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Teoría de Fricción

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General Friction Theory Viscosity Model for the

PC-SAFT Equation of State


Sergio E. Quinones-Cisneros
Institute of Physical Chemistry, University of Cologne, D-50939 Cologne, Germany

Claus K. Zeberg-Mikkelsen and Josefa Fernandez


Laboratorio de Propiedades Termofsicas, Depto. de Fsica Aplicada, Facultad de Fsica, Universidad de Santiago de
Compostela, E-15782 Santiago de Compostela, Spain

Josefa Garca
Departamento de Fsica Aplicada, Edicio de Ciencias Experimentales, Universidad de Vigo, E-36280 Vigo, Spain
DOI 10.1002/aic.10755
Published online January 13, 2006 in Wiley InterScience (www.interscience.wiley.com).

In this work, a general f-theory viscosity model based on the perturbed-chain statistical
associating uid theory (PC-SAFT) equation of state (EoS) has been developed for the
description of the viscosity behavior of the normal alkanes family (from methane to
n-octadecane). This general f-theory model has been shown to provide satisfactory results
for the modeling of the viscosity of the normal alkanes as well as carbon dioxide and
nitrogen over wide ranges of temperatures and up to 100 MPa. In addition, using simple
mixing rules, an evaluation of the model performance has been carried out for several
n-alkane and carbon dioxide n-alkane mixtures over wide ranges of temperature and
pressure. The chosen mixing rules provide good mixture viscosity prediction, close to or
within experimental uncertainty, which is satisfactory for most applications (industrial
and research). Further, the combination of the PC-SAFT EoS with the f-theory adds one
more thermophysical property to the list of properties for which this model already
delivers an improved representation, making the application potential for the PC-SAFT
EoS even wider. 2006 American Institute of Chemical Engineers AIChE J, 52: 1600 1610, 2006
Keywords: equation of state, hydrocarbon, mixture, modeling, f-theory, PC-SAFT, viscosity

Introduction
Within a wide range of engineering disciplines, viscosity is
an important uid property required in a large number of
applications such as the design of transport equipment, the
simulation of chemical processes, the simulation of petroleum
reservoirs, the blending and transportation of oil and gas,
lubrication, and refrigeration. In most of these applications, the
pressure and temperature dependencies of the viscosity are
Correspondence concerning this article should be addressed to S. E. QuinonesCisneros at seqc@mac.com.

2006 American Institute of Chemical Engineers

1600

April 2006

critical parameters. In some cases, such as the production of


deep-water petroleum reservoirs, a reservoir uid can go from
high-pressure and high-temperature conditions to ambient conditions, which would necessarily imply phase separation and
important compositional variations. Consequently, reliable and
accurate viscosity models are in increasing demand for applications covering everyday wider and more extreme ranges of
temperature, pressure, and composition. Thus, multiproperty
models capable of providing accurate description not only of a
uids phase and volumetric behavior but also of its transport
and thermophysical properties are required.
In terms of the viscosity, the friction theory ( f-theory)1 provides
a way to link accurate viscosity models to the repulsive and
Vol. 52, No. 4

AIChE Journal

attractive pressure terms of an equation of state (EoS). The basic


idea of this approach consists in making the analogy between
shear ow and two sliding surfaces under shear stress, which is
linked to normal stresses through temperature-dependent friction
coefcients. In the f-theory the normal stresses are given by the
repulsive and attractive contributions of the thermodynamic pressure and therefore the shear stress also naturally follows as a
balance between repulsive and attractive terms. The f-theory has
previously been related to the widely used cubic EoS of the van
der Waals type, such as the SoaveRedlichKwong (SRK),2 the
PengRobinson (PR),3 or the PatelTeja (PT).4 Further, the ftheory has been developed into a general model for these EoSs.5,6
Despite the simplicity of the cubic EoS, it has been shown that the
f-theory approach can provide, in a simple way, accurate viscosity
predictions and modeling results over wide ranges of temperature,
pressure, and composition for many uids of industrial importance
and complexity, such as CO2 hydrocarbons,7 light gases,8
refrigerants,9 lubricants,10 refrigerant lubricant,11 as well as
multicomponent mixtures ranging from natural gas12,13 to heavy
oils14-16 with viscosities ranging between 102 and 104 mPas (or
even higher).
However, to overcome the theoretical limitations intrinsic to
simple models such as the cubic EoS, molecular-based EoSs
have been developed with the aim of achieving a better description of the thermophysical properties that follows from
complex molecular physics, such as asymmetry, intricate molecular structure, and association, as well as their interactive
collective behavior (mixture properties). One of these molecular-based EoSs is the statistical association uid theory
(SAFT) introduced by Chapman et al.,17,18 which is based on
Wertheims thermodynamic perturbation theory of rst order.19-22 Along this line, several modications of the original
SAFT EoS have followed, among which is the perturbed-chain
statistical association uid theory (PC-SAFT) by Gross and
Sadowski,23 which has been attracting increasing interest (particularly for applications involving chain molecules).
Thus, in this work, a general f-theory model is introduced in
conjunction with the PC-SAFT EoS. Similar to other already
developed general f-theory models, this model is also derived
based on the viscosity behavior of the normal alkanes family,
from methane to n-octadecane. The applicability of this ftheory model is further illustrated for mixtures composed of
n-alkanes and carbon dioxide n-alkanes, which are of relevant industrial interest. Thus, by combining the PC-SAFT EoS
with the f-theory, in addition to the improved representation of
phase behavior and volumetric properties (among other thermophysical properties), an accurate simultaneous representation of the uid viscosity can also be achieved.

