Fluid Phase Equilibria 224 (2004) 157167

A simplified method for calculating saturated liquid densities

A. Mchaweha,1 , A. Alsaygha , Kh. Nasrifarb , M. Moshfeghianc,
a Department of Chemical Engineering, University of Qatar, Doha, Qatar
b Department of Energy and Process Engineering, Norwegian University of Science and Technology, N-7491 Trondheim, Norway
c Petroleum Research and Studies Center, Kuwait Institute for Scientic Research, Kuwait

Received 26 November 2003; received in revised form 1 May 2004; accepted 18 June 2004
Available online 6 August 2004

Abstract

A simplification for the NasrifarMoshfeghian (NM) liquid density correlation has been developed. A replacement for the Mathias and
Copeman temperature-dependent term with the original SoaveRedlichKwong equation of state (SRK EOS) temperature-dependent term
has been done. This replacement has overcome the limitations in use for the original model due to the Mathias and Copeman vapor pressure-
dependent parameters. The new correlation uses one characteristic parameter for each compound and suggests a value of zero for generalization
purpose. The revised model has been tested for pure compounds liquid density prediction of different types including paraffins, cyclo-
paraffins, olefins, diolefins, cyclic olefins, aromatics, ethers, liquefied inorganic gases and alcohols. The average absolute percent deviation
for 76 compounds consisting of 2379 experimental data points was found to be 0.58%. The simplified method was then used to predict the
saturated liquid density of multi-component systems. The average absolute percent deviation for 58 multi-component systems consisting of
978 experimental points was found to be 0.67%. Generalizing the correlation, by setting a value of zero for the characteristic parameter, gave
average absolute percent deviation of 2.01% for the same pure compounds and 1.57% for the 58 multi-component systems. The accuracy of
the simplified model has been compared with other correlations and equations of states.
2004 Elsevier B.V. All rights reserved.

Keywords: Liquid density; Equation of state; NasrifarMoshfeghian correlation

1. Introduction
Liquid density is needed for process simulation and equip-
ment design. For example, accurate predictions of liquid den-
sity are needed for calculating pressure drop in piping and
vessel sizing. Accurate liquid density is also essential for
custody transfer.
Nasrifar and Moshfeghian (NM) [1] evaluated the accu-
racy of four equations of state (EOSs) and 14 correlations
for the calculation of saturated liquid density of 18 refriger-
ants. They found that except for the chain-of-rotator-group-
contribution (CORGC) EOS [2], errors of more than 5% are
common for the cubic EOSs. They also concluded that al-
compound. These parameters are not readily available for all
Corresponding author.
E-mail address: mmosh@prsc.kisr.edu.kw (M. Moshfeghian).
1 Present address: Coiled Tubing Services, Well Services, Schlumberger.
though correlations are the most accurate and reliable way
for the prediction of saturated liquid density, they suffer from
shortcomings. For example, corresponding state liquid den-
sity, COSTALD [3], and SpencerDanner [4] modification
of Rackett [5], RackettSpencerDanner (RSD), give poor
results for the calculation of liquid density of He and H2 as
well as high deviation from the experimental data for multi-
component systems. Nasrifar and Moshfeghian [6] presented
a correlation which works in conjunction with the predictive-
SoaveRedlichKwong (PSRK) EOS [7]. Their correlation
requires three parameters for the Mathias and Copeman [8]
temperature-dependent term used in the PSRK EOS for each
compound. In addition, the complexity in the calculation
arises from the use of three different parameters for each
compounds. The Mathias and Copeman parameters [8] are
normally determined by regression of the vapor pressure data

0378-3812/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2004.06.054
158 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167

using the PSRK EOS [7]. The NM correlation cannot be used defined 0 as
for any compound that does not have the tabulated Mathias    
and Copeman parameters. Tr 1/3 Tr 2/3
0 = 1 + 1.1688 1 + 1.8177 1
In order to overcome this problem, a replacement for the
PSRK temperature-dependent term with the original SRK  3/3  
Tr Tr 4/3
term [9] was adopted. This replacement eliminates Math- 2.6581 1 + 2.1613 1 (7)
ias and Copeman parameters, namely C1 , C2 and C3 , so
the new correlation can be used without this limitation. where is the NM correlation adjustable parameter.
The accuracy of the proposed simplified model has been
tested against experimental data, other correlations and equa-
tions of state such as the volume translated SRK, VTSRK 4. Extension to multi-component systems
[10], NasrifarMoshfeghian, NM EOS [11], and modified
NasrifarMoshfeghian, MNM EOS [12]. Using the parameters found for pure refrigerants, without
further changes or using binary interaction parameters, Nas-
rifar and Moshfeghian extended their correlation to multi-
2. The PSRK EOS component systems and reported good accuracy [6]. Their
suggested mixing rules are:
Except for the Mathias and Copeman temperature-
dependent term, the PSRK EOS is similar to the original 
NC

SRK EOS. The PSRK EOS is defined as [7] mix = xi i (8)

i=1
RT a
P= (1) 
NC
v b v(v + b)
TCmix = xi TCi (9)
with the parameters b and a given by i=1

RTC 
NC 
NC
b = 0.08664 (2)
PC mix = x i x j i j (10)
i=1 j=1
R2 TC2
a = 0.42748 (3)  NC 4/3
PC 
Cmix = xi Ci 3/4 (11)
where is the Mathias and Copeman temperature-dependent i=1
term, which is a function of reduced temperature Tr = T/TC .
It is defined as Of course, the mixture molecular weight is given by the mole

