Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

237

Fig. 1. Liquid density percent deviation of this work as a function of reduced temperature for some of the chlorofluorocarbon refrigerants experimental data from Ref. w13x..

In the first step d has been taken equal to zero and for nearly 600 data points including a series of refrigerants d1, d 2 , d 3 and d 4 have been determined. Then in determining d , Eq. 14. has been optimized for each refrigerant using Eq. 6. . Again the nonlinear regression package w15x has been applied. The global constants are given in Table 1 and the characteristic parameters included in Table 3. Table 4 compares the calculations of liquid density of the proposed model, the COSTALD, RSD and Iglesias-Silva and Hall ISH. w7x correlations. Having a courteous comparison, the parameters for

Fig. 2. Liquid density percent deviation of this work as a function of reduced temperature for some of the hydrofluorocarbon refrigerants experimental data from Refs. w13,14x..

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Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

all of the correlations were determined using the experimental data of Table 2 and Eq. 14. . To show the predictability of the methods, some other experimental data not used for fits to those used for fits were added. As can be seen this work calculates the liquid densities with an average of AAPD AAAPD., i.e., the AAPD for all refrigerants including all experimental data points, equal to 0.42. The maximum deviation occurs for R-114 with an AAPD of 1.53 and the least for R-14 with an AAPD of 0.12. The AAAPD of COSTALD, RSD and ISH correlations are 0.52, 0.54 and 0.28 for the same number of data points, respectively. Obviously, the ISH correlation is the best, this work is the next and COSTALD and RSD are the third and the fourth. However, this superiority is in the expense of one more estimation parameter for each refrigerant. ISH correlation has two fitting parameters while the three others have one. Table 4 also compares the model results with optimized d and for the case in which d is zero. Clearly, d improves the results of the model; however, the AAAPD when d is taken zero is still less than 2.00 and without considering He and H 2 , the AAAPD is 1.49. In other words, Eq. 6. have the ability to calculate the liquid density of the refrigerants within 1.49% of experimental data and still not any other parameters in excess of those required for the calculation of vapor pressure or any other pure component properties by the PSRK EOS will be necessary. However, in this case the liquid density results for He and H 2 are not satisfactory. Figs. 1 and 2 show deviation plots for two categories of the refrigerants. Fig. 1 presents liquid density percent deviation LDPD. as a function of reduced temperature for some of the CFC refrigerants. Hence, LDPD is defined by: LDPD s 100

r CAL r EXP

y1

15 .

As can be seen the maximum LDPD through the reduced temperature range are 0.41, y0.32, y0.69 and y0.36 for CCl 3 F, CCl 2 F2 , CClF3 and C 2 Cl 3 F3 , respectively. These maximums occur near critical points. Fig. 2 demonstrates the LDPD of HFC refrigerants as a function of reduced temperature. The maximum LDPD of HFCs are y0.95, 0.74 and 0.88 for CHF3 , CH 3 CHF2 and CH 2 FCF3 , respectively. It is seen that LDPD of CHF3 changes fast through the given temperature range. Surprisingly, the LDPD plot for CH 2 FCF3 is different from the others. It shows a scatter plot. This can be explained if it is noted that the source of experimental data for CH 2 FCF3 is different from the source of other refrigerants. The ASHRAE w13x experimental data were smoothed whereas the Dupont w14x data were not. In order to predict the liquid density of multicomponent systems, Eqs. 8. 12. have been proposed as mixing rules. Eighteen LNG multicomponent systems have been considered for evaluation of Eq. 6. and their mixing rules. Table 5 shows the multicomponent systems, temperature ranges, sources and their code name. Table 6 presents the liquid density predictions by Eq. 6. and the proposed mixing rules. In addition, Table 6 shows the liquid density predictions of COSTALD, RSD and the Chain-of-Rotator-Group-Contribution CORGC. EOS w26x. The CORGC has shown its versatility for the prediction of liquid density of LNG systems w5x. For using the CORGC EOS the group parameters of Pults et al. w26x has been used along with the mixing rules given by Nasrifar and Moshfeghian w5x. Yet, the ISH correlation has not been extended to multicomponent systems and so was not used for the comparison. For this comparison, the pure refrigerant parameters optimized in this work for the three correlations are used. As can be seen, the proposed model with its mixing rules predicts the liquid density of LNG multicomponent systems better than the CORGC EOS and the two correlations.