The PC-SAFT Equation of State


In the PC-SAFT EoS,23 the molecules are assumed to be
chains formed by tangentially bonded spheres with the same
diameter and dispersive energy. It follows from the perturbation theory that the molecular interactions can be divided into
a repulsive and an attractive part of the potential. In this way,
the repulsive contribution is dened as a reference uid without
any attractive interactions. The attractive molecular interactions are treated as perturbations to the reference system. Based
on this, the PC-SAFT equation, when expressed in terms of the
compressibility factor Z, is given as the sum of the ideal gas
AIChE Journal

April 2006

Vol. 52, No. 4

contribution (Zid 1), a hard-chain contribution (Zhc), and a


perturbation contribution of the dispersive forces (Zdisp) accounting for the attractive interactions
Z Z id Z hc Z disp

(1)

The PC-SAFT approach is a modication of the SAFT equation


by Huang and Radosz.24,25 The only difference is that in the
PC-SAFT EoS the dispersive forces are accounted for by applying
a perturbation theory of second order using an expression for the
radial pair distribution of a hard-chain reference uid, whereas in
the SAFT equation24,25 a hard-sphere reference is used in the
dispersion term. The exact expressions and denitions for the Zhc
and Zdisp contributions can be found in Chapman et al.17,18 and
Gross and Sadowski.23 In general, Zhc is related to three pure
component parameters: the segment number mi, the segment diameter i, and the segment energy parameter i. Also Zdisp depends on these three parameters as well as the diameter and energy
between unlike segments, ij and ij, respectively. These two
parameters may be obtained by the BerthelotLorentz combining
rules (see Gross and Sadowski23). A binary interaction parameter
kij is introduced in the mixing rule for ij to correct the segment
segment interactions of unlike chains.

The Friction Theory


In the friction theory ( f-theory) for viscosity modeling,1 the
total viscosity is separated into a dilute gas viscosity term 0
and a residual friction viscosity term f

0 f

(2)

The dilute gas viscosity is dened as the viscosity given by the


kinematics of particles of a nite mass but at the zero density limit,
whereas the residual viscosity term is related to friction concepts
of classical mechanics. In analogy to the AmontonsCoulomb
friction law, in the friction theory the repulsive and attractive
contributions to the shear stress are modeled as perturbations away
from their corresponding normal stresses.1 Thus, assuming Newtonian behavior, the friction contribution to the viscosity can be
represented according to the following series:

a,i

p ai

p
r,i

i
r

(3)

where pa and pr are the attractive and repulsive contributions to


the thermodynamic pressure and the a/r,i are temperaturedependent friction parameters related to friction coefcients
between sliding surfaces. In terms of cubic EoS, because of the
strong high-pressure dominance of the repulsive term, a linear
model for the attractive contribution together with a quadric
model for the repulsive has been found to be sufcient to
achieve an accurate viscosity representation of a large number
of uids.1,5 That is, for the previous work related to simple
cubic EoS, such as the SRK or PR EoS, it has been shown that
the residual friction term can be accurately expressed by a
linear function of the attractive pressure pa and a quadratic
function in the repulsive pressure pr, that is,

f ap a rp r rrp r2

Published on behalf of the AIChE

DOI 10.1002/aic

(4)
1601

Figure 1. High-pressure pvT performance of the PR EoS and the PC-SAFT EoS for methane at the critical isotherm (190.6
K for the PR EoS and 191.4 K as predicted by the PC-SAFT EoS) ( ), at 100, 120, 140, 160, 180, 200, 250, 300, 350,
400, 500, and 600 K, and the phase boundary (); along with the densities by Younglove and Ely26 (}).