2

3 2
fraction average
= 1 + C1 (1 Tr0.5 ) + C2 (1 Tr0.5 ) + C3 (1 Tr0.5 ) ,

NC

Tr < 1 (4) MWmix = xi MWi (12)

i=1

where i is a dummy variable for each compound in the mix-

2
= 1 + C1 (1 Tr0.5 ) , Tr > 1 (5) ture, mix is the mixture characteristic parameter, x is the mole
fraction, TCmix is the mixture critical temperature, MWmix is
where C1 , C2 and C3 are vapor pressure-dependent parame- the mixture molecular weight, mix is the mixture term,
ters for each compound. These parameters for different com- and Cmix is the mixture critical density.
pounds are given elsewhere [6]. It should be noted that C1 , C2 , and C3 are needed to cal-
culate by Eqs. (4) and (5) for pure compounds and Eq. (10)
for mixtures.
3. The NM saturated liquid density correlation for
pure compounds
5. The simplied model
Nasrifar and Moshfeghian presented the following corre-
lation [6]: As shown above, the NM correlation requires three pa-

 rameters, C1 , C2 , and C3 for each compound, that are not
s = C 0 1 + ( 1)1/3 (6) readily available for all compounds. In the absence of these
three parameters, the NM correlation fails to predict the den-
where s and C are saturated liquid density and crit- sity of pure compounds and their mixtures. The proposed
ical density (1/VC ) of the compound, respectively. They modification overcomes this barrier by replacing the PSRK
 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167
parameter with the original SRK term SRK . The parameter
SRK does not require the Ci parameters. It is defined as [9]

 2
SRK = 1 + m(1 Tr ) (13)
where m is given by [9]
m = 0.480 + 1.574 0.1762 (14)
The revised model after replacement has the following gen-
eral formula:


s = C 0 1 + SRK (SRK 1)1/3 (15)
where C is the critical density and the parameter SRK is a
new characteristic parameter for each compound.
The parameter 0 is the reference density and calculated
by Eq. (7) but is replaced by SRK or
0 = 1 + 1.169 1/3 + 1.818 2/3 2.658 3/3 + 2.161 4/3
(16)
The temperature-dependent variable is defined by
Tr
=1 (17)
SRK
Due to this modification, a new optimization had to be
done to find the new adjustable parameter SRK . MathCAD
2001 nonlinear regression tool was used to find the new SRK
that minimizes the following objective function:
N 

0i
1/3
f (SRKi ) = expi MW V 1 + SRKi (SRKi 1)
C 7. Results and discussion
i=1
(18)
where exp is the experimental density at point i. The initial
guess for the above objective function was the old found by
Nasrifar and Moshfeghian in the original work [6].
Using the above equation, the values of SRK for 76 pure
compounds from different classes were determined. They are
given in Table 1 . The critical properties and acentric factors
required for different compounds were taken from reference
[5].
In order to make comparison on a fair basis, similar proce-
dure was applied using the same collected data bank to find
the optimized values of for the original NM correlation [6]
and ZRA for the RackettSpencerDanner equation [4,5]. The
new optimized values of and ZRA are presented in Table 1.
Table 1 also contains the literature values of ZRA . In cases
that ZRA was not available, ZC was listed instead of ZRA and
is identified by adding c to the right of their values.
5.1. The mixing rules
In order to extend the use of the new model to multi-
component systems, the same mixing rules used by Nasrifar
and Moshfeghian (Eqs. 812) have been applied but replacing
by SRK and replacing by SRK .
159
6. Generalizing the simplied model
The characteristic parameters for pure compounds were
found, in general, to have no relation with other parameters
such as acentric factor, , or critical temperature, TC . A plot of
all optimized SRK as a function produced scattered points
all over the page and a single generalized expression for all
compounds could not be found.
However, analysis for the pure compounds according to
their family (i.e. paraffins, olefins, aromatics, etc.) showed
that one could express the characteristic parameter for normal
paraffins (nC1 nC10 ) as a function of acentric factor. Linear
regression was used to find the following relation:
= 0.1596 0.0319 (19)
Therefore, the revised model may be simplified further
by deleting the adjusted parameter requirement, SRK . The
easiest way to generalize the new model was to set SRK
equal to zero at the cost of lowering the accuracy. Therefore,
the proposed generalized correlation is
s = C 0 (for pure compounds) (20)
and
mix = cmix 0mix (for multicomponent systems) (21)
where cmix and 0mix are given by Eqs. (11) and (16), re-
spectively.
7.1. Pure compounds
In order to evaluate the accuracy of the proposed simpli-
fied correlation, a data bank of experimental data for several
classes of chemical compounds was collected. The saturated
liquid density was calculated at each experimental temper-
ature and compared with the experimental density. Table 2
presents these comparisons for the simplified model identi-
fied by simplified NasrifarMoshfeghian (SNM) with the ad-
justed parameter for each compound, the generalized SNM
model, i.e. without any parameters, and the original NM cor-
relation with the optimized parameters and with set equal
to zero. Overall, the simplified model gives accurate predic-
tion with an average absolute percent deviation (AAPD) of
0.58% for all points. Considering the fact that the SNM mod-
els requires less parameters, i.e. no need for C1 , C2 , and C3 ,
its accuracy compares well with that of the original NM and
RackettSpencerDanner equation with AAPD of 0.54% and
0.55%, respectively. Table 2 also presents the accuracy of
the NM EOS, MNM EOS, SRK EOS and VTSRK method.
As was expected, the overall accuracy of the density corre-
lations, even in their generalized forms, is better than any
of the EOS approaches and VTSRK method. Table 2 indi-
cates that among the three equations of state, MNM has the
160 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167

