Fluid Phase Equilibria 317 (2012) 5258

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Fluid Phase Equilibria

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Prediction of volumetric properties of uids for oil and gas applications

Laura A. Pellegrini a , Stefania Moioli a, , Simone Gamba a , Paola Ceragioli b
a
Dipartimento di Chimica, Materiali e Ingegneria Chimica G. Natta, Politecnico di Milano, Piazza Leonardo da Vinci 32, I-20133 Milano, Italy
b
Eni E&P Division, Via Emilia 1, I-20097 San Donato Milanese, Milano, Italy

a r t i c l e i n f o a b s t r a c t

Article history: Cubic equations of state are commonly used by the petroleum industry for predicting the phase behavior
Received 27 October 2011 and the volumetric properties of hydrocarbon uids. However, the volumetric estimates are not as accu-
Received in revised form rate as vaporliquid equilibrium ones. The present work aims at improving the prediction of density by
13 December 2011
the use of a proper volume translation correlation. The proposed method, developed from experimental
Accepted 18 December 2011
data for alkanes up to twenty-four carbon atoms and for aromatic compounds up to nonylbenzene, shows
Available online 24 December 2011
its reliability for a wide range of temperatures, and for saturated and monophasic liquid and for single
components and mixtures as well.
Keywords:
Volume translation 2011 Elsevier B.V. All rights reserved.
SRK EoS
PR EoS
Pure compound
Mixture

1. Introduction with the consistency of VLE calculation ensured by Pneloux-like

Cubic equations of state, in particular the SoaveRedlichKwong
(SRK) EoS [1] and the PengRobinson (PR) EoS [2], have a good
accuracy in representing vaporliquid equilibrium (VLE) of uid
mixtures when dealing with hydrocarbons and related compounds.
In this case, binary interaction parameters (kij ) can be successfully
predicted [35]. Other methods based on non-classic mixing rules
[610] could be successfully used but in some cases, for instance
in reservoir conditions, they may be too demanding in terms of
computational time. This is the reason why SRK and PR EoSs are
widely used in commercial softwares to predict phase behavior and
properties of hydrocarbon uids.
However, these equations do not provide an accurate enough
estimation of volumetric properties (especially concerning with the
liquid phase). Since a reliable prediction of volumetric properties
is crucial in many applications such as, e.g., reservoir charac-
terization and design of pipelines and product facilities several
volume translation-based methods (that represent improvements
over the original correlation proposed by Pneloux et al. [11]) aim-
ing at enhancing the cubic EoS molar volume calculation, have been
proposed. These volume shift-based methods have the advantage
to retain the computational simplicity of a cubic EoS coupled
Corresponding author. Tel.: +39 02 2399 3237; fax: +39 02 7063 8173.
E-mail addresses: laura.pellegrini@polimi.it (L.A. Pellegrini),
stefania.moioli@mail.polimi.it (S. Moioli), simone.gamba@mail.polimi.it (S. Gamba),
Paola.Ceragioli@eni.com (P. Ceragioli).
translations.
Pneloux et al. [11] proposed a very simple correction c for SRK
calculated volumes:
c = vSRK vcor (1)
where c is the volumetric shift, vSRK
is the saturated liquid molar
volume calculated by the original EoS and vcor is the correct (exper-
imental) saturated liquid molar volume at TR = 0.7. The predictive
original correlation, proposed by Pneloux et al. [11] for SRK and
applicable to pure hydrocarbons up to n-decane, is:
 RT 
C
c = 0.40768 (0.29441 ZRa ) (2)
PC
where TC and PC are the critical properties of the pure compound
and ZRa is the Rackett compressibility factor.
Improved volume translation correlations found in literature
(i.e., correlations for c prediction) have been developed on the
basis of saturated liquid density data alone or, more seldom, exclu-
sively for compounds far from saturation [12]. They can or cannot
be temperature-dependent and they use as independent variable
either the molecular weight or the normal boiling point of the com-
ponent to be characterized [1216].
For the sake of completeness, it deserves to be mentioned that
literature also reports c correlations for both SRK and PR EoSs whose
parameters are based on critical compressibility factors (i.e., critical
volumes) [1720] and most of them, when dealing with the sub-
critical region, have been developed on the basis of saturated liquid
density data alone. In this work, NBP-based parameters have been