Also, part of the reason for proposing Eq. 4 as the main


model for cubic EoS was numerical efciency because models
of this type are used as core models in highly computational
demanding tools such as petroleum reservoir simulators. However, the applications that would be targeted by a model such
as the PC-SAFT EoS are of a different type (more focused on
the actual physics of the uids) and the model itself has a
substantially higher complexity than that of cubic EoSs. Therefore, for the PC-SAFT EoS a fully quadratic model (for both
the repulsive and the attractive pressure terms) of the form

f ap a aap a2 rp r rrp r2

(5)

pathological compressibility behavior illustrated by the PR EoS


isotherms in Figure 1, given that their problem lies in their
intrinsic failure to accurately represent the pressure dependency with the volume, especially its derivatives. On the other
hand, the performance of the PC-SAFT model, as illustrated in
Figure 1, is clearly superior one possible reason that the
PC-SAFT EoS delivers such an improved high-pressure compressibility performance may be linked to the step potential
used in its derivation (see Gross and Sadowski23).
In terms of viscosity, the PC-SAFT EoS also shows some
advantages, although not as obvious as in the case of their pvT
performance. To explore this issue let us consider a linear f-theory
model for both the PR EoS and the PC-SAFT EoS, that is,

is proposed.

f a p a rp r

(6)

Performance of the PC-SAFT EoS at elevated pressure


Before proceeding it is illustrative to underline some of the
basic motivations for extending the f-theory to the PC-SAFT
EoS. One of the problems encountered with the application of
cubic EoS based f-theory models to complex uids, such as
heavy or degraded reservoir uids, is the compressibility response of such simple models under high pressure.16 This
problem may be related to the mathematical and theoretical
limitations of the van der Waals repulsive term as it is extended
to high-pressure conditions. This issue not only pertains to
complex molecules but is also important even for simple molecules, such as methane. Indeed, one major problem that cubic
EoSs have is their poor high-pressure performance, even for
light uids of industrial relevance such as natural gas. This
problem is clearly illustrated in Figure 1 where a comparison of
the methane pvT methane performance between the PR EoS
and the PC-SAFT EoS is depicted along with the recommended
methane data by Younglove and Ely.26 It is clear that for
high-pressure applications involving large amounts of methane
(such as natural gas) the PR EoS, and for that matter all cubic
EoSs, will not perform in a satisfactory manner. Indeed, no
volume translation or any other articial scheme can correct the
1602

DOI 10.1002/aic

In the case of the PC-SAFT EoS, the dispersive term is identied as the attractive pressure pa term, that is,
p a p disp

(7)

whereas the repulsive pressure term pr is dened as


p r p id p hc

(8)

Regarding the temperature dependency of the friction constants, consistent with previous work,1 a simple exponential
dependency of the following form is suggested:

a a 1exp 1 a2 exp2 2

(9)

r b 1exp 1 b2 exp2 2

(10)

and

Published on behalf of the AIChE

April 2006

Vol. 52, No. 4

AIChE Journal

Figure 2. Linear PR and PC-SAFT f-theory viscosity models for methane, along with the recommended data by
Zeberg-Mikkelsen27 (F).

Thus, the corresponding linear f-theory models consist of four


adjustable parameters for each substance (a1, a2, b1, and b2).
Figure 2 shows a comparison of the viscosity results for the
methane correlations using the PR EoS and the PC-SAFT EoS. As
it appears from this gure the linear model seems to give good
results for both EoSs, although the PC-SAFT EoS delivers a better
performance in the region of transition between a light uid and a
dense one (reduced temperature between 0.8 and 1.2). On the
other hand, Figure 3 shows similar results but now for a correlation corresponding to a much heavier molecule: n-pentadecane. In

the case of the n-pentadecane correlations it is clear that, if the


range of application is to be extended up to 100 MPa, both linear
models fail to perform satisfactorily. Thus, similar to previous
works,1,5,6 for high-pressure applications a quadratic model will
still be required for an f-theory model based on the PC-SAFT EoS.
Finally, it is remarked that, because a highly accurate general
PC-SAFT f-theory viscosity model will be presented next, the
specic correlation parameters corresponding to the linear models
shown in Figures 2 and 3 are irrelevant because such correlations
were made for illustration purposes only.

