Cryogenics 43 (2003) 393398 www.elsevier.

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A comparison among ve equations of state in predicting the inversion curve of some uids
Behzad Haghighi
a b

a,*

, Mohammad Reza Laee b, Naser Seyed Matin

Thermodynamic and Transport Properties Research Laboratory, Department of Chemistry, Birjand University, P.O. Box 79, Birjand, Iran National Iranian Oil Company (NIOC), Research Institute of Petroleum Industry (RIPI) Qom Road, P.O. Box 18745-4391, Tehran, Iran Received 10 January 2003; accepted 27 March 2003

Abstract Five equations of state, modied PengRobinson by Danesh et al. (MPR1), modied SRK equation of state by Mathias and Copeman (MSRK), Vdw11, HarmensKnapp (HK) and modied PengRobinson equation of state by Ruzy (MPR2) were compared in predicting of the inversion curve of some uids. This enable us to judge the accuracy of the results obtained from dierent equations of state. MSRK and HK equations of state give good prediction of the low-temperatures branch of the inversion curve and are closely matched with the experimental inversion curve. As a corollary to the present study, we have perceived that the agreement of the MPR2 and Vdw11 equations of state with the inversion curve are inadequate. We also calculated maximum inversion temperature and maximum inversion pressure for every component used in this work. 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Equation of state; JouleThomson coecient; Inversion curve

The JouleThomson (JT) eect is of considerable importance in refrigeration and gas liquefaction processes. Under appropriate conditions, adiabatic throttling of gas will cause to lower its temperature, an endothermic eect that may be strong enough even to induce condensation. For this cooling to take place, the thermodynamic state of the uid must lie in the region bounded by the inversion curve or locus of points at which the JT coecient l is zero,  l oT oP  0
h

temperature. Knowledge of the inversion curve is obviously essential for good design and operation of JT cooling processes. Direct measurement of inversion points is dicult and unreliable. Near inversion conditions, the vanishing JT coecients imply that even large pressure change will produce very small temperature dierences, detectable only by extremely accurate measurement. It is generally preferable to make use of thermodynamic relation such as       1 oV RT 2 oZ l T 2 V CP oT P CP P oT P Eorts have been made to obtain generalized inversion curves from the known behavior of light uids. Gunn et al. [1] calculated inversion points from volumetric data of argon, carbon monoxide, ethylene, methane, nitrogen and xenon. Since the data did not cover the upper temperature branch of the inversion curve, they computed additional theoretical points for argon from a truncated virial EOS with second and third virial coecients based on the Kihara intermolecular potential. The entire set of points was then correlated by the empirical equation

As usually represented in pressure-temperature coordinates, the JT inversion curve extended from minimum temperature corresponding to a saturated state on the vapor pressure line, to a maximum temperature corresponding to the ideal-gas limit at zero density and pressure. The curve is parabolic in shape and exhibits a maximum or peak inversion pressure at an intermediate

Corresponding author. E-mail address: bhaghighi@birjand.ac.ir (B. Haghighi).

0011-2275/03/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved. doi:10.1016/S0011-2275(03)00095-X

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Nomenclature Abbreviations EOS equation of state HK HarmensKnapp MPR modied PengRobinson MSRK modied SoaveRedlichKwang Symbols a equation of state parameter b equation of state parameter c equation of state parameter m equation of state parameter P absolute pressure R universal gas constant T V absolute temperature volume

Greek symbols a equation of state parameter l JouleThomson coecient x acentric factor b equation of state parameter Subscripts C critical state variable H constant enthalpy r reduced state variable

Pr 36:275 71:598Tr 41:567Tr2 11:826Tr3 1:6721Tr4 0:091167Tr5 3

An alternative, somewhat simpler equation based on published inversion data for argon, ammonia, carbon dioxide, carbon monoxide, ethylene, methane, nitrogen and propane was proposed by Miller [2], Pr 24:21 18:54 0:825Tr2 Tr 4

