[ l l l l m

ELSEVIER
Fluid Phase Equilibria 117 (1996) .'~,4--355
A r e v i e w o f p r a c t i c a l c a l c u l a t i o n me t h o d s f or t he v i s c o s i t y o f l i qui d
h y d r o c a r b o n s a nd t he i r mi x t u r e s
Anil K. Mehrotra, Wayne D. Monnery and William Y. Svrcek
Department of Chemical and Petroleum Engineering, The University of Calgary,
Calgary, Alberta T2N 1N4, Canada
This paper reviews methods for the prediction and correlation of Newtonian viscosity for
pure components and mixtures of liquid hydrocarbons and petroleum fluids, which are suited for
practical engineering use. The methods reviewed were chosen because they are well known and
accepted or appear potentially promising. The methods are categorized as semi-theoretical or
empirical and further distinguished as predictive or correlative. The applicability and average
deviations for each method are discussed, with the recommended methods identified.
1. INTRODUCTION
Whereas the gas phase viscosity is primarily a function of momentum transfer by
translation of the molecules with relatively few collisions, the momentum transfer in dense gases
and liquids is dominated by collisions and interacting force fields between the densely packed
molecules. Theoretical description of liquids is difficult due to intermolecular forces, which consist
of the short range (repulsion and hydrogen bonding), wide range (electrostatic), and long range
(attraction) effects. There is no widely accepted simple theoretical method for liquid viscosity.
Several models for the viscosity of pure components and mixtures are available in
literature, summarized in a recent review by Monnery et al. (1995). Excellent reviews have also
been given by Reid et al. (1977, 1987), Touloukian et al. (1975), Stephan and Lucas (1979) and
Viswanath and Natarajan (1989). However, petroleum fluids were not covered in any of these.
Petroleum liquids are complicated undefined fluids which must be characterized to obtain relevant
parameters. This paper reviews the most widely known and accepted models for viscosity
prediction/correlation of hydrocarbon and petroleum liquids. Although models for petroleum liquids
depend on the characterization used, the discussion here will focus on viscosity calculation. Models
for pure components are categorized in Figure 1, and for mixtures in Figure 2. Semi-theoretical
models have a theoretical framework, but the parameters are determined from experimental data.
The available viscosity calculation methods and results are summarized in Tables 1 and 2.
2. PURE HYDROCARBONS AND THEIR MIXTURES
2.1. Semi-theoretical methods
Semi-theoretical models are based on the principle of corresponding states or may be
categorized as applied statistical mechanics models such as the reaction rate theory, hard sphere
theory, square well theory or their modifications. These methods give viscosity as a function of
t emperat ure and density (or volume), which necessitates the coupling of a density prediction
method with the viscosity model.
0378-3812/96/$15.00 1996 El sevi er Sci ence B.V. All rights reserved
SSDI 0378 - 3812(95)02971-0
A.K. Mehrotra et al. / Fluid Phase Equilibria 117 (1996) 344- 355 345
Liquid Viscosity ]
I " ' - - .
Semi
Theoretical
1
c o
R e a c t i o n R a t e
H a r d S p h e r e
Square Well
Lemaard-Jones
Modmed
Chapman-Enskog
I [ Theoretical
(Sta~stieal
Me~b~n~_es)
/ /
I Empirical
(generalized)
Andrade
Vogel
Walther/ASTM
Viscosity EOS
I Mixture Viscosity I
Parameter
Mixing
Rules
I
Mi xi ng of
Pure
Component
Viscosities
(Theoretical
or Emp/rical)
Figure 1. Liquid viscosity models. Figure 2. Liquid-mixture viscosity models.