Table 1
Pure compound references and their optimized parameters
Compound Reference NP Tr range SRK 100 NM 100 Literature ZRA Optimized ZRA
1,3-Butadiene [13] 62 0.390.98 0.57510 0.38368 0.2712 0.2709
1-Butene [13] 11 0.460.70 2.09626 2.08502 0.2736 0.2732
1-Hexene [13] 12 0.540.94 2.42033 3.29786 0.2658 0.2643
1-Octene [13] 9 0.460.59 1.37209 1.42577 0.2600 0.2636
1-Propanol [13] 20 0.510.94 0.13014 0.01884 0.2541 0.2522
Acetic acid [14] 31 0.490.99 1.03473 0.74804 0.2225 0.2242
Acetone [14] 22 0.370.99 1.75281 1.61910 0.2477 0.2452
Acetylene [13,15] 20 0.620.91 0.07747 0.16669 0.2709 0.2700
Ammonia [16] 87 0.490.99 6.79976 6.95179 0.2465 0.2476
Argon [16] 80 0.560.99 3.25962 3.30836 0.2922 0.2929
Benzene [13,15] 73 0.501.00 1.44502 1.49163 0.2698 0.2683
Benzoic acid [13] 6 0.540.60 2.68664 1.65903 0.2484c 0.2483
Biphenyl [13,15] 23 0.440.93 4.33458 5.73051 0.2614c 0.2573
Butane [15,16] 79 0.330.99 0.13196 1.38194 0.273 0.2732
Carbon dioxide [15] 78 0.710.96 1.54186 1.56544 0.2722 0.2718
Carbon monoxide [13,15] 34 0.510.95 0.80200 0.65938 0.2896 0.2893
Chlorine [13,15] 38 0.440.96 1.30100 1.14069 0.2776 0.2767
Chlorobenzene [13] 15 0.460.91 4.46227 4.51904 0.2648c 0.2613
Chloroethane, R-160 [15] 18 0.530.71 6.09099 6.26916 0.2654 0.2677
cis-2-Butene [13] 7 0.510.65 1.12156 0.10363 0.2701 0.2708
cis-2-Pentene [13] 14 0.430.68 5.68825 6.03064 0.2671 2.7014
Cumene [13] 11 0.430.58 3.93381 4.30876 0.2617 2.6178
Cyclohexane [13] 9 0.510.64 0.45300 0.51907 0.2729 0.2729
Cyclohexene [13] 5 0.510.56 2.70939 2.73252 0.2797c 0.2730
Cyclopentane [13] 7 0.510.61 0.28797 0.70482 0.2745 0.2747
Cyclopentene [13] 5 0.560.64 1.79061 1.79997 0.2793c 0.2744
Decane [13,15] 19 0.420.97 5.12504 4.84551 0.2507 0.2522
Ethane [13] 25 0.331.00 1.46429 1.57101 0.2808 0.2807
Ethene [14] 17 0.370.94 0.46558 0.92536 0.2745 0.2815
Ethylbenzene [13] 24 0.300.67 2.94376 2.76001 0.2631c 0.2621
Ethylcyclopentane [13] 5 0.500.55 0.94253 0.87615 0.269c 0.2681
Ethylether [13] 21 0.590.99 0.10621 0.01280 0.2632 0.2644
Flourine [13] 19 0.370.97 3.03979 2.82235 0.2887 0.2884
H2 S [16] 14 0.770.98 0.59860 1.90606 0.2855 0.2825
Hydrogen [17] 20 0.420.99 19.75170 19.08160 0.306 0.3242
Isobutane [14] 45 0.280.98 3.10327 2.58999 0.2754 0.2749
Isobutylene [15] 9 0.490.68 0.98728 1.25487 0.2728 0.2728
Isopentane [13] 31 0.330.99 0.09888 0.14613 0.2717 0.2720
Isoprene [13] 5 0.590.65 4.21712 3.83292 0.265c 0.2649
Isopropanol [13] 32 0.380.99 1.10422 1.82015 0.2493 0.2517
Krypton [17] 16 0.240.96 4.50251 0.69000 0.2901 0.2901
Methane [16] 59 0.481.00 3.20525 3.17189 0.2892 0.2891
Methanol [15] 34 0.350.99 0.71947 0.93665 0.2334 0.2368
Methylcyclohexane [17] 30 0.480.98 0.57591 0.61382 0.2704 0.2700
Methylcyclopentane [13] 7 0.490.59 0.59017 0.53044 0.2711 0.2712
n-Butanol [13] 6 0.490.56 0.23343 0.85546 0.2538 0.2587
Neon [13] 39 0.550.99 5.63803 5.67280 0.3085 0.3076
n-Heptane [15] 24 0.361.00 1.87922 1.72683 0.2604 0.2609
n-Hexane [17] 33 0.360.99 1.19300 0.83596 0.2635 0.2644
Nitrogen [17] 31 0.510.98 0.79463 0.86475 0.2900 0.2895
Nonadecane [16] 23 0.421.00 3.71806 3.76801 0.2236 0.2283
Nonane [17] 25 0.390.99 3.60629 3.45148 0.2543 0.2547
Normal deuterium [17] 21 0.490.99 5.33454 4.23635 0.3144c 0.3124
n-Pentane [16] 22 0.320.99 0.62738 0.42676 0.2684 0.2686
Octadecane [17] 23 0.411.00 9.08709 8.60145 0.2275 0.2369
Octane [13] 17 0.420.99 3.64147 3.35286 0.2571 0.2564
Oxygen [17] 27 0.351.00 2.70491 2.93678 0.2905 0.2892
Pentadecane [17] 29 0.401.00 6.93421 7.12624 0.2429c 0.2385
Pentaflourochloroethane [15] 90 0.530.96 2.62285 3.95272 0.2729 0.2742
Phenylether [13] 15 0.640.83 1.76731 2.29413 0.2446 0.2523
Propadiene [13] 5 0.520.62 10.90360 10.52730 0.2584 0.2666
Propane [17] 33 0.271.00 0.25595 0.59160 0.2766 0.2767
Propene [15] 41 0.240.99 1.47939 1.23096 0.2779 0.2767
 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167 161

Table 1 (Continued).
Compound Reference NP Tr range SRK 100 NM 100 Literature ZRA Optimized ZRA
R-134 [15] 90 0.510.95 8.66475 8.68993 0.2713 0.2794
R-245 [16] 22 0.450.99 1.16965 0.76389 0.2675c 0.2663
R-32 [16] 16 0.571.00 6.66817 6.47377 0.2405c 0.2450
R-40 [16,13] 122 0.420.94 7.86026 7.73701 0.2679 0.2679
R-500 [15] 109 0.530.95 2.47818 1.74516 0.2813c 0.2756
R-502 [15,16] 86 0.480.96 0.54781 0.12267 0.2749c 0.2733
R-C318 [15,13] 64 0.520.95 1.04585 4.85882 0.2794c 0.2715
Sulfur dioxide [16] 23 0.460.98 3.29577 2.98628 0.2661 0.2658
Tetrachlouromethane, R-10 [16] 92 0.441.00 1.31517 1.33355 0.2722 0.2781
Toluene [15,13] 24 0.461.00 1.39931 1.48249 0.2644 0.2648
trans-2-Butene [13] 7 0.520.66 0.19733 0.20335 0.2720 0.2724
Xenon [16] 12 0.590.97 1.27292 1.40308 0.2829 0.2881
Total number of points: 2379.