Figure 3. Linear PR and PC-SAFT f-theory viscosity models for n-pentadecane, along with the recommended data by
Zeberg-Mikkelsen27 (F).
AIChE Journal

April 2006

Vol. 52, No. 4

Published on behalf of the AIChE

DOI 10.1002/aic

1603

The general viscosity model


Based on the general concepts of the f-theory, a general
quadratic viscosity model has been derived and coupled to the
PC-SAFT EoS. Given the already intrinsic complexity of the
PC-SAFT model and for the sake of accuracy, we propose a
residual friction contribution model that is quadratic on both
the repulsive and the attractive terms and is dependent on two
scaling parameters, a and r:

f a a

pa
pa
aa
pc
pc

r r

pr
pr
rr
pc
pc

(11)

For the model proposed in Eq. 11 the reduced friction coefcients a , aa , r , and rr have been found to correlate with the
temperature T and the segment number m in an accurate manner for the normal alkanes family. It should also be pointed out
that, for proper functional reduction, pc must always be the
critical pressure that follows from satisfying the critical conditions with the PC-SAFT EoS for a given pure component (not
a tabulated pc).
For the temperature- and segment number dependent reduced friction coefcients the following empirical expressions have been found appropriate to describe the viscosity
up to 100 MPa of pure n-alkanes ranging from methane to
n-octadecane:

a a 0,0 a 1,0exp 1 1 a2,0 exp2 2 1 a3,0 exp3 3 1

a1,1 exp 1 1 a2,1 exp2 2 1 a3,1 exp3 3 1


m

a1,2 exp 1 1 a2,2 exp2 2 1 a3,2 exp3 3 1


(12)
m2

r b 0,0 b 1,0exp 1 1 b2,0 exp2 2 1 b3,0 exp3 3 1

b1,2 exp 1 1 b2,2 exp2 2 1 b3,2 exp3 3 1


(13)
m2

and where Tc must also be the critical temperature that satises


the critical conditions with the PC-SAFT EoS (not a tabulated Tc).
Clearly, the actual friction coefcients in Eq. 5 will follow
from the reduced ones according to the following expressions:

A 0,1 A 0,2
2
m
m

A 2,1exp2 2 1 A3,1 exp3 3 1


m

A2,2 exp2 2 1 A3,2 exp3 3 1


(14)
m2

rr B 0,0

b0,1 b0,2
2
m
m

b1,1 exp 1 1 b2,1 exp2 2 1 b3,1 exp3 3 1


m

aa A 0,0

a0,1 a0,2
2
m
m

B 0,1 B 0,2
2
m
m

B 2,1exp2 2 1 B3,1 exp3 3 1


m

B2,2 exp2 2 1 B3,2 exp3 3 1


(15)
m2

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DOI 10.1002/aic

Tc
T

(16)

a
pc

(17)

r r

r
pc

(18)

aa a

aa
p 2c

(19)

rr r

rr
p c2

(20)

and

with

a a

The universal friction constants (ai,j, Ai,j, bi,j, and Bi,j) in Eqs.
1215 have been estimated using a database containing
smoothed experimental viscosities of normal alkanes from

Published on behalf of the AIChE

April 2006

Vol. 52, No. 4

AIChE Journal

Table 1. Scaling Parameters ,a and ,r for the General PCSAFT f-Theory Viscosity Model
Compound

,a (P)*

,r (P)

Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Decane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Octadecane
Carbon dioxide
Nitrogen

8.15957
9.04189
1.29954
6.24267
6.42895
17.0600
32.7790
49.7901
78.6746
94.6198
84.6536
98.6187
102.101
93.7225
104.067
16.1322
2.28277

48.7410
49.9325
65.0437
75.2528
75.1365
86.3043
98.8131
112.585
133.007
140.528
142.394
142.742
147.090
145.777
150.037
119.251
57.7935

Table 2. Friction Constants for the General PC-SAFT


f-Theory Viscosity Model
Attractive Friction
Constants

*1 P 104 mPa s.