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239

Table 5 List of LNG multicomponent systems used for comparisons Systema 0.0475y0.4924.N2 q0.5075y0.9525.C 1 0.0593N2 q0.9407C 2 0.0201y0.0674.N2 q0.9326y0.9798.C 3 0.3546y0.6800.C 1 q0.3199y0.6454.C 2 0.2954y0.8579.C 1 q0.1420y0.7046.C 3 0.7798y0.9278.C 1 q0.0721y0.7798. i-C 4 0.0593N2 q0.8907C 1 q0.04998 n-C 4 0.8604C 1 q0.0460C 2 q0.0470C 3 q0.0457 i-C 4 0.049N2 q0.8060C 1 q0.0468C 2 q0.0482C 3 q0.05 i-C 4 0.7644y0.9737.C 1 q0.0080y0.0073.C 2 q0.0034y0.02612.C 3 0.0505y0.338.N2 q0.3414y0.8409.C 1 q0.1086y0.3206.C 2 0.497y0.0995.N2 q0.7977y0.9055.C 1 q0.0497y0.1028.C 3 0.0425N2 q0.8130C 1 q0.0475C 2 q0.0487C 3 0.85443C 1 q0.05042C 2 q0.04038C 3 q0.02577 i-C 4 q0.02901 n-C 4 0.0490N2 q0.8060C 1 q0.0468C 2 q0.0482C 3 q0.05iC 4 0.0554N2 q0.7909C 1 q0.0560C 2 q0.0500C 3 q0.0477 n-C 4 0.0425N2 q0.8130C 1 q0.0475C 2 q0.0487C 3 q0.0242 i-C 4 q0.0241 n-C 4 0.8513C 1 q0.0576C 2 q0.0481C 3 q0.0430 n-C 4
a

T Range K. 95140 105120 105115 105140 105130 120130 110125 115135 115130 105125 105120 105120 105120 105120 105120 105110 105120 115135

Source w23x w23x w23x w23x w23x w23x w24x w24x w24x w25x w25x w25x w25x w25x w25x w25x w25x w24x

Code name LDS1 LDS2 LDS3 LDS4 LDS5 LDS6 LDS7 LDS8 LDS9 LDS10 LDS11 LDS12 LDS13 LDS14 LDS15 LDS16 LDS17 LDS18

C 1, C 2 , C 3 , n-C 4 and i-C 4 stand for CH 4 , C 2 H 6 , C 3 H 8 , n-C 4 H 10 and i-C 4 H 10 , respectively.

Table 6 Ability of different methods for the calculation of liquid density of multicomponent LNG systems Code name LDS1 LDS2 LDS3 LDS4 LDS5 LDS6 LDS7 LDS8 LDS9 LDS10 LDS11 LDS12 LDS13 LDS14 LDS15 LDS16 LDS17 LDS18 Average
a
100 AAPD s NPTS NPTS i

NPTS 21 4 6 20 20 4 4 5 4 10 7 4 4 4 4 2 4 5

AAPD a This work 0.68 0.62 0.71 0.17 0.11 0.88 0.17 0.28 0.15 0.19 0.39 0.25 0.20 0.10 0.23 0.40 0.21 0.30 0.33 CORGC 0.48 0.55 0.96 0.21 0.18 0.37 1.60 1.02 1.11 0.19 0.51 0.15 0.13 0.14 0.84 0.31 0.23 0.24 0.43 COSTALD 1.08 0.03 0.22 0.05 0.48 1.51 0.75 0.42 0.71 0.32 0.80 0.74 0.46 0.41 0.77 0.81 0.67 0.33 0.55 RSD 1.26 0.50 1.30 0.73 0.90 1.72 0.79 0.31 0.70 0.99 1.00 0.54 0.11 0.30 0.30 0.12 0.21 0.23 0.81

r CAL i r EXP i

y1 .

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Kh. Nasrifar, M. Moshfeghian r Fluid Phase Equilibria 153 (1998) 231242

Fig. 3. Ability of different methods for the prediction of liquid density of 0.0425 N2q0.8130 CH4q0.0475 C2H6q0.0487 C3H8q0.0241 n-C4H10q0.0242 i-C4H10 system experimental data from Ref. w25x..