Eqs. (3) and (4) are two-parameter corresponding state correlations that give comparable results, since they drive from data for the same or very similar uids, described as gases that have small, nearly spherical molecules with acentric factor x close to zero, and as most gases that have a critical compressibility factor ZC of 0.29. The JT coecient is sensitive to small deviation in temperature and pressure. Hence, it is useful to test the applicability of an equation of state. To date, inversion curves have been calculated for several equation of state. As reported by Juris and Wenzel [3], prior to 1970 JT inversion curves had been calculated only for the van der Waals, Dieterici, Lennard-JonesDevonshire, and De BoerMichels equations of state. Juris and Wenzel apparently unaware of Millers work, compared Eq. (3) with predictions from the van der Waals, dieterici, Berthelot, RedlichKwang, truncated virial (with second and third virial coecients taken respectively from the Pitzer and ChuehPrausnitz correlations), SuBeattieBridgman, several reduced forms of the BendictWebRubin, and MartinHou EOSs. Miller calculated the inversion curves for the generalized RedlichKwang and Martin equations of state, and suggested a corresponding state correlation of JT inversion data in terms of reduced temperature and pressure, the SoaveRedlichKwang, PengRobinson,

PerturbedHardChain, and LeeKesler EOS, were tested by Dilay and Heidemann [4] for their ability to predict the JT inversion curves. Haghighi and Seyed Matin [5] calculated JT inversion curves for modied PatelTeja, modied PengRobinson by MelhemSaini Goodwin, IwaiMargerumLu, modied Redlich Kwang by SouahiSatorAlbaneKiesChitoure and the four parameter TrebbleBishnoi equations of state. Maghari and Seyed Matin [6] predicted the JT inversion curve from some van der Waals type equations of state. Keshavarzi et al. [7] proposed that all points on the inversion curve represent the attractive branch of the eective pair potential. They concluded that the most dense part of the inversion curve corresponds to liquid state. Zhu [8] used potential energy to study JT expansion. Colina et al. [9] used a molecular based equation of state, the Soft-SAFT equation, to predict complete JT inversion curves for carbon dioxide and the n-alkane series, including heavy n-alkanes up to octatetracontane (n-C48 H98 ). Colina and Fuentes [10] recommended a modied van der Waals equation of state to improve the prediction of the inversion curve of air. Colina and Fuentes [11] predicted inversion curve and third virial coecients of carbon dioxide at high temperatures. The adiabatic JT eect dened as Eq. (1), where l is the JT coecient. Depending on the operating condition the value of l can be positive or negative. The locus of point where l 0 is called the JT inversion curve. The inversion condition is given by the following equation     oPr oPr Tr Vr 0 5 oTr Vr oVr Tr The method of calculation is as follow: using a given EOS, the expressions for oPr =oTr Vr and oPr =oVr Tr are obtained, and Eq. (5) can be written as f Tr ; Vr 0. Consequently, for any chosen reduced volume, Vr the reduced inversion temperature can be found, and then

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the reduced inversion pressure can be calculated from the EOS. However, the inversion curve can be obtained in terms of Tr and Pr . The maximum inversion temperature can also be found when Pr tends toward zero. In this work, we employ ve dierent equations of state to predict the inversion curve of some uids. The equations of state used in this work are: 1.1. MPR1 [12] EOS P RT aC aTr V b V 2 2Vb b2 6

 t0

RTC 0:03479 0:0937x 0:16606x2 PC 0:12499x3  

 tC

RTC PC

3 ZC 8

b 7:35356 24:5176x 9:19829x2 ZC 0:289 0:0701x 0:0207x2 1.4. HK [16] EOS P RT a V b V 2 bcV c 1b2
2 R2 T C PC

