Teoría de Fricción
Teoría de Fricción
Teoría de Fricción
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.
1600
April 2006
AIChE Journal
April 2006
(1)
0 f
(2)
a,i
p ai
p
r,i
i
r
(3)
f ap a rp r rrp r2
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 (}).
f ap a aap a2 rp r rrp r2
(5)
is proposed.
f a p a rp r
(6)
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)
(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
April 2006
AIChE Journal
Figure 2. Linear PR and PC-SAFT f-theory viscosity models for methane, along with the recommended data by
Zeberg-Mikkelsen27 (F).
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
DOI 10.1002/aic
1603
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 0,1 A 0,2
2
m
m
rr B 0,0
b0,1 b0,2
2
m
m
aa A 0,0
a0,1 a0,2
2
m
m
B 0,1 B 0,2
2
m
m
1604
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
April 2006
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
*1 P 104 mPa s.
April 2006
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
(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
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)
zi
x im i i
MW iF w
(28)
with
m
x MW
n
Fw
(22)
i i
i1
(29)
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
z
n
i a,i
i1
1606
DOI 10.1002/aic
i1
a,i
z i a,i
p c,i
(24)
() 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
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.
April 2006
(30)
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.
DOI 10.1002/aic
Figure 9. Temperature dependency of adjusted PCSAFT kij binary interaction parameters for
methane n-decane (F).
April 2006
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.
10.
11.
12.
13.
14.
Greek letters
0
f
,a
,r
a
r
aa
rr
15.
16.
17.
18.
19.
20.
Literature Cited
1. Quinones-Cisneros SE, Zeberg-Mikkelsen CK, Stenby EH. The friction theory (f-theory) for viscosity modeling. Fluid Phase Equilib.
2000;169:249-276.
2. Soave G. Equilibrium constants from a modied RedlichKwong
equation of state. Chem Eng Sci. 1972;27:1197-1203.
3. Peng D-Y, Robinson DB. A new two-constant equation of state. Ind
Eng Chem Fundam. 1976;15:59-64.
4. Patel NC, Teja AS. A new cubic equation of state for uids and uid
mixtures. Chem Eng Sci. 1982;37:463-473.
5. Quinones-Cisneros SE, Zeberg-Mikkelsen CK, Stenby EH. One parameter friction theory models for viscosity. Fluid Phase Equilib.
2001;178:1-16.
6. Quinones-Cisneros SE, Zeberg-Mikkelsen CK, Stenby EH. General one
parameter friction theory viscosity model for the PatelTeja EOS. Con-
AIChE Journal
April 2006
21.
22.
23.
24.
25.
26.
DOI 10.1002/aic
1609
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
ane, ethane, propane, isobutane, and normal butane. J Phys Chem Ref
Data. 1987;16:577-798.
Zeberg-Mikkelsen CK. Viscosity Study of Hydrocarbon Fluids at
Reservoir ConditionsModeling and Measurements. PhD Thesis.
Lyngby, Denmark: Technical University of Denmark; 2001.
Vogel E, Kuchenmeister C, Bich E, Laesecke A. Reference correlation
of the viscosity of propane. J Phys Chem Ref Data. 1998;27:947-970.
Lee AL, Ellington RT. Viscosity of n-decane in the liquid phase.
J Chem Eng Data. 1965;10:101-104.
Carmichael LT, Berry VM, Sage BH. Viscosity of hydrocarbons:
n-Decane. J. Chem Eng Data. 1969;14:27-31.
Knapstad B, Skjlsvik PA, ye HA. Viscosity of pure hydrocarbons.
J Chem Eng Data. 1989;34:37-43.
Knapstad B, Skjlsvik PA, ye HA. Viscosity of the n-decane
methane system in the liquid phase. Ber Bunsenges Phys Chem.
1990;94:1156-1165.
Oliveira CMBP, Wakeham WA. The viscosity of ve liquid hydrocarbons
at pressures up to 250 MPa. Int J Thermophys. 1992;13:773-790.