lowest error. Even though volume translation of SRK im-
proves its accuracy from 12.46% to 8.01% AAPD, but it
is not as good as that of MNM with an overall AAPD of
5.30%.
Based on the compounds classifications, Table 3 shows the
comparison results between the simplified model and other
correlations and the equations of state. From Table 3, it is
obvious that the simplified model, even though requires less
parameters, gives almost the same overall accuracy as the
original NM correlation and even better than the RSD equa-
tion. For the paraffins, cyclic paraffins, halogenated paraffins,
olefins and cyclic olefins and aromatics, the RSD method
gives better accuracy; however, for ethers, liquid inorganic
gases, alcohols and miscellaneous compounds, the SNM is
more accurate. Table 3 also shows that the average absolute
percent deviation of the simplified model without any param-
eters (SRK = 0). It can be noted that the accuracy of SNM is
comparable with other methods.
Fig. 1 is a deviation plot for the SNM model for the pre-
diction of saturated liquid density of paraffinic hydrocarbons
(nC1 nC6 ) given in Table 1. The total number of points shown
in Fig. 1 is 251 and the average of liquid density percent devi-
ations (LDPDs) is 0.166%. The maximum deviations with
respect to experimental data occurred for n-butane with an av-
erage value of 0.27% and the smallest errors for n-hexane
0.02%. Liquid density percent deviation is defined as
 
CAL EXP
LDPD = 100 (22)
EXP
Fig. 2 is a deviation plot for the simplified model for the
prediction of saturated liquid density of halogenated paraf-
fins given in Table 1. The total number of points shown in

Fig. 1. Deviation plot for normal paraffins using the simplified model.
162 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167