2 R2 T C RTC aC 0:45724 b 0:0778 PC PC p 2 a 1 m0 1 Tr m0 1:21m

m 0:3796 1:485x 0:1644x2 0:01667x3 1.2. MSRK [13] EOS RT a P V b V V b aC 0:4286 a aC aTr aTr 1 C1 1 p p 2 Tr C2 1 Tr p 3 2 C3 1 Tr for Tr 6 1 for Tr > 1
2 R2 T C PC

aC Xa

b Xb

RTC PC

7 RTC PC

b 0:10770 0:76405n 1:24282n2 0:96210n3 1 3n c1 bn n 0:3211 0:08x 0:0384x2 Xa 1 3n 3n2 bn3 6n bn Xb bn a aC aTr  aTr x 6 0:2 A 0:5 0:27767x 2:17225x2 B 0:022 0:338x 0:845x2 x > 0:2 A 0:41311 1:14657x B 0:0118 aTr 1 0:6258 1:5227x ln Tr 0:1533 0:41x ln Tr
2

b 0:08664

p 2 aTr 1 C1 1 Tr

1 A1

 2 p 1 Tr B 1 Tr

for Tr 6 1

The values of pure-component temperature parameters (C1 C3 ) are given in Table 1. 1.3. Vdw11 [14,15] EOS P RT a V t b V t2   2 2  27 R TC a aC a a 64 PC
2 Tr0:5 2

a 1 m1

Tr > 1

m 0:48553 1:624x 0:21884x    1 RTC b 8 PC t t0 tC t0 expbj1 Tr j

1.5. MPR2 [17,18] EOS P RT aT ~ e e ~ e b V V 4:82843b V aC 0:5724

2 RTC PC

10

e V V c c 0:40768
C3 1.3447 0.5751 0.6603 1.7387

Table 1 Pure-component temperature parameters (Eq. (7)) Component Carbon dioxide Methane Ethane Propane C1 0.8659 0.5472 0.8479 0.7517 C2 )0.4386 )0.3992 )0.3421 )0.6277

RTC 0:29441 ZC PC

m 0:37464 1:485x 0:26992x2 aT aC 1 m1 Tr0:44

2

RTC ~ b 0:04557 PC

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6 5 4 Tr 3 2 1 6 5 4 Tr 3 2 1 0 0 2 Exp. 4 6 Pr Vdw11 8 10 HK 5 4
4.5 4 3.5 3 2.5 2 1.5 1 0.5 0 0 2 4 Exp. HK 6 Pr MPR1 MSRK Vdw11 8 10 12 14

The calculated JT inversion curves from various equation of state are shown in Figs. 15, for Ar, CO2 , CH4 , C2 H6 , C3 H8 , respectively. The inversion curve predicted by MPR1 equation of state shows good predictions at low temperatures. The

0 0 2 4 6 Pr Exp. Vdw11 MPR1 MSRK MPR2 HK 8 10 12 14

12

Fig. 4. Same as Fig. 3 for C2 H6 . (d) Exp., (- - -) MPR1, () MSRK, ( ) MPR2, (---) HK, (---) Vdw11. Experimental data adopted from Ref. [19].

Fig. 1. JT inversion curves for Argon. (d) Exp., (- - -) Vdw11, () HK. Experimental data adopted from Ref. [19].

3 Tr 2 1 0 0 2 4 Exp. Vdw11 6 Pr MPR1 MSRK MPR2 HK 8 10 12 14

Tr

Fig. 5. Same as Fig. 3 for C3 H8 . (d) Exp., (- - -) MPR1, () MSRK, ( ) MPR2, (---) HK, (---) Vdw11. Experimental data adopted from Ref. [19].

Fig. 2. JT inversion curves for CO2 . (d) Exp., (- - -) Vdw11, () MSRK, ( ) HK, (---) MPR1. Experimental data adopted from Ref. [19].