0378-3812/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.uid.2011.12.022
 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258 53

developed, since in petroleum industry NBP is used to characterize a) 0.036

oil cuts as well and it is a readily available datum. Moreover, sim-
ple correlations that allow the estimation of NBP and TC for heavy 0.032
hydrocarbons have already been developed [21,22]. 0.028
A comparison between the prediction capability over a wide

c* [dm3/mol]
range of temperature and pressure for several c correlations, has 0.024
been reported by de SantAna et al. [23]. Good prediction capability n-Nonane SRK EoS
0.020 n-Nonane PR EoS
was shown by Jhaveri and Youngren [14] and Ungerer and Batut
[12] correlations. 0.016 n-Butylbenzene SRK EoS
Jhaveri and Youngren [14] proposed a volume shift parameter n-Butylbenzene PR EoS
expressed as a dimensionless factor s: 0.012

c 0.008
s= (3)
b
0.004
where b is the co-volume and s is a power function of the molecular
weight: 0.000
0.42 0.47 0.52 0.57 0.62 0.67 0.72
1d
s= (4) TR
MW e
0.036
Values of coefcients d and e for the light components up to n- b)
hexane and for n-alkylcyclohexanes and n-alkylbenzenes were SRK EoS
0.030
determined [14].
PR EoS
Ungerer and Batut [12] suggested an expression linearly depen- 0.024
dent on temperature:

c* [dm3 /mol]
0.018
c(T ) = A T + B (5)
0.012
where both A and B are linearly dependent on the molecular weight
(MW): 0.006
3
A [cm /(mol K)] = 0.023 0.00056MW (6) 0.000
3
B [cm /mol] = 34.5 0.4666MW (7)
-0.006
The above expression has been developed on the basis of high pres-
-0.012
sure experimental liquid molar volume of some hydrocarbons up
0.70 0.75 0.80 0.85 0.90 0.95 1.00
to 13 carbon atoms.
In their comparison work, de SantAna et al. [23] also reported TR
the drawbacks of the analyzed correlations that are applied to PR
Fig. 1. Difference (c*) between the liquid molar volume predicted by the EoSs
EoS. In particular, the correlations developed using saturated liquid
without volume shift and the experimental molar volume (in monophasic liquid
molar volumes give good results at low pressure while the correla- conditions) for: (a) n-nonane and n-butylbenzene; (b) n-butane.
tion by Ungerer and Batut [12] quickly diverges when approaching
the critical temperature (also for TR < 0.95) in saturated liquid vol- molar volume (i.e., the experimental value of c, indicated as c*) has
ume prediction. been determined. Thus c* has been computed as:
The present work aims at improving c prediction for a wider
range of operating conditions, i.e. not only for saturated but also c = vcalc
EoS without volume shift
vexp (8)
for liquid phase conditions, checking the reliability of the proposed The critical parameters of pure compounds were taken from Reid
volume translation when extended to mixtures. In order to develop et al. [24] and from Yaws [25].
an expression valid for a wider range of compounds, both in satu- An initial distinction between components in saturation condi-
rated and monophasic liquid state, many set of experimental data tion and components in single phase condition was made, in order
have been considered. These concern alkanes up to twenty-four to develop a complete study of the matter.
carbon atoms, aromatic compounds and acid gases, such as carbon
dioxide and hydrogen sulde. 2.1. Monophasic liquid conditions