C o r r e s p o n d i n g s t a t e s
According to t he principle of corresponding states, a dimensionless property of one
substance is equal to t hat of another (reference) substance when both are evaluated at t he same
reduced conditions. Ely and Hanley (1981a) proposed t he extended corresponding states model:
= , , ~ - 2/ 3 ~ m ( 1)
~i(P, T) r l o ( p h i o , T / f i o ) ( Mi / Mo ) 1 / 2 "%o i,o
h i , o -- ( Y c , i / V c , o ) ~i,0 -- (Pc,o/Pc,i) i,0
(2)
f i , o --" (T ,i/Te,o) O i,o
(3)
where 0i, o and i,0 are shape factors. To calculate viscosity, reference fluid viscosity and density
correlations are required along with critical properties, acentric factor and molar mass. Met hane
as t he reference fluid was chosen because of t he availability of highly accurate reference fluid
viscosity and P - V - T correlations. A difficulty in using CH 4 as a reference fluid is t hat its freezing
point is T r = 0.48, which is well above t he reduced t emperat ures of other fluids in t he liquid state.
To overcome this, Ely and Hanley (1981a) extrapolated t he density correlation for CH 4 and added
an empirical correction for non-correspondence and extended t he viscosity correlation of Hanley et
al. (1975). Results are satisfactory for n-paraffins with AADs typically within 5-10%, but are
markedl y poor for isomeric paraffins and napht henes with AADs as high as 55% (Monnery et al.,
1991). The model was tested on mostly paraffinic binary mixtures, with an overall AAD of 7.0%.
Ely (1982) modified t he El y-Hanl ey model to partially correct for non-correspondence
between t he reference fluid and pure high molar mass fluids, and for size and mass differences in
mixtures. The non-correspondence was addressed by changing t he reference fluid from met hane
to propane, since propane has t he lowest reduced triple point amongst paraffins. For t he same test
components used by Ely and Hanley (1981a), t he viscosity predictions usi ng t he propane reference
were much t he same as before. In addition to using a better reference fluid, Ely (1984) developed
simpler shape factor correlations. The resulting shape factors being i ndependent of density are
computationally advantageous, removing t he need for iterative density calculations. Viscosity
results with this model were essentially t he same as those with earlier models.
346 A. K. Me hr ot r a et al. / Fl ui d Ph a s e Equi l i br i a 117 ( 1996) 3 4 4 - 3 5 5
Table 1
Summar y of calculation met hods for viscosity of liquid hydrocarbons and mi xt ures
Syst em
Test fluids
Reference Number Type AAD (%)
Basi s
Pure/Mix
Mix
Pure/Mix
Pure/Mix
Mix
Pur e
Pur e
Pur e
Pur e
Pure/Mix
Pure/Mix
Pure
Pur e
Pure
Mix
Pure
PurefMix
Pur e
Pure/Mix
Mix
Mix
Pure
Mix
Mix
Allan & Teja (1991) 2-3, 5.8
Asfour et al. (1991) <1.0
Assael et al. (1992a, b, c) 2.8, 4.0, 5.0
Cao et al. (1992) 1.1, <1.0, <5.0
Chhabra (1992) 135 NP/ P 7.0
Chung et al. (1984, 1988) 37, 80 NP/ P/ PH 3-4, <9.0
Collings & McLaughlin (1980) 14 NP/ P 2-70
Du & Guo (1991) 26 NP 9.3
Dymond (1974) 4 NP 1-7
Ely (1982) 35, 26 NP 8.4, 5.3
El y & Hanl ey (1981a, b) 35, 26 NP 8.4, 7.0
Heckenberger & St ephan (1991) 23 NP 4.7
Hwang & Whi t i ng (1987) 38 NP/ P/ PH 5.3
Lawal (1986) 24 NP 5.9
McAllister (1960) 4 NP/ P/ PH 0.5-15.8
Mehrot ra (1991a, b) 273, 89 NP
Orbey & Sandl er (1993) 50, 4 NP
Orrick & Erbar (Reid et al.) 188, 35 NP/ P/ PH
Pedersen et al. (1984) 15, 12 NP
Sheng & Lu (1990) 3 NP
Teja & Rice (1981) 6, 11, 6 NP/ P/ PH
van Velzen et al. (1972 a, b) 314, 35 NP/ P/ PH
Wei & Rowley (1984, 1985) 54 NP/ P/ PH
Wu (1986) 88 NP/ P/ PH
69, 11 NP
4 NP
16, 7, 37 NP/P, NP
>300, >200 NP/ P/ PH
Pred/ Corr
Pred
Pred/ Corr
Pred/ Corr
Pred
Pred/ Corr
Pred
Pred
Pred/ Corr
Pred
Pred
Pred
Pred/ Corr
Pred
Corr
2.3-35, 6.6-12.5 Pred
3-10, 2.4 Pred/ Corr
15.0, 14.8 Pred
8.1, 6.4 Pred
_<0.5 Pred
0.7, 2.5, 9.0 Pred/ Corr
<15.0, 10.8 Pred
2.7-4.4 Pred
3.8-7.4 Pred
Pure = pure component; Mix = mixture; NP = non-polar; P = polar; PH = polar hydrogen bonding;
Pred = predictive; Corr = correlative; Pred/Corr = predictive with adjustable parameter(s).