Table 2
The AAPDa of several saturated liquid density correlation for pure compounds
Compound SNM SNM NM NM ( RSD RSD NM EOS MNM EOS SRK EOS VTSRK
() ( = 0) () = 0) literature optimized EOS
1,3-Butadiene 0.38 0.57 0.14 0.27 0.27 0.16 8.60 8.39 16.65 11.71
1-Butene 0.06 1.56 0.10 1.56 0.29 0.05 0.49 0.59 7.00 4.40
1-Hexene 0.37 1.92 0.41 2.48 1.13 0.28 2.21 1.88 12.63 3.24
1-Octene 0.28 1.20 0.21 1.23 2.52 0.08 6.57 5.93 10.66 1.06
1-Propanol 0.74 0.74 0.90 0.90 1.63 1.31 16.92 5.59 14.91 5.64
Acetic acid 0.56 0.89 0.48 0.66 2.75 2.68 24.36 22.13 33.64 26.63
Acetone 0.90 1.20 1.05 1.26 1.95 0.24 12.63 13.40 24.06 15.77
Acetylene 0.28 0.29 0.47 0.50 0.60 0.28 3.52 3.25 12.70 5.37
Ammonia 0.16 4.25 0.11 4.22 0.72 0.19 14.29 14.67 23.75 15.85
Argon 0.20 1.64 0.25 1.80 0.70 0.46 8.00 7.06 10.00 14.27
Benzene 0.79 1.02 0.74 0.94 0.89 0.65 8.72 8.61 17.50 11.34
Benzoic acid 0.05 2.42 0.11 1.61 0.17 0.16 20.89 4.87 17.58 6.80
Biphenyl 1.05 4.02 1.19 4.95 3.71 1.17 3.75 3.48 15.71 5.93
Butane 0.38 0.39 0.19 0.22 0.19 0.18 4.36 4.30 11.91 7.93
Carbon dioxide 0.06 0.78 0.11 0.74 0.29 0.26 1.64 1.48 11.18 3.76
Carbon monoxide 0.43 0.61 0.34 0.47 0.42 0.42 2.09 1.71 3.26 7.88
Chlorine 0.12 0.74 0.12 0.59 0.48 0.37 4.70 4.63 9.37 4.27
Chlorobenzene 1.45 4.15 1.33 4.01 2.84 1.23 4.71 5.15 14.81 5.36
Chloroethane, R-160 0.19 4.29 0.14 4.33 1.51 0.08 2.94 2.80 10.24 0.73
cis-2-Butene 0.09 0.85 0.12 0.14 0.47 0.07 0.38 0.37 8.19 3.09
cis-2-Pentene 0.07 4.30 0.12 4.48 2.05 0.06 2.99 2.12 8.10 3.43
Cumene 0.15 3.35 0.08 3.58 0.05 0.04 2.86 0.94 12.70 1.18
Cyclohexane 0.15 0.34 0.07 0.40 0.10 0.10 1.58 1.47 6.79 4.78
Cyclohexene 0.05 2.11 0.02 2.11 4.30 0.04 1.99 1.76 6.76 5.15
Cyclopentane 0.04 0.19 0.03 0.52 0.10 0.02 1.57 1.69 5.94 5.74
Cyclopentene 0.57 1.33 0.56 1.33 3.11 0.55 1.47 1.58 6.12 5.26
Decane 0.96 4.15 0.73 3.92 1.11 1.05 7.52 4.88 18.16 9.00
Ethane 0.73 1.14 0.55 1.23 0.36 0.36 4.21 3.95 9.42 9.05
Ethene 0.19 0.28 0.08 0.60 4.39 0.24 1.92 1.71 5.86 6.35
Ethylbenzene 0.68 2.66 0.46 2.51 0.74 0.20 7.47 4.65 19.16 15.47
Ethylcyclopentane 0.06 0.77 0.04 0.72 0.62 0.01 3.11 1.85 9.17 2.59
Ethylether 0.32 0.33 0.25 0.29 0.79 0.24 5.05 4.73 15.36 7.52
Flourine 0.22 1.64 0.18 1.55 0.24 0.18 2.27 2.21 3.63 9.93
H2 S 0.52 0.56 0.14 0.73 1.42 0.94 3.02 2.87 12.43 6.50
Hydrogen 1.58 6.22 1.70 6.09 9.54 1.07 28.06 3.19 11.63 20.34
Isobutane 0.56 2.49 0.43 2.20 0.36 0.21 1.70 1.77 8.16 5.97
Isobutylene 0.10 0.79 0.12 0.97 0.08 0.08 0.57 0.64 7.14 4.24
Isopentane 0.56 0.57 0.43 0.44 0.32 0.31 3.42 3.04 10.35 5.64
Isoprene 0.06 2.85 0.10 2.63 0.09 0.03 7.00 6.53 12.31 1.91
Isopropanol 0.94 1.24 0.73 1.61 2.30 2.15 26.93 11.58 18.22 8.82
Krypton 3.31 3.31 3.27 3.27 3.89 3.89 5.26 7.27 6.60 5.56
Methane 0.46 1.56 0.28 1.71 0.25 0.24 3.21 3.48 5.72 9.84
Methanol 1.73 2.10 1.37 1.97 3.89 3.65 23.24 11.54 26.99 18.60
Methylcyclohexane 0.49 0.57 0.33 0.49 0.56 0.45 9.07 7.78 15.65 9.78
Methylcyclopentane 0.07 0.51 0.04 0.44 0.08 0.03 1.70 1.28 7.69 4.03
n-Butanol 0.11 0.33 0.15 0.77 3.45 0.33 13.96 13.87 12.14 0.33
Neon 0.46 2.94 0.33 3.09 0.59 0.37 11.99 9.17 8.94 18.54
n-Heptane 0.51 1.52 0.43 1.28 0.31 0.24 5.10 4.14 15.31 5.99
n-Hexane 0.28 0.82 0.16 0.63 0.46 0.25 4.70 3.74 14.15 4.98
Nitrogen 0.25 0.48 0.15 0.49 0.43 0.42 3.02 2.66 5.03 9.33
Nonadecane 3.71 5.21 3.89 5.64 4.17 1.77 57.18 11.24 29.04 20.97
Nonane 0.66 2.92 0.48 2.66 0.49 0.48 4.84 4.69 17.48 8.32
Normal deuterium 1.42 1.99 1.18 1.92 1.28 0.96 14.82 3.05 8.32 16.29
n-Pentane 0.38 0.61 0.22 0.35 0.16 0.14 3.48 2.84 11.98 4.84
Octadecane 1.21 7.04 1.04 6.52 6.78 0.26 48.73 9.56 23.95 15.34
Octane 0.51 2.69 0.30 2.39 0.65 0.40 3.43 3.92 16.51 7.41
Oxygen 0.29 1.40 0.21 1.59 0.75 0.30 3.62 3.94 5.00 10.68
Pentadecane 1.04 5.31 1.13 5.40 3.10 0.20 33.73 7.00 23.71 15.11
Pentaflourochloroethane 0.12 1.51 0.21 2.50 0.77 0.15 3.62 3.30 7.97 4.17
Phenylether 0.24 1.27 0.72 1.73 5.20 0.44 4.58 3.05 16.28 7.05
Propadiene 0.12 7.22 0.16 7.08 5.73 0.06 8.74 8.12 11.90 1.11
Propane 0.49 0.50 0.34 0.51 0.67 0.67 4.08 3.70 10.76 7.91
Propene 0.57 1.27 0.45 1.04 0.90 0.68 8.04 10.61 14.06 13.00
 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167 163

Table 2
The AAPDa of several saturated liquid density correlation for pure compounds
Compound SNM SNM NM NM ( RSD RSD NM EOS MNM EOS SRK EOS VTSRK
() ( = 0) () = 0) literature optimized EOS
R-134 3.64 8.42 3.79 8.45 7.33 3.05 10.84 10.23 2.52 8.03
R-245 0.39 0.82 0.30 0.60 0.83 0.37 7.38 6.52 15.79 8.70
R-32 1.05 4.55 1.04 4.35 3.77 1.24 15.27 15.57 24.43 17.41
R-40 0.41 5.10 0.29 4.95 0.18 0.18 5.64 5.16 11.44 1.59
R-500 0.32 1.76 1.07 0.05 3.21 0.24 10.62 10.92 3.90 7.22
R-502 0.23 0.50 0.10 0.13 0.91 0.07 1.60 1.56 9.17 4.42
R-C318 0.29 0.87 0.48 3.15 4.74 0.16 7.21 6.45 6.89 4.69
Sulfur dioxide 0.37 2.08 0.44 1.87 0.63 0.58 2.72 2.97 12.98 4.09
Tetrachlouromethane, R-10 0.12 0.80 0.18 0.90 3.81 0.29 5.63 5.80 10.39 8.79
Toluene 0.43 1.22 0.36 1.19 0.31 0.28 3.11 3.39 13.83 4.56
trans-2-Butene 0.11 0.18 0.15 0.23 0.25 0.07 1.79 1.58 7.02 4.36
Xenon 0.32 0.56 0.16 0.67 3.09 0.12 2.31 3.58 7.45 7.83
Maximum AAPD 3.71 8.42 3.89 8.45 9.54 3.89 57.18 22.13 33.64 26.63
Overall AAPD 0.58 2.01 0.54 2.02 1.72 0.55 8.28 5.30 12.46 8.01