2. Determination of the difference between the molar
volumes calculated by the equations of state (SRK, PR) and
the experimental values
As already stated in Section 1, SRK and PR EoSs are widely used
in commercial softwares both in reservoir and downstream equip-
ment and this is the reason why these two equations have been
considered in this work.
In order to focus on the volume translations to be applied, liq-
uid molar volumes have been calculated by the SRK and PR EoSs
(without considering any volume shift) and compared with the
corresponding experimental values. That is, the difference between
the liquid molar volume predicted by the EoSs and the experimental
Experimental data for alkanes [2635] and aromatic compounds
[36,37] have been taken from literature.
In Fig. 1, c* values are shown for some of the analyzed compo-
nents.
For the experimental conditions considered, cubic equations
of state give a better prediction of volumetric properties for aro-
matic compounds than for alkanes with the same number of carbon
atoms; it has to be taken into account that experimental values for
the former ones are available at lower reduced temperature than
the latter ones.
c* varies with both temperature and pressure. Generally, pres-
sure has not so great an inuence as temperature has: huge
pressure variations cause c* variations which are comparable (same
54 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258
0.120
n-Heptane SRK EoS
0.100
n-Heptane PR EoS
0.080 Benzene SRK EoS
c* [dm3/mol]
Benzene PR EoS
0.060
0.040
0.020
0.000
-0.020
0.3 0.4 0.5 0.6 0.7 0.8
TR
Fig. 2. Difference (c*) between the liquid molar volume predicted by the EoSs with-
out volume shift and the experimental molar volume (for saturation conditions) for
n-heptane and benzene.
order of magnitude) to those generated by temperature variations
of only few Kelvins. The little inuence of pressure on the obtained
results of volume translation allows us to assume, as already done
in literature, that c could be expressed as a function of tempera-
ture alone, instead that as a function of temperature and pressure,
leading to a simpler expression.
2.2. Saturated conditions
Saturated liquid density experimental data have been taken
from several sources for both n-alkanes [26,30,3848] and aromatic
compounds [4960].
In Fig. 2, some results for saturated density c* are shown.
The values of c* strongly increases when approaching the crit-
ical temperature as expected since cubic EoSs are not able to well
represent properties of a compound near its critical point.
The same c* behavior can be also observed, for carbon dioxide
and hydrogen sulde whose experimental data [61,62] are avail-
able in literature.
3. Determination of the expression for the volumetric
translation and relevant parameters
The aim of the work is to develop a new expression for c to be
easily implemented in commercial softwares. As already stated in
Section 1, no previous work in literature provided correlations valid
for compounds both in liquid phase and at saturation conditions.
As a matter of fact, implementing a single expression, valid for
both cases and wide temperature ranges, is, when possible, gen-
erally simpler and less demanding than considering two different
correlations.
For the sake of simplicity, two different functions, one for each
hydrocarbon family (alkanes and aromatics), have been developed.
By the new proposed correlation c is calculated accounting
for the given compound characteristics (normal boiling point and
critical temperature) and the operating conditions (temperature).
Dependence on pressure is neglected, according to its denitely
lower inuence, as derived from the previous analysis.
By observing Figs. 1 and 2, it can be noticed that the dependence
of c on the reduced temperature TR is, as expected, strongly con-
ditioned by the proximity to the critical point (i.e., c varies more
strongly when the reduced temperature approaches 1).
For the range of operating conditions of interest (that comprises
reduced temperatures lower than 0.95) the following expression,
with quadratic dependence on TR , has been developed:
c(TR ) = A TR2 + B TR + D (9)
A, B and D depend on the reduced normal boiling point of the given
compound (NBPR ) according to:
A = a1 NBPR2 + a2 NBPR + a3 (10)
B= b1 NBPR2 + b2 NBPR + b3 (11)
D= d1 NBPR2 + d2 NBPR + d3 (12)
The proposed general expression is then:
c(TR ) = a1 NBPR2 TR2 + a2 NBPR TR2 + a3 TR2 + b1 NBPR2 TR
+ b2 NBPR TR + b3 TR + d1 NBPR2 + d2 NBPR + d3 (13)
0.9 1.0
3.1. n-Alkanes and aromatic compounds
Values of parameters for Eq. (13) are reported in Table 1 for both
alkanes and aromatic compounds.
In the following the comparison between the performances of
the proposed correlation and the correlation by Ungerer and Batut
[12], applicable to PR EoS alone, is made, based on the absolute
average deviations (AAD%) of predicted molar volumes. Table 2
reports the range of the operating conditions (temperature and
pressure) for the considered experimental data for both saturated
molar liquid densities and monophasic liquid densities. In order
to calibrate the above-mentioned c correlations, compounds over
a wider molecular weight range than that used by Ungerer and
Batut [12], have been considered. In particular, while Ungerer and
Batut considered n-alkanes from n-C6 to n-C13 and aromatics from
benzene to hexylbenzene (as reported by de SantAna et al. [23]),
n-alkanes from C3 to n-C24 and aromatics from benzene to nonyl-
benzene have been taken into account in this work.
Table 3 reports the ADD% of predicted molar volumes (saturated
liquid conditions alone, monophasic liquid conditions alone and
both conditions) obtained by applying: (1) no volume shift to SRK
and PR; (2) volume shift values predicted by Eq. (9) (for TR < 0.95)
to SRK and PR; (3) volume shift values predicted by Ungerer and
Batut correlation (for TR < 0.95) to PR. It has to be highlighted that,
for comparison purposes, we have extended the Ungerer and Batut
correlation expressed by Eqs. (5)(7) also for heavy hydrocarbons,
that is we have not employed a correlation that requires the knowl-
edge of an experimental value of the molar volume [12], using the
critical parameters reported by Reid et al. [24] and Yaws [25].
By observing Table 3 some remarks can be done.
As for saturated liquid density data, for the considered com-
pounds, the unshifted PR EoS assures better volumetric predictions
than the unshifted SRK (especially for aromatics). The application
of the volume shift correlation developed in this work assures an
improvement upon volumetric estimates for both EoSs, and the rel-
ative improvement is greater for SRK than PR, even if the shifted PR
still works better than shifted SRK. Comparing the performances of
the proposed correlation with those of the Ungerer and Batut cor-
relation, the former gives rise to smaller AAD% for n-alkanes from
C3 to C6 plus C8 and for all the considered aromatic compounds.
The use of a c correlation with quadratic dependence on TR
allows one to obtain a better molar volume calculation when
approaching the critical temperature as shown by Fig. 3 that reports
the percent relative error ( %) on molar volume. % is computed
as:
vcalc vexp
%= 100 (15)
vexp
 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258 55