Table 2
Resul t s of different calculation met hods for viscosity of crude oil fractions
Crude oil fraction (AAD, %)
Reference Method Ameri can Arabi an Ot her Basi s
Ami n & Maddox (1980) Emp, Andrade 10.1 - 10.6
Bal t at u (1982) Corresponding st at es 6.6 - 6.6
Beg et al. (1988) Emp, Andrade 11.1 7.0 5.5
Chung (1989) modified Chapman-Enskog 8. 3 - 3.7
Dut t (1990) Emp, Vogel 6.8 5.3 3.8
Mehrot ra (1995) Emp, Wal t her 1.7 1.0 -
Emp, generalized 3.5 2.5 -
Orbey & Sandl er (1993) Emp, modified Andrade 4.7 6.1 5.9
Put t agunt a et al. (1992) Emp, similar to Wal t her 0.6 2.1 -
Pred
Pred
Pred
Pred
Pred
Corr
Pr ed
Pred
Corr
Emp = empirical; Pred = predictive; Corr = correlative
A.K. Mehrotra et al. / Fluid Phase Equilibria 117 (1996) 344-355 347
Hai l e et al. (1976), Hwang and Whiting (1987) and Monnery et al. (1991) have at t empt ed
to i mprove t he met hod by usi ng viscosity as a conformal equat i on and/or maki ng empirical
modifications to t he shape factors. For 38 compounds, t he modified met hod of Hwang and Whi t i ng
(1987) showed significant i mprovement for branched-al kanes, napht henes, some aromatics, and
vari ous polar and associating compounds wi t h overall AADs of 5.3%. Wi t h generalized correlations,
Monnery et al. (1991) predi ct ed viscosities of 46 common hydrocarbons wi t h an AAD of about 6%.
Peder sen et al. (1984) proposed a similar approach for hydrocarbon and crude oil viscosities:
B x ( P , T ) _ _ . ( T c , x / T c , o ) - l / 6 ( P c , x / P c , o ) 2 / 3 ( M x / M o ) l / 2 ( a T V , x / { X T V , O ) B o ( P o , T o ) (4)
whe r e To* =T( Tc, o/Tc, x)(U~TG, O /(ZTG, x), Po = P( Pc , o/Pc, x)({~TG, O /~TG, x) a nd a TV i s t he Tha m- Gubbi ns
rot at i onal coupling coefficient. According to Pedersen et al., difficulties in represent i ng polydisperse
mi xt ures (such as crude oils) were associated wi t h t he comput at i on of average mol ar mass. The
resul t s i ndi cat ed t hat larger molecules made a great er contribution to t he viscosity t han t he smal l er
ones. The mi xt ure molar mass was calculated empirically as: M m = M n + b l ( M w - M n ) , where b 1
is a fi t t ed constant. { ~PG wa s also det ermi ned empirically from t he mi xt ure mol ar mass and
reduced density. The mi xt ure viscosity was calculated from Equat i on (4) wi t h t he mixing rul es
provided for pseudo-critical properties. Pure component and mi xt ure viscosities were correl at ed
wi t hi n 6-8%. Peder sen and Fredensl und (1986) ext ended t he met hod of Pedersen et al. (1984) to
T r < 0.4 (below t he freezing point of CH 4) by modifying t he equat i ons for M m and {XTG.