Estrada-Baltazar A, Alvarado JFJ, Iglesias-Silva GA, Barrufet MA. Experimental liquid viscosities of decane and octane decane from 298.15
K to 373.15 K and up to 25 MPa. J Chem Eng Data. 1998;43:441-446.
Tohidi B, Burgass RW, Danesh A, Todd AC. Viscosity and density of
methane methylcyclohexane from (323 to 423) K and pressures to
140 MPa. J Chem Eng Data. 2001;46:385-390.
Audonnet F, Padua AAH. Viscosity and density of mixtures of methane and n-decane from 298 to 393 K and up to 75 MPa. Fluid Phase
Equilib. 2004;216:235-244.
Fenghour A, Wakeham WA, Vesovic V. The viscosity of carbon
dioxide. J Phys Chem Ref Data. 1998;27:31-44.
Stephane K, Krauss R, Laesecke A. Viscosity and thermal conductivity of nitrogen for a wide range of uid states. J Phys Chem Ref Data.
1987;16:993-1023.
Chung T-H, Ajlan M, Lee LL, Starling KE. Generalized multiparameter correlations for nonpolar and polar uid transport properties. Ind
Eng Chem Res. 1988;27:671-679.
Poling BE, Prausnitz JM, OConnell JP. Properties of Gases and
Liquids. New York, NY: McGraw-Hill; 2000.
Diller DE. Measurements of the viscosity of compressed gaseous and
liquid methane ethane mixtures. J Chem Eng Data. 1984;29:215-221.
Giddings JG, Kao JTF, Kobayashi R. Development of a high-pressure
capillary-tube viscometer and its application to methane, propane, and
their mixtures in the gaseous and liquid regions. J Chem Phys. 1966;
45:578-586.
Carmichael LT, Berry V, Sage BH. Viscosity of a mixture of methane
and n-butane. J Chem Eng Data. 1967;12:44-47.
Berstad DA. Viscosity and Density of n-Hexane, Cyclohexane and
Benzene, and Their Mixtures with Methane. PhD Thesis. Trondheim,
Norway: Norges Tekniske Hgskole; 1989.
Barrufet MA, Hall KR, Estrada-Baltazar A, Iglesias-Silva GA. Liquid
viscosity of octane and pentane octane mixtures from 298.15 K to
373.15 K up to 25 MPa. J Chem Eng Data 1999;44:1310-1314.
Estrada-Baltazar A, Iglesias-Silva GA, Barrufet MA. Liquid viscosities of pentane and pentane decane from 298.15 K to 373.15 K and
up to 25 MPa. J Chem Eng Data. 1998;43:601-604.
Assael MJ, Charitidou E, Dymond JH, Papadaki M. Viscosity and
thermal conductivity of binary n-heptane n-alkane mixtures. Int J
Thermophys. 1992;13:237-249.
Aleskerov MA, Mamedov A, Khalilov AK. Experimental study of the
dependence of the dynamic viscosity of the binary liquid mixture
heptane octane versus temperature and pressure. Neft Gaz Izv Vyss
Uceb Zav. 1979;22:58-60.
Assael MJ, Karagiannidis L, Papadaki M. Measurements of the viscosity of n-heptane n-undecane mixtures at pressures up to 75 MPa.
Int J Thermophys. 1991;12:811-820.
Ducoulombier D, Zhou H, Boned C, Peyrelasse J, Saint-Guirons H,
Xans P. Condensed phases and macromolecules. Pressures (11000
bars) and temperatures (20 100C) dependence of the viscosity of
liquid hydrocarbons. J Phys Chem. 1986;90:1692-1700.
1610
DOI 10.1002/aic
51. Iglesias-Silva GA, Estrada-Baltazar A, Hall KR, Barrufet MA. Experimental liquid viscosity of pentane octane decane mixtures from
298.15 K to 373.15 K up to 25 MPa. J Chem Eng Data. 1999;44:
1304-1309.
52. Wichterle I, Kobayashi R. Vaporliquid equilibrium of methane
ethane system at low temperatures and high pressures. J Chem Eng
Data. 1972;17:9-12.
53. Davalos J, Anderson WR, Phelps RE, Kidnay AJ. Liquidvapor equilibria at 250.00 K for systems containing methane, ethane, and carbon
dioxide. J Chem Eng Data. 1976;21:81-84.