Table 1
Values of parameters [dm3 /mol] of Eq. (13) for n-alkanes and aromatic compounds.

EoS a1 a2 a3 b1 b2 b3 d1 d2 d3

SRK 21.3255 25.8953 7.8799 35.7567 44.4897 13.869 17.3989 21.7999 6.8411
Alkanes
PR 30.36181 37.8911 11.83722 43.5755 54.72416 17.205 18.15158 22.9152 7.235538

SRK 2.5944 5.0989 2.2989 2.4950 1.7780 0 0 0 0.0448

Aromatics
PR 1.2821 2.4957 1.0056 1.1547 2.5958 1.1052 1.2487 1.1566 0.2528

a) b) 18
30
This work SRK TR<0.95 This work SRK TR<0.95
27 15
This work PR TR<0.95 This work PR TR<0.95
24 12 UB PR TR<0.95
UB PR TR<0.95
21
9
18
6
15

%
%

12 3

9 0
6 -3
3
-6
0
-9
-3
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
TR
TR

c) 18 d) 18
This work SRK TR<0.95
15 This work SRK TR<0.95
15 This work PR TR<0.95
This work PR TR<0.95
12 UB PR TR<0.95
UB PR TR<0.95
9 12

6
9
3
%
%

0 6
-3
3
-6
-9 0
-12
-3
-15
0.4 0.5 0.6 0.7 0.8 0.9 1.0
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
TR TR

e) 18
This work SRK TR<0.95
15
This work PR TR<0.95

12 UB PR TR<0.95

9
%

-3

-6
0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
TR

Fig. 3. Percent relative error ( %) on saturated liquid volume calculations obtained by applying different c correlations: (a) propane; (b) n-heptane; (c) n-undecane; (d)
benzene; (e) ethylbenzene.
56 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258