6 5 4 Tr 3 2 1 0 0 2 4 Exp. Vdw11 6 Pr MPR1 MSRK MPR2 HK 8 10 12 14

Fig. 3. JT inversion curves for CH4 . (d) Exp., (- - -) MPR1, () MSRK, ( ) MPR2, (---) HK, (---) Vdw11. Experimental data adopted from Ref. [19].

low-temperature region of the inversion curve is well matched by MPR1 equation of state for hydrocarbons. The predicted maximum inversion pressure is less than the reference value. The deviation of MPR1 predictions from experimental data occurs at reduced pressure above 10 for hydrocarbons and above 9 for carbon dioxide. MPR1 equation of state gives poor prediction for dierent uids at the peak of the curves. This equation also gives poor results in the vicinity of critical point. The inversion curve predicted by MSRK equation of state shows good predictions at low temperatures. The low-temperature region of the inversion curve is well matched by MSRK equation of state for hydrocarbons. Therefore, the MSRK equation can safely be considered as a reference for the evaluation of the low-temperature inversion curve predicted by other equations of state. The maximum inversion pressure is comparable to that obtained from the reference values for ethane and propane. Therefore, the eect of pressure on the ability of

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this equation to predict the derived properties is negligible. The inversion locus predicted by the VdW11 equation of state does not agree with experimental data in any region.The predicted inversion temperatures are above the reference values especially at high temperatures for hydrocarbons. The maximum inversion pressure is considerably less than the reference values. Therefore, the weakness of this equation cannot be set within reliable limits of operating conditions. The inversion curve locus predicted using the HK equation of state is as good as that predicted by MPR1 equation of state at low temperatures. The deviation of HK predictions from experimental data occurs at reduced pressure above 10 for hydrocarbons and carbon dioxide and above 8 for Argon. The inversion locus predicted by the MPR2 equation of state does not agree with experimental data in any region. The maximum inversion pressure is considerably less than the reference values. The maximum inversion pressure, Pr;max and the corresponding temperature, Tr;i for the ve equations are calculated and given in Table 2. The maximum inversion temperature, Tr;max obtained in the ideal-gas limit

Table 3 The used values of the acentric factors and the critical state constants have taken from Ref. [19] for each uid Name Argon Carbon dioxide Methane Ethane Propane TC (K) 150.86 304.21 190.564 305.32 369.83 106 PC (Pa) 4.9 7.39 4.59 4.85 4.21 VC (m3 /K mol) 0.075 0.095 0.099 0.146 0.200 ZC 0.292 0.277 0.286 0.279 0.273 Acentric factor 0.000 0.224 0.011 0.098 0.149

(Pr ! 0), is also calculated and shown in Table 2. The used values of the acentric factors and the critical state constants have taken from Ref. [19] for each uid and have been presented in Table 3. Acknowledgements Financial support received from the Research Council of the University of Birjand is gratefully acknowledged. Heartfelt thanks go to Mrs. Faranak Valimehr and Ms. Vida Noushinfar for their generous help. References

Table 2 The calculated maximum inversion pressures Pr;max the corresponding temperature Tr;i and maximum inversion temperature Tr;max Equation of state MPR1 Component Methane Ethane Propane Carbon dioxide Methane Ethane Propane Carbon dioxide Argon Methane Ethane Propane Carbon dioxide Argon Methane Ethane Propane Carbon dioxide Methane Ethane Propane Pr;max 13.1888 13.4217 13.6864 13.9073 12.0637 12.2117 12.2398 12.4591 7.6497 8.0909 8.1676 8.3232 8.2673 10.1932 10.2097 10.2889 10.3290 10.4163 7.9945 8.3751 8.6999 Tr;i a 2.1 2.05 1.85 1.63 2.65 2.5 2.2 2.43 2.49 2.9 2.5 2.6 2.43 1.91 1.91 1.79 1.7 1.63 2.1 2.05 1.85 Tr;max 4.7507 4.0521 3.7442 3.3834 5.5893 5.0914 4.8324 4.5952 4.3049 4.2499 3.8569 3.6555 3.3955 4.8402 4.7672 4.2550 3.9993 3.6806 5.8030 5.1099 4.8119

MSRK

VdW11

HK

MPR2

a The number of signicant gures are exactly adopted from their reference values [19].

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