methane to n-octadecane over wide ranges of temperature and


pressure.27 This database was also used to derive the previously
published general f-theory models for the SRK, PR, and PT
EoSs.5,6 Essentially, the model parameterization follows the
same ideas as for the previous general models, that is, a
perturbation away from the critical isotherm. However, a major
difference with cubic EoSs follows from the fact that in the
case of the PC-SAFT EoS (as well as all more advanced EoSs)
the model does not deliver a universal critical compressibility
(Zc), which is reected in the mathematical form of Eqs. 1215.
Additionally, for the sake of accuracy and model exibility two
scaling parameters (a and r), rather than one, have been
introduced. The regression of the general PC-SAFT f-theory
model parameters has been carried out iteratively with alternate
optimizations of the scaling parameters in Eq. 11 and the
universal constants in Eqs. 1215 until a quadratic residual
dened by relative viscosities was minimized. The obtained
scaling parameters are given in Table 1, whereas the universal
friction constants in Eqs. 1215 are given in Table 2.
In Table 3, the corresponding average absolute deviation
(AAD) and maximum absolute deviation (MxD) obtained by
the model are reported along with the temperature range and
the maximum applicable pressure. The deviations reported in
Table 3 for the general PC-SAFT f-theory are excellent and
satisfactory for most engineering applications. The maximum
deviations are reasonably low values that are found in regions
that correspond to extreme conditions of high experimental
uncertainty, that is, around the critical point, at a light gas
phase, or for a phase at low-temperature and high-pressure
conditions.
In Figure 4 a very good agreement between the predicted
viscosities of propane and the recommended values of Vogel et
al.28 is shown. In the case of the 600 K isotherm a higher
deviation is observed, which may be explained by the fact that
such an isotherm is outside the tuning range of all models,
given that no experimental information is available up to that
temperature. Actually, any application of the general PC-SAFT
f-theory model outside the ranges reported in Table 3 ought to
be considered as extrapolations. However, in Figure 5 the
deviation between the predicted viscosities of n-decane by the
AIChE Journal

April 2006

Vol. 52, No. 4

Repulsive Friction
Constants

a 0,0
a 1,0
a 2,0
a 3,0
a 0,1
a 0,2
a 1,1
a 2,1
a 3,1
a 1,2
a 2,2
a 3,2

0.144998
0.0305382
0.223166
0.00686973
2.37354
1.55529
0.555650
1.31634
0.331436
1.93953
1.02853
0.132005

b 0,0
b 1,0
b 2,0
b 3,0
b 0,1
b 0,2
b 1,1
b 2,1
b 3,1
b 1,2
b 2,2
b 2.0

0.333075
0.302822
0.145200
0.0149881
0.154596
0.0122148
0.0391957
0.435213
0.0866662
0.175047
0.655495
0.247205

A 0,0
A 0,1
A 0,2
A 2,1
A 3,1
A 2,2
A 3,2

0.00157800
0.00142498
0.0222979
0.00681810
0.000466511
0.0258567
0.0110935

B 0,0
B 0,1
B 0,2
B 2,1
B 3,1
B 2,2
B 3,2

0.000574904
0.000374863
0.00262223
0.000466001
0.00182595
0.00494766
0.00374101

general PC-SAFT f-theory model and experimental literature


values29-36 in the range 278 478 K is shown up to 150 MPa.
This gure reveals that a satisfactory extrapolation to pressures
higher than the reported range (0 100 MPa) in Table 3 is
achieved.
Further, the general PC-SAFT f-theory model has been applied to the viscosity modeling of carbon dioxide37 and nitrogen.38 The estimated scaling parameters for these two compounds are reported in Table 1, whereas the modeling results
are given in Table 3.
For pure alkanes higher than n-hexane (m 3.0576) a
simple correlation between the viscosity scaling parameters a
and r and the segment number m can be obtained with the
following asymptotic expressions:

a 124.491 5.88015/m 1023.46/m2

(21)

and
Table 3. Modeling Deviation Results for the PC-SAFT
f-Theory Viscosity Model
Compound

T/T c
Range

Max
P/P c

AAD%

MxD%

Methane
Ethane
Propane
n-Butane
n-Pentane
n-Hexane
n-Heptane
n-Octane
n-Decane
n-Dodecane
n-Tridecane
n-Tetradecane
n-Pentadecane
n-Hexadecane
n-Octadecane
Carbon dioxide
Nitrogen

0.552.50
0.351.60
0.301.29
0.351.04
0.641.16
0.561.08
0.501.00
0.451.00
0.450.76
0.450.60
0.440.53
0.420.54
0.440.58
0.410.52
0.420.55
0.661.97
0.634.75

20.0
11.3
13.0
18.0
30.0
35.0
35.0
40.0
48.0
55.0
60.0
60.0
65.0
70.0
80.0
13.5
29.4

1.08
0.76
1.18
1.21
1.32
1.52
0.97
1.02
0.70
0.97
1.24
1.38
0.88
1.11
1.39
4.35
3.20

