Correlation

pubs.acs.org/IECR

A Modeling Framework for Predicting and Correlating Viscosities

of Liquids in Wide Range of Conditions
Ilya Polishuk*
Department of Chemical Engineering & Biotechnology, Ariel University, 40700 Ariel, Israel
S Supporting Information
*

ABSTRACT: This communication reports a modeling framework for estimating viscosities in a wide range of conditions that
couples the critical point-based revised perturbed chain statistical association uid theory equation of state (CP-PC-SAFT EoS)
and the modied YarrantonSatyro correlation (MYS), yet is generalized by SAFT molecular parameters. The proposed
approach requires as an input just critical constants and the triple point liquid densities, while the same triplet of MYS parameters
can predict viscosities of wide variety of compounds including n-alkanes (from methane and until n-octadecane), various
aromatic and nonaromatic hydrocarbons, and oxygenated organic substances. In addition, it can yield particularly accurate
predictions for saturated and single-phase viscosities of asymmetric mixtures. Consequently, this modeling framework is
characterized by an enhanced predictive character.

the MYS parameters. Later on, Abolala et al.23 have successfully

coupled MYS with SAFT-VR-Mie24 EoS for modeling viscosities
of additional imidazolium-based ionic liquids.

INTRODUCTION
Quantitative correlation of liquid viscosities in wide range of
conditions may present diculties even for the multiparameter
reference correlations.13 Consequently, predicting these data
is an exceptionally challenging task. The phase diagrams of
viscosities are much more sophisticated in comparison to
equilibrium thermodynamic properties such as densities or
sound velocities. Unlike these properties, viscosities can rapidly
change in the relatively narrow ranges of temperatures. This
phenomenon becomes particularly pronounced at high
pressures and in vicinity of solidication. In addition, the
values of viscosities are strongly dependent on molecular size
and geometry. As a result, light and heavy compounds with
similar densities may have viscosities varying by orders of
magnitude. This feature indicates that a major progress in
predicting viscosities can be achieved by considering the
molecular parameters of theoretically based approaches such as
molecular simulations or various versions of the statistical
association uid theory (SAFT) equations of state (EoS).
Among the innovative studies implementing the molecular
parameters for estimating viscosities, the molecular approach of
de Wijn et al.4,5 should be noticed. In this respect, the
contributions of Galliero,6 Zhao et al.,7 Quinones-Cisneros
et al.,8 Tan et al.,9 and Quinones-Cisneros and Deiters10 should
be acknowledged as well. It has also been demonstrated
that qualitatively accurate results can be achieved by providing
various viscosity models by densities or residual entropies
generated by SAFT equations with further generalization of the
viscosity coecients not only by molecular weights,11,12 but
also by SAFT molecular parameters.1315
In the previous study,16 a modeling framework coupling
SAFT+Cubic17,18 with the density-based modied Yarranton
Satyro1922 correlation (MYS) comprising the molecular diameter
of that EoS has been proposed. It has been shown that this
approach allows predicting viscosities of sets of compounds, such
as n-alkanes along with some heavy compounds, certain homologues series of ionic liquids, etc., while using the same triplets of
2015 American Chemical Society

METHODS
This communication reports the preliminary results of an
attempt of further enhancing the predictive character and
transparency25 of the SAFT-MYS modeling framework, which
have been achieved by two modications. The rst one is
implementing the recently proposed26,27 critical point (CP)based version modifying the popular perturbed-chain (PC)SAFT EoS. The details of this model are provided in the
Supporting Information. Unlike many SAFT approaches whose
substance-dependent parameters are typically evaluated by
tting relatively large and sometimes vague experimental
databases, CP-PC-SAFT applies their standardized numerical
solution at the characteristic states, namely the critical points.
In addition, it requires one liquid density point datum, normally
at the triple point. In other words, this approach can be
characterized by an advanced predictive capacity thanks to the
substantial reduction of the required experimental data.
A second modication made in the current revision of the
MYS is a further introduction of the CP-PC-SAFTs molecular
parameters in its expression in empirical manner. In particular,
by following the regularities exhibited by the results, it has been
found that an MYS parameter c1 responsible for estimating
the viscosity data at the ambient conditions can typically
be correlated by m (the eective chain length), while c2, a
parameter responsible for the temperature dependence of
viscosity, can often be related with m3. In addition, responsible
for the pressure dependence parameter, c3 is apparently proportional to /kb (segment energy parameter divided by
Received:
Revised:
Accepted:
Published:
6999