The AAAPDs are 0.33, 0.43, 0.55 and 0.81 for the model in this work, the CORGC EOS, COSTALD and RSD, respectively. The total number of points for these comparisons was 132. These data points were consisted of 2, 3, 4, 5 and 6 component LNG systems. It should be noted that no adjustable parameter or curve fitting was performed in predicting the liquid densities of these mixtures. Fig. 3 presents a deviation plot for liquid density of N2 q CH 4 q C 2 H 6 q C 3 H 8 q n-C 4 H 10 q iC 4 H 14 multicomponent system. Although with opposite trends, the model introduced here and the CORGC EOS and RSD show merely the same ability for this system and they predict better than COSTALD. However, as indicated by Table 6, the COSTALD generally predicts the liquid density of LNG mixture better than RSD.

6. Conclusion Using the PSRK EOS w2x, the vapor pressure of 28 refrigerants have been calculated. In this respect c1, c 2 and c 3 , the parameters of Mathias and Copeman w1x temperature dependent term for relevant refrigerants have been optimized and reported. Of course some of them including the parameters of the hydrocarbon refrigerants have been reported before w2x and what are reported in this work are the revised parameters. Nevertheless, the use of the revised parameters with Eq. 6. are not essential inasmuch as they depend on vapor pressure and so any c1, c 2 and c 3 by any worker could be used. A correlation and a set of mixing rules for the calculation of saturated liquid density of pure refrigerants and LNG multicomponent systems have been developed. The correlation uses a characteristic parameter for each refrigerant; however, if the parameter is not available, a value of zero could be used. Except for He and H 2 an AAPD of less than 1.49 could be supposed if d is taken equal to 0. Moreover, use of the characteristic parameter, d , improves the prediction of liquid density for pure

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241

refrigerants and multicomponent LNG systems to within 0.42% of experimental data. In a word, a saturated liquid density model has been developed that can be used in conjunction with the PSRK EOS and still not more than one fitting parameter for each component in excess of those required for the calculation of other properties by the PSRK EOS will be necessary. Even with d equal to zero a saturated liquid density with a deviation less than 1.49% for pure refrigerants could be expected.

7. Nomenclature a b c1 , c 2 , c 3 d1 , d 2 , d 3 , d 4 f P R T X Greek letters d r V Subscript c m r attraction parameter in the PSRK EOS, Pa m6rkmol 2 excluded molar volume in the PSRK EOS, m3rkmol parameters of Mathias and Copeman equation, Eq. 4. global constants in Eq. 7. temperature dependent function given by Eq. 4. pressure, Pa universal gas constant, 8314 Pa m3rkmol K temperature, K molar volume, m3rkmol mole fraction characteristic parameter for each component molar liquid density, kmolrm3 objective function critical mixture reduced

References
w1x w2x w3x w4x w5x w6x w7x w8x w9x w10x w11x w12x w13x w14x P.M. Mathias, T.W. Copeman, Fluid Phase Equilib. 13 1983. 91108. T. Holderbaum, J. Gmehling, Fluid Phase Equilib. 70 1991. 251265. M. Moshfeghian, A. Shariat, R.N. Maddox, Chem. Eng. Comm. 73 1988. 205215. M. Zia-Razzaz, M. Moshfeghian, Fluid Phase Equilib. 91 1993. 239263. Kh. Nasrifar, M. Moshfeghian, Fluid Phase Equilib. 112 1995. 8999. A. Boushehri, F.S. Hashemi, T. Keshavarzi, Fluid Phase Equilib. 129 1997. 6167. G.A. Iglesias-Silva, K.R. Hall, Fluid Phase Equilib. 131 1997. 97105. R.W. Hankinson, G.H. Thomson, AIChE J. 25 1979. 653663. C.F. Spencer, R.P. Danner, J. Chem. Eng. Data 18 1973. 230234. K. Fischer, J. Gmehling, Fluid Phase Equilib. 112 1995. 122. A. Keshtkar, F. Jalali, M. Moshfeghian, Fluid Phase Equilib. 140 1997. 107128. G. Soave, Chem. Eng. Sci. 4 1972. 11971203. ASHRAE, American Society of Heating and Refrigeration and Air Conditioning Engineer, New York, 1989. Dupont, Technical Information, Thermodynamic properties of HCFC-123 and HFC-134a, 1990.

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