Table 2 Table 3
Experimental range for the data considered in this work. Absolute average deviations (AAD%) on predicted molar volumes without and with
different c values for TR < 0.95.
Compound Type of T [K] (TR < 0.95) T [K]/P [bar] (TR < 0.95)
dataa Compound No volume shift This work Ungerer and
Batut
S 100350
Propane
M 166.2348.0/0.474597.7 SRK PR SRK PR PR
S 135400 Saturated liquid density data
n-Butane
M 310.9377.6/4.137689.5 Propane 10.05 4.74 4.48 3.03 14.30
n-Butane 11.23 3.52 2.67 2.19 8.09
S 143443
n-Pentane n-Pentane 12.22 2.33 1.13 0.95 4.34
M 348423/80.7647.1
n-Hexane 14.77 1.99 1.47 1.09 3.50
S 193478 n-Heptane 16.19 3.00 3.33 2.73 2.38
n-Hexane n-Octane 18.00 4.23 2.42 2.03 3.63
M 310.9477.6/6.64672.5
n-Nonane 18.53 5.01 4.20 3.90 1.79
S 183513 n-Decane 20.21 6.54 5.27 4.95 2.54
n-Heptane
M 277.6423.15/1.51690.3 n-Undecane 20.88 7.19 5.85 5.97 1.92
n-Octane S 333533 n-Dodecane 23.90 9.87 5.01 4.92 4.57
Benzene 12.10 2.61 0.97 0.89 5.10
S 223533 Toluene 14.57 1.71 2.49 0.96 2.57
n-Nonane
M 303.15423.15/0.703691.5 Ethylbenzene 15.35 2.27 2.56 0.60 2.10
n-Propylbenzene 17.44 4.15 2.32 1.43 2.84
n-Decane S 244583
CO2 12.12 2.91 1.87 1.72
S 253573 H2 S 5.76 6.64 1.38 1.23
n-Undecane
M 303.15423.15/50500
Monophasic liquid density data
n-Dodecane S 263623 Propane 4.95 6.66 1.13 0.44 11.97
n-Tridecane M 303.15423.15/50500 n-Butane 6.60 5.25 3.54 1.66 4.93
n-Heptadecane M 323.15573.15/50500 n-Pentane 5.74 5.34 8.46 4.10 0.85
n-Eicosane M 373.15573.15/50500 n-Hexane 9.83 2.43 6.88 3.56 1.25
n-Tetracosane M 333.5371.2/20.7120.7 n-Heptane 12.23 0.97 4.84 2.61 0.64
Benzene S 279533 n-Nonane 16.50 4.30 6.21 4.06 0.55
n-Undecane 20.11 7.35 8.44 6.38 0.24
S 178553
Toluene n-Tridecane 24.73 11.58 9.23 7.38 2.40
M 323423/34.2647.4
n-Heptadecane 32.34 18.48 3.16 2.78 10.25
S 203583 n-Eicosane 36.46 22.26 2.67 1.98 13.91
Ethylbenzene n-Tetracosane 56.58 40.28 2.99 1.97 25.62
M 293.1353.1/1400
Toluene 10.81 1.03 0.82 0.45 0.76
n-Propylbenzene S 193373 Ethylbenzene 13.85 1.53 0.78 0.15 1.11
n-Butylbenzene M 293.1353.1/1400 n-Butylbenzene 16.51 4.04 2.56 1.32 3.12
n-Hexylbenzene M 293.1353.1/1400 n-Hexylbenzene 21.79 8.86 0.55 0.21 1.29
n-Octylbenzene M 293.1353.1/1400 n-Octylbenzene 25.82 12.56 1.26 1.01 0.42
n-Nonylbenzene M 293.1353.1/1400 n-Nonylbenzene 25.96 12.73 0.74 0.30 0.28
a
S: saturated liquid densities; M: monophasic liquid densities. Both saturated and monophasic liquid density data
Propane 5.30 6.52 1.36 0.62 12.14
n-Butane 7.30 4.99 3.41 1.74 5.42
As for monophasic liquid density data, still the unshifted PR EoS
n-Pentane 8.75 3.95 5.06 2.64 2.47
assures better volumetric predictions than that the unshifted SRK. n-Hexane 11.76 2.26 4.77 2.59 2.13
Better performances in volumetric estimates are obtained by the n-Heptane 13.47 1.61 4.37 2.65 1.18
proposed c correlation for C3 , n-C4 , n-C17 , n-C20 , n-C24 while, as n-Nonane 17.26 4.57 5.46 4.00 1.01
expected, due to the experimental data used by Ungerer and Batut n-Undecane 20.59 7.25 6.81 6.12 1.30
Toluene 13.03 1.43 1.81 0.75 1.83
to calibrate their expression [23], the Ungerer and Batut corre- Ethylbenzene 14.87 2.03 1.98 0.45 1.78
lation works better for n-C6 n-C13 alkanes. Both correlations are
satisfactory for aromatics even if Eq. (13), with the exception of
n-octylbenzene, gives rise to smaller AAD%. binary [6380] and ternary [79,80] mixtures reported in literature
have been used for comparison.
3.2. Carbon dioxide and hydrogen sulde The volume translation for mixtures is calculated as follows
[11]:
Due to the lack of experimental data of monophasic liquid densi-
ties for carbon dioxide and hydrogen sulde, values of parameters 
NC

for these compounds have been obtained by taking into account c= xi ci (16)
only experimental data at saturation conditions. Experimental tem- i=1
perature range for carbon dioxide is 217286 K (TR < 0.95) while for
hydrogen sulde is 188350 K (TR < 0.95). where NC is the number of components in the mixture and ci the
The correlations developed for these two acidic gases have the volume shift parameter of the component i.
same form of Eq. (9); values of parameters A, B and D are reported
in Table 4. The comparison between the molar volume calcula- Table 4
tion with and without volume shift, based on AAD%, is reported Values of parameters [dm3 /mol] for carbon dioxide and hydrogen sulde.
in Table 3.
Range EoS A B D