a AAPD = 100

s cali
NPT

NPTs exp i 1 .
i

Table 3
AAPDs for prediction of the saturated liquid densities of different classes of compounds using different methods
Class Number of SNM SNM NM NM ( RSD RSD NM EOS MNM EOS SRK EOS VTSRK
points () ( = 0) () = 0) literature optimized EOS
Paraffins 487 0.83 2.46 0.71 2.34 1.29 0.45 12.65 4.82 15.11 9.22
Cyclic paraffins 58 0.16 0.48 0.10 0.51 0.29 0.12 3.41 2.81 9.05 5.38
Halogenated paraffins 709 0.68 2.86 0.76 2.94 2.71 0.58 7.08 6.83 10.27 6.58
Olefins and cyclic olefins 229 0.22 1.78 0.21 1.82 1.75 0.18 3.75 3.67 9.81 4.91
Aromatics 170 0.76 2.74 0.69 2.86 1.42 0.60 5.10 4.37 15.62 7.31
Ethers 36 0.28 0.80 0.49 1.01 3.00 0.34 4.82 3.89 15.82 7.29
Liquid inorganic gases 539 0.65 1.95 0.58 1.94 1.63 0.70 7.19 4.70 9.30 10.34
Alcohols 92.00 0.88 1.10 0.79 1.31 2.82 1.86 20.26 10.65 18.07 8.35
Miscellaneous 59.00 0.50 1.5 0.55 1.18 1.62 1.03 19.29 13.47 25.09 16.40
Overall AAPD 2379 0.55 1.74 0.54 1.77 1.84 0.65 9.28 6.13 14.24 8.42

Fig. 2. Deviation plot for halogenated paraffins using the simplified model.
164 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167

Table 4
Multi-component systems AAPD for the simplified model
Reference Components NP Correlation (%AAPD) EOS (%AAPD)

1 2 3 4 5 6 7 8 SNM () SNM ( = 0) NM () NM ( = 0) RSD optimized NM MNM SRK VT SRK

[18,19] N2 C1 29 0.73 2.27 0.65 2.20 1.21 1.77 1.30 0.97 1.75
[18] N2 C2 4 0.09 1.08 0.11 1.39 0.07 4.13 3.36 4.24 1.43
[18] N2 C3 6 1.03 0.79 0.11 0.39 0.78 3.88 2.92 7.71 0.15
[18,19] C1 C2 39 0.19 1.72 0.13 1.85 0.16 1.93 2.67 1.89 1.71
[18,19] C1 C3 32 0.34 1.51 0.23 1.80 0.67 1.21 2.09 2.46 1.48
[18,20] C1 iC4 24 0.58 0.97 0.31 1.25 1.18 0.94 1.07 2.72 1.27
[18,20] C1 nC4 23 0.75 0.95 0.30 1.44 1.06 5.22 0.56 7.32 5.39
[19,21] N2 C1 C2 11 0.35 2.01 0.42 2.09 1.23 0.61 1.19 0.44 2.42
[19,21] N2 C1 C3 4 0.15 1.82 0.21 1.87 1.43 0.59 0.81 0.83 2.14
[22] N2 C1 nC4 4 0.14 1.77 0.15 1.92 1.76 1.25 0.49 0.74 1.99
[19,21] C1 C2 C3 14 0.26 1.45 0.08 1.61 0.53 1.75 2.34 2.84 1.48
[22] C1 C2 C3 iC4 9 0.58 1.16 0.36 1.38 1.19 0.59 0.73 1.71 1.48
[22] C1 C2 C3 nC4 9 0.26 1.59 0.13 1.79 1.42 0.84 0.58 1.51 1.80
[21] N2 C1 C2 C3 4 0.13 1.95 0.15 1.96 0.91 0.38 1.31 0.74 1.96
[21] N2 C1 C2 C3 iC4 4 0.14 1.59 0.15 1.81 1.21 0.43 1.20 1.43 1.91
[21,22] N2 C1 C2 C3 nC4 6 0.25 1.61 0.22 1.78 1.11 0.51 0.94 1.46 1.85
[22] N2 C1 C2 C3 iC4 nC4 15 0.32 1.53 0.24 1.63 0.81 0.46 1.02 1.28 1.56
[22] N2 C1 C2 C3 iC4 nC4 iC5 nC5 13 0.37 1.45 0.21 1.59 0.63 0.59 1.27 1.75 1.54
[22] C1 C2 C3 iC4 nC4 iC5 nC5 9 0.59 1.86 0.46 2.00 1.00 0.85 1.54 1.72 1.98
[19,21] C1 C2 C3 iC4 nC4 12 0.42 1.44 0.25 1.59 0.74 0.47 1.23 1.59 1.51
[23] 1-PrOH nC7 24 1.96 1.40 2.09 1.53 2.16 8.30 6.05 12.24 2.84
[24] 1-PrOH Acetone 17 1.00 0.71 1.22 0.86 1.85 16.47 6.30 16.54 2.37
[23,25] 1-BuOH C7 40 1.01 0.37 1.05 0.92 0.37 6.00 7.20 16.16 8.46
[25] 1-BuOH C5 17 1.21 0.84 1.32 1.50 0.38 5.21 6.93 9.48 3.96
[25] 1-BuOH C6 17 1.23 0.67 1.24 1.36 0.44 5.77 3.70 10.84 4.15
[25] 1-BuOH C8 17 1.27 0.52 1.30 0.73 0.53 15.81 11.96 32.95 25.14
[24] MeOH 1-PrOH 25 1.47 1.19 1.61 1.23 2.94 21.53 5.82 18.12 2.55
[26] C10 CO2 48 3.74 6.55 4.08 6.72 3.64 8.11 2.98 19.33 4.17
[28] Cyc-C6 C3 11 0.38 0.14 0.37 0.58 0.13 0.64 0.61 7.45 1.33
[27,29] Cyc-C6 C6 78 0.39 0.22 0.26 0.31 0.09 2.02 1.20 8.84 1.74
[27] Cyc-C6 C7 33 0.85 0.33 0.81 0.38 0.34 2.90 2.00 9.36 2.08
[29] Cyc-C6 C8 33 0.49 0.96 0.45 0.91 0.44 2.00 1.76 11.06 1.31
[29] Cyc-C6 C9 33 0.19 1.33 0.20 1.27 0.83 0.76 2.34 12.12 1.18
[29] Cyc-C6 C10 33 0.15 2.09 0.14 0.95 1.32 2.49 2.82 13.32 1.10
[28] C 6 H6 nC4 10 1.90 1.31 2.63 1.46 2.06 1.49 1.47 6.44 2.90
[30] C10 C9 11 0.21 4.13 0.16 3.39 0.10 2.36 3.49 16.54 1.10
[30] C8 C9 11 0.30 2.90 0.26 2.76 0.60 1.29 2.61 14.90 1.17
[30] C7 C10 11 0.19 3.08 0.14 2.93 0.22 2.38 2.88 15.05 1.30
[30] C7 C9 11 0.16 2.25 0.12 2.16 0.19 1.63 2.42 14.02 1.33
[30] C7 C8 11 0.51 1.81 0.42 1.73 0.63 2.85 1.91 13.15 1.44
[30] C6 C10 11 0.21 2.74 0.17 2.60 0.46 2.39 2.62 14.49 1.26
[30] C6 C9 11 0.18 1.90 0.08 1.83 0.15 1.20 2.15 13.39 1.31
[30] C6 C8 11 0.53 1.46 0.34 1.40 0.45 2.44 1.60 12.45 1.42
[30] C6 C7 11 0.46 0.78 0.24 0.79 0.22 2.86 1.37 11.34 1.65
[30] C5 C6 11 0.38 0.30 0.12 0.36 0.06 2.04 0.98 9.65 1.36
[30] C5 C7 11 0.34 0.65 0.18 0.68 0.08 2.53 1.36 10.60 1.34
[30] C5 C8 11 0.41 1.33 0.27 1.28 0.26 2.11 1.61 11.78 1.10
[30] C5 C9 11 0.09 1.76 0.09 1.71 0.41 0.83 2.18 12.81 0.98
[30] C5 C10 12 0.24 2.62 0.23 2.48 0.82 2.49 2.65 13.98 0.90
[31] R-32 R-134a 43 0.86 2.46 1.06 2.15 1.66 10.59 10.74 21.86 10.65
[18] iC4 nC4 4 1.08 2.47 0.16 1.72 0.49 0.90 0.67 8.77 0.21
[18] C3 nC4 8 0.95 0.86 0.45 0.41 0.58 2.19 1.52 8.10 0.60
[18] C3 iC4 8 0.87 2.16 0.14 1.50 0.57 2.42 1.63 8.09 0.29
[18] C2 nC4 8 0.45 0.35 0.34 0.87 0.92 2.77 2.12 6.81 2.19
[18] C2 iC4 6 0.36 0.24 0.09 0.36 0.43 3.25 2.49 6.26 0.57
[18] C2 C3 12 0.33 0.47 0.20 0.69 0.30 3.53 2.72 5.80 0.94
[32] C3 nC8 12 3.44 4.71 3.71 4.84 2.47 9.23 9.03 21.78 14.72
[24] Acetone MeOH 1-PrOH 4 1.38 0.76 1.47 0.78 2.03 18.11 4.25 19.16 1.48
Maximum Absolute Percent Deviation (AAPD) 3.74 6.55 4.08 6.72 3.64 21.53 11.96 32.95 25.14
Average Absolute Percent Deviation (AAPD) 0.67 1.57 0.59 1.61 0.87 3.63 2.70 9.32 2.61
Total number of experimental points: 978.