54. Miller RC, Kidnay AJ, Hiza MJ. Liquid vapor equilibria in methane
ethene and in methane ethane from 150.00 to 190.00 K. J Chem
Thermodyn. 1977;9:167-178.
55. Gupta MK, Gardner GC, Hegarty MJ, Kidnay AJ. Liquidvapor equilibria for the N2 CH4 C2H6 system from 260 to 280 K. J Chem
Eng Data. 1980;25:313-318.
56. Wei MS-W, Brown TS. Vapor liquid equilibria for the ternary
system methane ethane carbon dioxide at 230 K and its constituent binaries at temperatures from 207 to 270 K. J Chem Eng Data.
1995;40:726-731.
57. Raabe G, Janisch J, Koefoed J. Experimental studies of phase equilibria in mixtures relevant for the description of natural gases. Fluid
Phase Equilib. 2001;185:199-208.
58. Koonce KT, Kobayashi R. A method for determining the solubility of
gases in relatively nonvolatile liquids. Solubility of methane in ndecane. J Chem Eng Data. 1964;9:490-494.
59. Koonce KT, Kobayashi R. Vaporliquid equilibrium coefcients determined by gasliquid partition chromatography. The systems methanepropanen-decane and methanepropanen-heptane. J Chem Eng
Data. 1964;9:494-501.
60. Beaudoin JM, Kohn JP. Multiphase and volumetric equilibria of the
methanen-decane binary system at temperatures between 36 and
150C. J Chem Eng Data. 1967;12:189-191.
61. Wiese HC, Reamer HH, Sage BH. Phase equilibria in hydrocarbon
systems phase behavior in the methanepropanen-decane system.
J Chem Eng Data. 1970;15:75-82.
62. Lin H-M, Sebastian HM, Simnick JJ, Chao K-C. Gasliquid equilibrium in binary mixtures of methane with n-decane, benzene, and
toluene. J Chem Eng Data. 1979;24:146-149.
63. Srivastan S, Darwish NA, Gasem KAM, Robinson RL Jr. Solubility of
methane in hexane, decane, and dodecane at temperatures from 311 to
423 K and pressures to 10.4 MPa. J Chem Eng Data. 1992;37:516-520.
64. de Witt J, Thodos G. Viscosities of binary mixtures in the dense
gaseous state: The methane carbon dioxide system. SPE Paper
1335, 1977.
65. Diller DE, van Poolen LJ, dos Santos FV. Measurements of viscosities
of compressed uid and liquid carbon dioxide ethane mixtures.
J Chem Eng Data. 1988;33:460-464.
66. Diller DE, Ely JF. Measurements of the viscosities of compressed
gaseous carbon dioxide, ethane, and their mixtures at temperatures up
to 500 K. High Temp High Pressures. 1989;21:613-620.
67. Cullick AS, Mathis ML. Densities and viscosities of mixtures of
carbon dioxide and n-decane from 310 K to 403 K and 7 to 30 MPa.
J Chem Eng Data. 1984;29:393-396.
68. Barrufet MA, El-Sayed Salem SK, Tantawy M, Iglesias-Silva GA.
Liquid viscosities of carbon dioxide hydrocarbons from 310 K to
403 K. J Chem Eng Data. 1996;41:436-439.
69. Garca J, Lugo L, Fernandez J. Phase equilibria, PVT behavior, and
critical phenomena in carbon dioxide n-alkane mixtures using the
perturbed-chain statistical associating uid theory approach. Ind Eng
Chem Res. 2004;43:8345-8353.
70. Quinones-Cisneros SE. Barotropic phenomena in complex phase behaviour. Phys Chem Chem Phys. 2004;6:2307-2313.
71. Latte T, Bessie`res D, Pineiro MM, Daridon J-L. Simultaneous estimation of phase behaviour and second derivative propertes using
SAFT-VR approach. J Chem Phys. 2005; in press.
Manuscript received Sept. 2, 2005, and nal revision received Nov. 21, 2005.
April 2006
AIChE Journal