April 18, 2015

June 1, 2015
June 23, 2015
June 23, 2015
DOI: 10.1021/acs.iecr.5b01468
Ind. Eng. Chem. Res. 2015, 54, 69997003

Correlation

Industrial & Engineering Chemistry Research

replace the MYS reference temperature of 330 K by Ttriple point +

120 K. After some additional minor changes, the resulting
revised MYS has been obtained as

Boltzmanns constant), and even better correlation is achieved

by /kbm1/4. And nally, to cover light and heavy compounds
by the same triplet of c1-c3, it has been found expedient to

MW 4

T
c1 m + ln 1 + c2v 4m3 ln TTP + 120
(mPa s) = 0.1exp
cP

1.04v exp / k b (P3 / v)T mv

exp
3
NAvm(*)

}{

1 + 0

(1)

Here, v is the molar volume (L/mol) yielded by CP-PCSAFT, P is pressure (bar), T is temperature (K), is the
segment diameter (), MW is the molecular weight (g/mol),
and NAv is Avogadro number. 0 is the zero density viscosity,
typically having a negligible small contribution to the viscosities
of liquids. It can been obtained using the Chung et als
correlation28 and implemented to mixtures according to the
mixing rule of Wilke.29 It should be pointed out that the regular
SAFTs mixing rule for can yield satisfactory results for
viscosities of symmetric mixtures. However, an overall accuracy
of the current approach is improved by implementing a slightly
modied mixing rule specic for eq 1:
* =

i j xixj(miimjj)1.05 ij 3
i (ximii)2.1

(2)

and m = ximii, TTP = xiTTP,ii, MW = xiMw,ii. Remarkably,

eq 2 is closer the regular SAFTs mixing rule (see the
Supporting Information) than the previously proposed
method.30
An additional advantage of the proposed approach is the fact
that the following triplet of adjustable parameters

Figure 1. Schematic representation of the proposed modeling framework.

c1 = 0.27
c 2 = 2.5 1011
c3 = 2.1

(3)

yields satisfactorily accurate results for particularly large variety

of hydrocarbons and their mixtures. Consequently, in many
cases, it can be considered as an entirely predictive method,
whose schematic representation is depicted by Figure 1.

RESULTS AND CONCLUSIONS

An improvement achieved by generalizing the MYS parameters
by /kb, , and m instead of MW can be demonstrated while
considering two compounds with dierent chemical backgrounds and the almost identical molecular weights. By chance,
the density and viscosity data are available31,32 for a pair of such
compounds, namely, n-octane and dipropyl ketone at the same
temperature (283 K, see Figure 2). In this case, the success of
generalizing the MYS parameters with MW is dened only by
the mutual densityviscosity interrelation of the compounds
under consideration. As seen, dipropyl ketone has a higher
density, whose value at the atmospheric pressure is reached by
n-octane only around 2800 bar. Coincidentally, the viscosity of
dipropyl ketone is higher as well. However, its value at the
atmospheric pressure is reached by n-octane at the much lower
pressure around 400 bar. Consequently, an attempt to
generalize c1c3 for n-octane and dipropyl ketone only by

Figure 2. Comparison of densities and viscosities of n-octane (283.15 K)

and dipropyl ketine (283 K). Points, experimental data.31,32 Lines on the
density plot, predictions of CP-PC-SAFT.
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Figure 3. Saturated high pressure viscosities of asymmetric n-alkane systems. Points, experimental data.3336 Lines, predictions of the proposed
approach.