Fig. 2 is 345 and the average of liquid density percent devia-
tions is 0.095%. The maximum deviations with respect to
experimental data occurred for R-32 with an average value
of 0.183% and the smallest error was found 0.033% for
R-160.
7.2. Multi-component systems
As it was done for pure compounds, experimental data
bank was composed for different multi-component systems.
The saturated liquid densities of 58 multi-component systems
Table 5
The AAPDsa for 17 multi-component systems using different methods
System Range T (K) Reference NP SNM NM RSD optimized NM EOS MNM EOS SRK EOS VTSRK EOS
(0.04750.4924)N2 + (0.50750.9525)C1 94140 [18] 29 0.73 0.65 1.21 1.77 1.30 0.97 1.85
0.0593 N2 + 0.9407 C2 105120 [18] 4 0.09 0.11 0.07 4.13 3.36 4.24 1.43

A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167

(0.02010.0674)N2 + (0.93260.9798)C3 105115 [18] 6 1.03 0.11 0.78 3.88 2.92 7.71 0.15
(0.35460.6800)C1 + (0.31990.6454)C2 105140 [18] 39 0.19 0.13 0.16 1.93 2.67 1.92 1.67
(0.29540.8579)C1 + (0.14200.7046)C3 105130 [18] 32 0.34 0.23 0.57 1.21 2.09 2.46 1.48
(0.7798)C1 + (0.07210.7798)iC4 120130 [18] 24 0.58 0.31 1.18 0.94 1.07 2.72 1.27
0.0593N2 + 0.8907C1 + 0.04998nC4 110125 [22] 4 0.14 0.15 1.76 1.25 0.49 0.74 1.99
0.8604C1 + 0.0460C2 + 0.0470C3 + 0.0457iC4 115135 [22] 9 0.58 0.36 1.19 0.59 0.73 1.71 1.48
(0.76440.9737)C1 + (0.00800.0073)C2 + (0.00340.02612)C3 105125 [21] 14 0.26 0.08 0.53 1.75 2.35 2.84 1.48
(0.05050.338)N2 + (0.34140.8409)C1 + (0.10860.3206)C2 105120 [21] 11 0.35 0.42 1.23 0.61 1.19 0.44 2.42
(0.4970.0995)N2 + (0.79770.9055)C1 + (0.04970.1028)C3 105120 [21] 4 0.15 0.21 1.43 0.59 0.81 0.83 2.14
0.0425N2 + 0.8130C1 + 0.0475C2 + 0.0487C3 105120 [21] 4 0.13 0.15 0.91 0.38 1.31 0.74 1.96
0.85443C1 + 0.05042C2 + 0.04038C3 + 0.02577iC4 + 0.02901nC4 105120 [21] 12 0.42 0.25 0.74 0.47 1.23 1.59 1.51
0.0490N2 + 0.8060C1 + 0.0468C2 + 0.0482C3 + 0.05iC4 105120 [21] 4 0.14 0.15 1.21 0.43 1.20 1.43 1.91
0.0554N2 + 0.7909C1 + 0.0560C2 + 0.0500C3 + 0.0477nC4 105110 [21] 6 0.25 0.22 1.11 0.51 0.94 1.46 1.85
0.0425N2 + 0.8130C1 + 0.0475C2 + 0.0487C3 + 0.0242iC4 + 0.0241nC4 105120 [21] 15 0.32 0.24 0.81 0.46 1.02 1.28 1.56
0.8513C1 + 0.0576C2 + 0.0481C3 + 0.0430nC4 115135 [22] 9 0.26 0.13 1.42 0.84 0.58 1.51 1.80
Overall AAPD 226 0.35 0.23 0.96 1.28 1.49 2.03 1.64