4.52
4.83
4.75
9.14
9.08
16.5
8.07
7.74
2.50
5.40
2.96
4.49
4.91
7.15
7.94
15.0
14.9

Published on behalf of the AIChE

DOI 10.1002/aic

1605

z z
n

aa

i aa,i

i1

i1

z z
n

i r,i

i1

r,i

i1

z z
n

rr

a,i

i rr,i

i1

i1

r,i

aa,i
2
p c,i

(25)

r,i
p c,i

(26)

rr,i
2
p c,i

(27)

where in all cases the subindex i denotes the corresponding


pure component property. However, in the case of the PCSAFT EoS a modied estimation of the mass-weighted fraction
zi appeared to give improved results. Thus, in this work, the
mass weighted zi fraction is estimated using the relation
Figure 4. Viscosity of propane at various isotherms vs.
pressure p predicted by the general PC-SAFT
f-theory model (), along with the recommended values of Vogel et al.28 (F).

zi

x im i i
MW iF w

(28)

with
m
x MW
n

r 160.376 44.6249/m 852.173/m 2

Fw

(22)

The required dilute gas viscosity term has been calculated by


the dilute gas viscosity model of Chung et al.,39 which can
represent the dilute gas viscosity of a wide range of uids
(including those studied in this work) within an uncertainty of
1.5%. In this dilute gas viscosity model the tabulated values for
the critical molar volume and the critical temperature are
required along with the acentric factor and the molecular
weight. In this work the required tabulated parameters have
been taken from Poling et al.40 However, it should be pointed
out that as the compound becomes heavier (above n-decane)
the dilute gas limit contribution becomes less important and it
may even be neglected, given that such uids will likely be of
relevance only for condensed phases.

i i

i1

(29)

where x is the mole fraction, MW is the molar mass, m is the


segment number, and is the segment energy parameters in the
PC-SAFT EoS. Thus, for mixture calculations Eqs. 24 27 are
substituted in Eq. 5 and the pa and pr are taken directly from the
PC-SAFT EoS according to Eqs. 7 and 8 and using the EoS
mixing rules suggested by Gross and Sadowski.23

Application to Mixtures
In the case of an n-component mixture the total viscosity can
be expressed with basically the same type of mixing rules as in
previous works.1,5,6 That is, in the case of the dilute gas
viscosity, the mixture contribution may be approximated using
the following mixing rule:

x ln
n

0 exp

0,i

(23)

i1

and, consistent with previous works, the mixture mixing rules


for the friction coefcients are given by

z
n

i a,i

i1

1606

DOI 10.1002/aic

i1

a,i
z i a,i
p c,i

Figure 5. Comparison of viscosities for n-decane vs.


pressure p shown as the deviation (c/e 1)
100 between the calculated values by the
general PC-SAFT f-theory model (c) and the
experimental values (e).

(24)

Published on behalf of the AIChE

() Lee and Ellington29; (E) Carmichael et al.30; () Knapstad et al.31,32; (F) Oliveira and Wakeham33; () EstradaBaltazar et al.34; () Tohidi et al.35; () Audonnet and Padua 36;
() Ducoulombier et al.50

April 2006

Vol. 52, No. 4

AIChE Journal

Table 4. Predictive Results for the General PC-SAFT f-Theory Model Applied to n-Alkane Mixtures
System

NM*

NP**

T (K)

P (MPa)

AAD%

MxD%

C1 C241
C1 C342
C1 n-C443
C1 n-C644
C1 n-C1032,36
n-C5 n-C845
n-C5 n-C1046
n-C6 n-C747
n-C7 n-C848
n-C7 n-C947
n-C7 n-C1149
n-C8 n-C1034
n-C10 n-C1650
n-C5 n-C8 n-C1051
n-C10 n-C12 n-C14 n-C1650

3
4
1
3
7
9
9
2
4
2
2
9
3
15
1

250
282
104
53
200
295
312
53
172
57
57
324
54
530
18

120300
311411
278478
293451
292431
298373
298373
303323
292480
303323
303323
298373
313353
298373
313353

1.535
0.155
0.136
1543
9.876
0.125
0.125
0.172
0.149
0.172
0.172
0.125
0.1100
0.125
0.1100

3.35
2.36
4.50
4.93
6.84
3.98
3.17
1.19
2.68
1.11
3.29
2.97
3.44
3.41
1.25

19.9
6.57
7.95
12.1
21.9
12.4
14.3
3.68
9.22
3.19
7.21
6.37
9.33
15.7
4.62

*Number of mixtures.
**Number of points.