SRK 0.3423 0.5327 0.2102

4. Results for binary and ternary mixtures CO2
PR 0.3045 0.4804 0.1873

The proposed correlation, developed for pure compounds, has SRK 0.0955 0.1205 0.0389
H2 S
PR 0.0804 0.1059 0.0313
been veried for mixtures of hydrocarbons. Experimental data of
 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258 57

Table 5
Absolute average deviations (AAD%) on predicted molar volumes for binary and ternary mixtures without and with different c values for TR < 0.95.

Mixture T [K] P [bar] N No volume shift This work Ungerer and Batut

SRK PR SRK PR PR

nC2 nC5 277.6510.9 13.788689.4 1363 10.42 7.09 6.94 6.46

nC3 nC4 289.15333.15 2.58496.5 523 8.65 6.01 2.18 1.73
nC4 nC10 310.9510.9 13.789689.5 597 13.36 3.07 7.37 4.55 2.96
nC5 nC6 298.15348.15 1400 210 9.46 2.53 2.78 1.11 1.07
nC5 nC7 298.15348.15 1400 180 10.42 1.70 3.44 1.73 0.67
nC6 nC7 293.15348.15 1400 230 11.80 0.68 3.18 1.60 0.40
nC6 nC8 293.15298.15 1.013 20 13.88 1.23 3.13 2.46 0.95
nC6 nC9 298.15 1.013 9 15.88 2.97 3.58 2.78 0.37
nC6 nC10 293.15298.15 11000 50 17.11 4.35 5.36 4.33 1.29
nC6 nC14 298.15 1.013 3 35.07 20.40 1.31 1.07 12.48
nC7 nC8 293.15298.15 1.013 20 15.32 2.48 3.41 2.59 0.45
nC7 nC9 298.15 1.013 9 15.02 2.25 5.14 4.25 1.39
nC7 nC10 293.15298.15 1.013 20 18.35 5.30 5.90 4.97 0.86
nC7 nC12 293.15298.15 1.013 14 21.01 7.77 7.46 6.42 1.17
nC7 nC14 293.15298.15 1.013 14 32.42 18.04 0.71 0.47 10.13
nC7 nC16 298.15 1.013 3 27.65 13.87 9.65 8.90 4.66
nC7 nC22 303.15343.15 1.013 27 35.33 20.73 4.37 4.32 11.80
nC7 nC24 313.15343.13 1.013 21 40.51 25.39 1.77 1.07 16.24
nC8 nC9 298.15 1.013 9 17.58 4.60 5.19 4.15 0.46
nC8 nC10 293.15298.15 1.013 20 18.70 5.66 6.66 5.51 0.44
nC8 nC11 293.15313.15 1.013 22 19.25 6.13 6.87 5.70 0.27
nC8 nC13 293.15313.15 1.013 22 22.12 8.78 8.10 6.97 1.41
nC8 nC14 293.15298.15 1.013 14 32.97 18.57 1.37 1.08 9.81
nC8 nC15 293.15313.15 1.013 22 24.23 10.73 10.04 8.90 2.30
nC8 nC16 298.15 1.013 3 28.14 14.34 10.14 9.29 4.42
nC9 nC10 298.15 1.013 9 19.57 6.46 7.09 5.86 0.31
nC9 nC12 298.15 1.013 3 22.59 9.25 8.75 7.52 0.93
nC9 nC14 298.15 1.013 3 33.63 19.18 1.92 1.55 9.65
nC9 nC16 298.15 1.013 3 28.61 14.78 10.86 9.93 4.23
nC10 nC12 298.15 1.013 3 23.30 9.92 9.79 8.48 0.90
nC10 nC13 293.15313.15 1.013 22 23.56 10.14 9.78 8.49 1.28
nC10 nC14 298.15358.15 11000 22 34.41 20.24 3.07 2.13 10.01
nC10 nC15 293.15313.15 1.013 22 25.51 11.95 11.60 10.29 2.11
nC11 nC13 293.15313.15 1.013 22 24.42 10.94 10.61 9.28 1.39
nC11 nC15 293.15313.15 1.013 22 26.29 12.68 12.39 11.04 2.18
nC12 nC14 298.15 1.013 3 35.66 21.09 4.54 4.17 9.83
nC12 nC16 298.15358.15 1.013 7 29.70 15.77 11.20 10.23 4.41
nC13 nC15 293.15313.15 1.013 22 28.31 14.54 13.37 12.06 2.93
nC14 nC16 293.15298.15 1.013 14 39.80 24.92 7.59 7.33 11.80
nC16 nC20 293.15343.15 1.013 35 39.70 24.89 10.37 9.94 11.27
H2 SnC7 310.9394.3 1.59993.345 38 17.57 4.74 0.88 1.34
H2 SnC10 277.594444.261 13.79689.476 481 17.92 5.52 7.92 5.43
BenzenenC6 298.15313.15 1.013 30 39.47 29.09 27.92 27.89 28.88
BenzenenC10 298.15 1.013 9 31.58 39.13 44.71 44.38 41.27
BenzenenC12 298.15313.15 1.013 23 18.05 5.95 4.17 3.78 2.71
Benzeneo-xylene 298.15 1.013 5 12.29 0.83 0.66 0.38 0.82
Benzenep-xylene 298.15 1.013 5 13.78 1.46 0.36 0.65 1.26
ToluenenC5 298.15 1.013 10 10.95 1.58 0.40 0.20 1.07
ToluenenC10 298.15 1.013 5 17.83 4.86 4.78 3.94 0.28
ToluenenC14 298.15 1.013 5 34.76 20.15 1.88 1.50 12.13
Tolueneo-xylene 298.15 1.013 5 13.61 1.05 0.65 0.23 0.75
Toluenep-xylene 298.15 1.013 5 14.96 2.24 0.15 0.82 0.47
o-XylenenC6 298.15 1.013 5 13.02 0.53 1.21 0.54 0.68
o-XylenenC10 298.15 1.013 5 18.22 5.26 5.45 4.37 0.72
o-XylenenC14 298.15 1.013 5 34.13 19.62 1.09 0.97 10.68
o-Xylenep-xylene 298.15 1.013 5 15.49 2.77 0.64 0.37 0.65
m-XylenenC6 298.15 1.013 9 14.87 2.13 0.86 0.21 0.04
p-XylenenC6 298.15 1.013 5 14.20 1.45 0.50 0.33 0.51
p-XylenenC10 288.15308.15 1.013 60 18.86 5.82 4.45 3.38 0.21
p-XylenenC14 298.15 1.013 5 35.07 20.45 1.52 1.48 11.49
nC5 nC6 nC7 298.15348.15 1400 315 14.95 2.46 0.73 0.99 2.58
nC7 nC20 nC24 303.15343.15 1.013 28 37.02 22.28 2.33 2.59 13.20