MW cannot be eective. Indeed, consideration of c1c3

independently of the SAFT molecular parameters (which
intrinsically reect the molecular geometry and chemical
background) is equivalent to application of c1c3 attached
by /kb, , and m one compound to another. Figure 2
demonstrates that the results of such a practice are particularly
inaccurate. Remarkably, similar eects are observed while the
viscosity parameters of one compound are transferred to
another even within the homologues series of compounds
such as n-alkanes also in the cases of other viscosity approaches.16
Predictions yielded by the proposed modeling framework
for viscosities of representative pure compounds in wide variety
of conditions, including various aromatic and nonaromatic
hydrocarbons and oxygenated organic substances, can be found
in the Supporting Information. These results are compared
with the previous modeling framework.16 It should be pointed
out that unlike CP-PC-SAFT, implementation of SAFT+Cubic
comprises adjustment of the pure compound parameters. In
particular, for n-alkanes, the parameter m and in the cases of
other nonassociating compounds two parameters, namely m
and c, are tted to the experimental data. Consequently, a
comparison between these modeling frameworks can hardly be
considered as entirely fair. Nevertheless, to make this
comparison more equitable, a triplet of parameters evaluated
for n-alkanes has been implemented for all the considered
compounds. Although the overall AAD% are typically similar
for both approaches, it can be seen that the proposed modeling

framework is usually advantageous when predicting the higher

values of viscosity. At the same time, it should be emphasized
that eq 3 is still not universal. Numerous compounds, such as
benzene, carbon dioxide, nitrogen, acetone, 1-alkanols, haloorganic substances, etc., require dierent values of c1c3.
Moreover, the current predictive parametrization scheme26,27 of
CP-PC-SAFT can hardly be applied for modeling heavy
compounds whose reported critical constants can often be
deceptive. In such cases, the model could be tted to the data
similarly to other SAFT equations. Development of the
pertinent generalized parametrization scheme is currently
under progress, and the preliminary results indicate that the
triplets of c1c3 parameters covering heavy aromatic substances
and series of ionic liquids could be proposed as well.
Figure 3 depicts the predictions of eqs 13 for saturated
viscosities of asymmetric n-alkane systems. The binary
parameter k12 = 0.022 has been previously26 evaluated for
the available in wide PVT range VLE of the system methane+ndecane. Particular tting of other systems included by Figure 3
has not been performed since their VLE data cover much
narrower condition ranges. However, the same value of k12
yields good results for VLE of methane+n-octadecane and
ethane+n-tetradecane as well. In the case of the available VLE
in ethane+n-octadecane, the zero k12 seems to be appropriate.
The gure demonstrates that the proposed approach yields
particularly accurate predictions of the challenging viscosity
data under consideration.
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DOI: 10.1021/acs.iecr.5b01468
Ind. Eng. Chem. Res. 2015, 54, 69997003

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Industrial & Engineering Chemistry Research

Figure 4. Single phase high pressure viscosities of mixtures at the elevated pressures. Points, experimental data.3740 Lines, predictions of the
proposed approach.

compared. Comprehensive comparison of the results for

methane, n-dodecane, methyl n-hexyl ketone, and dipropyl
ether. Details of the CP-PC-SAFT EoS and the values of its
substance specic parameters. The Supporting Information is
available free of charge on the ACS Publications website at
DOI: 10.1021/acs.iecr.5b01468.

Figure 4 considers the single-phase viscosities of additional

mixtures at the elevated pressures. Two of them, namely
methane+n-decane37 and methane+toluene,38 so far have been
treated by the previous approach,30 which contrary to the
current one has applied dierent values of c1c3 for all three
compounds under consideration. However, the overall
predictions of the rst system are more accurate (AAD% =
10.25% vs 13.09%) and slightly disadvantageous in the case of
the second one (AAD% = 6.623% vs 5.151%).
As seen, the proposed approach requiring an input of critical
constants and the triple point liquid densities can predict
viscosities of a wide variety of compounds including n-alkanes
(from methane and until n-octadecane), various aromatic and
nonaromatic hydrocarbons, and oxygenated organic substances.
In addition, it can yield particularly accurate predictions for
saturated and single-phase viscosities of asymmetric mixtures.
Further eorts will be focused on accumulating the high
pressure viscosity data of additional compounds and mixtures
to delineate the validity range of the proposed approach and
develop the MYS c1c3 parameters for groups of compounds
mismatching the triplet given by eq 3.

AUTHOR INFORMATION

Corresponding Author

*E-mail: polishuk@ariel.ac.il. Phone: +972-3-9066346. Fax:

+972-3-9066323.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
The author would like to thank Professor Ilmutdin Abdulagatov
from the National Institute of Standards and Technology for
the fruitful discussion and kind supply of unreachable data sets.

ASSOCIATED CONTENT

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S Supporting Information
*

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DOI: 10.1021/acs.iecr.5b01468
Ind. Eng. Chem. Res. 2015, 54, 69997003