n-Alkane mixture results


A thorough evaluation of the PC-SAFT friction theory mixing rules has been performed on several binary through quaternary mixtures. The resulting AAD and MxD values are
reported in Table 4 along with the number of points (NP),
number of mixtures (NM), and the temperature and pressure
ranges. In general, it can be appreciated from Table 4 that the
accuracy of the mixture predictions is within or close to the
experimental uncertainty. The larger deviation found for the
methane n-decane system may arise from factors such as the
experimental uncertainty itself or the large acentric difference
between methane and n-decane. In fact, this system also provided the largest deviations in the PR and SRK f-theory models,1,5 which in the last cases are slightly higher than for the
PC-SAFT f-theory model. Figures 6 and 7 show the viscosity
prediction for the binary system methane propane and the
quaternary system n-decane n-dodecane n-tetradecane
n-hexadecane, respectively. A comparison of the general PCSAFT f-theory model with the other general f-theory models
for the PR, SRK, or PT EoS5,6 shows that similar results are

Figure 6. Viscosity of the binary methane propane


mixture at various isotherms vs. pressure p
predicted by the general PC-SAFT f-theory
model for 22.07 mol % methane () and for
79.1 mol % methane ( ), along with the experimental values of Giddings et al.42 (F).
AIChE Journal

April 2006

Vol. 52, No. 4

obtained for the studied n-alkane mixtures, although a more


accurate EoS is used in this work. This supports the prodigious
effort that has been given to tuning the scaling parameters of
the cubic EoS. However, it is to be expected that as chain
molecules become larger an EoS such as the PC-SAFT should
deliver a more robust overall performance (including phase and
density behavior) than that of a cubic EoS.
In this work, the required binary interaction parameters kij in
the PC-SAFT EoS were taken from Gross and Sadowski.23 For
mixtures where no kij parameters are reported in Gross and
Sadowski, it was found appropriate to use kij 0.01, except for
methane ethane and methane n-decane. For the system
methane ethane, the kij was determined by tting PC-SAFT
to experimental isothermal vaporliquid equilibria (VLE) measurements52-57 in the range 150 280 K. The temperature dependency of the kij is shown in Figure 8, revealing that the kij
values appear to follow a linear behavior as a function of the
temperature:
k ij 0.033594 0.00015494T

(30)

Figure 7. Viscosity of the quaternary mixture 31.44 mol


% n-decane 26.26 mol % n-dodecane
22.55 mol % n-tetradecane 19.75 mol %
n-hexadecane at various isotherms vs. pressure p predicted by the general PC-SAFT ftheory model (), along with the experimental
values of Ducoulombier et al.50 (F).

Published on behalf of the AIChE

DOI 10.1002/aic

1607

Conclusion

Figure 8. Temperature dependency of adjusted PCSAFT kij binary interaction parameters for
methane ethane (F).

where T is given in K.
An adjustment of the kij for methane n-decane has also
been performed to better reproduce the VLE behavior of this
system within the temperature range of the considered viscosity
data. The reason is that the kij value of 0.056 reported in Gross
and Sadowski23 was correlated against VLE data in the range
423 to 583 K, which is outside the temperature range of the
considered viscosity data. The temperature dependency of the
estimated Kij values obtained by tting the PC-SAFT EoS to
experimental VLE data 58-63 is shown in Figure 9, revealing a
linear dependency as a function of the temperature, which can
be expressed as
k ij 0.035905 0.00019412T

(31)

with T given in K.

Carbon dioxide n-alkane mixtures


In addition to the viscosity prediction of n-alkane mixtures
and to illustrate the capability of the general PC-SAFT f-theory
model to more dissimilar mixtures, the viscosities of mixtures
composed of carbon dioxide n-alkanes have been predicted.
The obtained AAD and MxD values are reported in Table 5
along with NP, NM, and the temperature and pressure range. In
general it can be appreciated from Table 5 that the obtained
results are satisfactory and close to the uncertainty reported for
the experimental viscosities.
For carbon dioxide mixtures the required binary interaction
parameters kij in the PC-SAFT EoS were taken from Gross and
Sadkowski,23 except for carbon dioxide ethane, where the
reported kij 0.09 in Garca et al.69 was used. For mixtures,
where no kij parameters are given in Gross and Sadkowski,23
the reported uniform value kij 0.12 as suggested in Garca et
al.69 was used. For this type of mixtures the results obtained
with the general PC-SAFT f-theory are better than those obtained by the general PT, PR, and SRK f-theory models.5,6 In
the case of the general PC-SAFT f-theory model an overall
AAD% of 4.58 is obtained compared with the 6.48, 5.67, and
6.83% obtained with the PT, PR, and SRK EoS general ftheory models, respectively.
1608