Results are reported in Table 5, where the absolute average devi-
ations on predicted molar volumes without and with different c
values are shown. Binary interaction parameters kij have been set
equal to zero.
SRK and PR EoSs give better results when corrected with
a proper volume shift c. For PR EoS, the proposed correlation
improves the prediction of mixtures volume more than the one
by Ungerer and Batut [12,23].
5. Conclusions
This paper is focused on a method to determine the volume shift
of the EoSs SRK and PR with the aim of improving their prediction
58 L.A. Pellegrini et al. / Fluid Phase Equilibria 317 (2012) 5258
of volumetric properties of uids of paramount importance in oil
and gas industry.
To obtain an accurate expression of c a new general relation is
proposed with a quadratic dependence on reduced temperature
(for TR < 0.95).
The proposed expression has improved the accuracy in deter-
mining the volumetric translation for the equations of state SRK and
PR, being able to predict the parameter c in a wide range of temper-
atures for both monophasic liquid and saturated liquid conditions
of pure compounds. In particular, for saturated liquid volume, the
quadratic dependence on reduced temperature improves the molar
volume calculation when the critical point is approached.
By a comparison based on AAD%, it is shown the extent of the
improvement upon the unshifted EoS volume calculations. More-
over, a comparison between the performances of the proposed
correlation and another correlation (valid for the PR EoS alone)
reported in literature [12,23] is made in order to show for each com-
pound (for given operating conditions) which correlation is better
to employ when dealing with PR EoS.
SRK is the EoS that presents the greatest deviations from exper-
imental points when applied without volume shift and thus the
proposed correlation can be a valid choice when SRK EoS is used.
The new expression of volume translation has also been applied
in mixture molar liquid volume calculation. Results show a good
agreement between experimental and calculated values.
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