a AAPD = 100

s cali
NPT

NPTs exp i 1 .
i

165
166 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167
consisting of 978 points were calculated using the simplified
model and then a comparison with the experimental data was
done. Table 4 shows the average absolute percent deviation
for the tested mixtures for the two cases: the simplified model
with the adjusted parameter for each compound (SRK ) and
the generalized model (SRK = 0). From this table, one can
see that the overall average absolute percent deviation for all
systems is 0.67% with the adjusted parameters and 1.57% for
the generalized model. Table 4 also presents the AAPD for the
two cases of the original NM correlation, RSD equation, NM
EOS, MNM EOS, SRK EOS and VTSRK. Table 4 indicates
that the accuracy of the SNM method is the second after the
original NM correlation. From Table 4, it can be seen that the
MNM EOS (AAPD = 2.70%) is the most accurate among the
three equations of state and almost as accurate as the volume
translated SRK (AAPD = 2.61%).
Furthermore, 17 LNG multi-component systems have
been considered for evaluation of the SNM with respect
to other methods and the comparison results are shown in
Table 5. The methods tested are: the simplified model with
the adjusted parameters, the original NM correlation, RSD,
and NM EOS, MNM EOS, SRK EOS and VTSRK. Table 5
shows the multi-component systems, the temperature range
and the source of experimental data. From Table 5, it is obvi-
ous that the simplified model gives accurate results and it is
second most accurate with respect to all other methods. The
original NM correlation also gives excellent predictions for
the tested systems. It is interesting to note that for the LNG
systems consisting of mostly methane, the NM EOS gives
the most accurate results among the equations of states. It
should be mentioned that NM EOS was developed based on
light hydrocarbon components and its accuracy decreases for
heavier hydrocarbons.
8. Conclusions and recommendations
The liquid density correlation by Nasrifar and Mosh-
feghian has been modified. The PSRK EOS temperature-
dependent term has been replaced with the original SRK EOS
temperature-dependent term. The SRK term does not require
any parameters, whereas the PSRK term requires three pa-
rameters for each compound. In order to maintain, or im-
prove, the accuracy of the modified correlation, the adjusted
parameters have been re-optimized. The simplified model
has been tested for 76 pure compounds consisting of 2379
experimental points and 58 multi-component systems con-
sisting of 978 points. The average absolute percent devia-
tion was 0.58% for the pure compounds and 0.67% for the
multi-component systems. The simplified model has been
generalized by setting a value of zero for the only fitting pa-
rameter. The generalized correlation gave AAPD of 2.01%
for the pure compounds and 1.57% for the multi-component
systems. Near the critical point (reduced temperature in the
range 0.971.00), the density of 45 pure compounds consist-
ing of 114 points has been calculated using the simplified
correlation and then compared with the experimental data.
Average absolute percent deviation for these compounds was
found to be 1.28%.
In order to make fair comparison with the original
NasrifarMoshfeghian correlation and the SpencerDanner
modification of Rackett equation, the adjustable parameters
in these two methods, namely and ZRA , were re-optimized
using the same pure component data bank and the same
procedure as was done for the proposed model. The op-
timized parameters determined in this work are reported
in Table 1. In all three methods, SNM, NM and RSD, the
optimized parameters were used to predict the liquid density
of mixtures without any further fitting or optimization. In
case of equations of states, no fitting was done and no binary
interaction parameters were used. The proposed simplified
model has shown comparable accuracy with the original
NasrifarMoshfeghian method and the SpencerDanner
modification of Rackett equation for pure components
but is a little less accurate than the original NM but more
accurate than the SpencerDanner modification of Rackett
equation for multi-component systems. Its accuracy is much
better than that of the three equations of state tested and the
volume translated SRK EOS for pure compounds and multi-
component systems. The modified NasrifarMoshfeghian
EOS gave the best results among the three equations of state
tested.
In the light of the results obtained in this study and in order
to improve the accuracy of the proposed model even further,
it is recommended that the global expression for 0 , Eq. 16,
be optimized based on the SRK temperature-dependent term.
It is also recommended that the generality of the original
NasrifarMoshfeghian correlation be explored and tested
further using other equations of state temperature-dependent
term. The authors have already undertaken the study on
these items and preliminary results are promising.
List of symbols
a attraction parameter, Pa m6 k mol2
b molecular co-volume, m3 k mol1
C1 , C2 , C3 parameters of Mathias and Copeman, Eq. (4)
EOS equation of state
F objective function
MNM modified NasrifarMoshfeghian
MW molecular weight
NC number of components
NM NasrifarMoshfeghian
NP number of points
P pressure, Pa
R universal gas constant, 8.314 J mol1 K1
T temperature, K
SNM simplified NasrifarMoshfeghian
SRK SoaveRedlichKwong
N, V Specific volume, m3 mol1
VTSRK volume translated SoaveRedlichKwong
RSD SpencerDanner modification of Rackett
X liquid mole fraction
 A. Mchaweh et al. / Fluid Phase Equilibria 224 (2004) 157167 167

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