DOI 10.1002/aic

A general f-theory viscosity model coupled to the PC-SAFT


EoS has been developed. This f-theory model has been shown
to provide satisfactory results for the modeling of the viscosity
of the normal alkanes family, carbon dioxide, and nitrogen. In
addition, an evaluation of the performance of the general
f-theory model has been performed for several n-alkane and
carbon dioxide n-alkane mixtures over wide ranges of temperature and pressure, showing a good prediction of the viscosity within uncertainties satisfactory for most industrial and
research applications. This accurate viscosity prediction is
achieved using simple mixing rules for the friction coefcients.
Further, the general PC-SAFT f-theory model can potentially
be extended to the viscosity modeling and prediction of crude
oils based on the mass characterization procedure already introduced in an f-theoryrelated work16the subject of a forthcoming report. In addition, the general PC-SAFT f-theory
approach will also be applied to other asymmetric mixtures
such as refrigerant lubricant systems.
In addition, despite the fact that the more accurate PC-SAFT
EoS has been applied, it should be noted that the performance
of the general PC-SAFT f-theory model for the considered
mixtures in this work is practically similar to the performance
of the general f-theory models based on the SRK, PR, and PT
EoSs.5,6 The reason is certainly related to the fact that the
f-theory is built on a balance between attractive and repulsive
contributions, which makes it a more robust approach compared to models that directly depend on densityalthough the
model indirectly does depend on density. However, the combination of the f-theory with a more theoretically sound EoS,
such as the SAFT models, does provide extended advantages
regarding other phase and thermophysical properties as well as
a more theoretically sound description of the uid physics. For
example, it would be of theoretical and industrial relevance to
have an accurate representation of transport properties linked to
other thermophysical properties or complex phenomena such
as the barotropic behavior (recently discussed also using the
PC-SAFT model as the reference EoS70) or to models capable
of delivering an accurate representation of high-order derivatives because many important thermophysical properties do
depend of such derivatives.71

Figure 9. Temperature dependency of adjusted PCSAFT kij binary interaction parameters for
methane n-decane (F).

Published on behalf of the AIChE

April 2006

Vol. 52, No. 4

AIChE Journal

Table 5. Predictive Results for the General PC-SAFT f-Theory Model Applied to Carbon Dioxide n-Alkane Mixtures
System
CO2
CO2
CO2
CO2
CO2
CO2

C164
C265,66
n-C1067,68
n-C5 n-C1068
n-C4 n-C6 n-C1068
n-C5 n-C6 n-C7 n-C1068

NM*

NP**

T (K)

P (MPa)

AAD%

MxD%

3
6
6
2
2
2

132
362
69
10
10
8

323474
210500
311403
354401
324395
360395

3.470
2.161
6.735
2.54.9
2.54.9
2.54.9

2.95
5.60
2.60
1.50
7.61
2.80

8.76
22.2
12.7
3.26
17.9
6.04

*Number of mixtures.
**Number of points.

Acknowledgments
Financial funding of S.E.Q.-C. and C.K.Z.-M. was provided by two
grants from Xunta de Galicia. This work was supported by the Spanish
Science and Technology Ministry (PPQ2002-3262), European Union
(FEDER), and Xunta de Galicia (PGIDIT03PXIC20608PN).

7.

8.

Notation
kij
MW
m
p
pa
pc
pdisp
pid
phc
pr
R
T
Tc
v
vc
x
Z
z

9.

binary interaction parameter


molecular weight
molecular segment number
pressure
attractive pressure
critical pressure
dispersive pressure
ideal pressure (P RT/v)
hard-core pressure
repulsive pressure
universal gas constant
temperature
critical temperature
molar volume
critical molar volume
mole fraction
compressibility factor
volume-weighted fraction

10.

11.

12.

13.

14.

Greek letters

0
f
,a
,r

a
r
aa
rr

15.

molecular segment energy parameter


viscosity
dilute gas viscosity
residual friction term
attractive viscosity scaling parameter
repulsive viscosity scaling parameter
reciprocal reduced temperature dened in Eq. 16
linear attractive friction coefcient
linear repulsive friction coefcient
quadratic attractive friction coefcient
quadratic repulsive friction coefcient
molecular segment diameter
acentric factor

16.

17.

18.

19.
20.

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