The t hr ee- par amet er corresponding st at es met hod is based on an analogy of t he Pi t zer et
al. (1955a,b) expansi on of t he compressibility factor in acentric factor, Z = Z ~~ + ~Z ~1), where Z (1)
= ~ Z / ~ c o . Lee and Kesler (1975) expressed t he expansion of t he compressibility factor in t erms of
t he acentric factor as Z = Z + ( ~ c o r ) ( z r - Z ), where Z is t he compressibility of a simple (spherical)
reference fluid and co r and Z r are t he acentric factor and compressibility factor of a nonspheri cal
reference fluid. Teja et al. (1981) modified t he expansion such t hat t he simple fluid was not
necessari l y ret ai ned as one of t he references, resul t i ng in: Z = Z rl + [(co - corl)/(co r2 - o r l ) ] ( z r 2 - zrl),
where r l and r2 refer to two nonspherical reference fluids similar to t he pure component of i nt erest
or, for mi xt ures, to t he key const i t uent s of t he mixture. They applied this approach to viscosity:
l n( ~TR) = l n ( ~ T R )rl + [(CO - ~0rl)/((0 r2 - c o r l ) ] ( l n ( ~ T R )r2 - l n ( ~ T R ) r l ) (5)
where ~ r n = Yc2/ 3/ ( MTc )1/2" They t est ed t he met hod for 6 nonpolar+nonpolar mi xt ures wi t h t he two
component s comprising t he bi nary as t he reference components and a fitted bi nary i nt eract i on
paramet er. The met hod correlated nonpolar+nonpolar syst ems wi t h an AAD of 0.7%.
Tej a and Thur ner (1986) rest at ed t he Tej a-Ri ce (1981) viscosity met hod in t erms of Pc,
i nst ead of Vc, wi t h t he reducing par amet er described as : ~TR = Tcl/6/(M1/2Pc2/3). They adopt ed t he
mixing rul es of Wong et al. (1984) wi t h essentially t he same results. Wu and Asfour (1992) applied
t he Tej a-Ri ce (1981b) met hod in t erms o f P c wi t h t he mixing rules of Wong et al. to t er nar y and
quat er nar y n-al kane liquid mi xt ures to det ermi ne t he opt i mum reference fluids.
Aasberg-Pet ersen et al. (1991) proposed a met hod based on t he Tej a-Ri ce (1981b) met hod
wi t h t he reduct i on par amet er in t erms of critical pressure and molar mass as t he t hi rd par amet er
i nst ead of t he acentric factor. The met hod was t est ed at pressures as high as 70 MPa. For 12
paraffins and 6 aromatics, deviations were 5-39% and 10-35%, respectively. The AAD was 7.4%
for several bi nary mixtures, and 6.4% for t he crude oil dat a of Pedersen et al. (1984).
A 4- par amet er corresponding st at es method, analogous to t he Lee- Kesl er (1975) method,
involving 3 fixed reference fluids (CH4, n-CsHls and H20) was developed by Okeson and Rowley
(1991). For 28 hydrocarbons, t he overall AAD was 7.9%, compared to 8.3% for TRAPP.
R e a c t i o n r a t e t h e o r y
The react i on rat e t heory of Eyri ng and coworkers st at es t hat a liquid is densel y popul at ed
by molecules wi t h a few " holes" , which give t he liquid a new degree of translation. Viscous flow
348 A. K. Mehr ot r a et al. / Fl ui d Phas e Equi l i bri a 117 ( 1996) 3 4 4 - 3 5 5
is considered a " reaction" in which a molecule sometimes acquires t he activation energy necessary
to slip over a potential energy barri er and move to t he next equilibrium position. The resul t i ng
equat i on for liquid viscosity is (Glasstone et al., 1941):
T I -_- ( N A h / V ) e (aF' /R T) (6)
The t heory could reproduce viscosity vs. t emper at ur e behaviour, and gave some theoretical
significance to t he empirical Andrade (1934) equation ( ~ = Ae B/ T) , but it overpredicted viscosities
by 2-3 t i mes for most liquids (Kincaid et al., 1941).
McAllister (1960) applied Eyring' s equation for t he ki nemat i c viscosity of bi nary mixtures:
l nv x31nv 1 3 2 2
= +X2 l nv 2 3Xl x21nv12 + + 3XlX2 lnv21 - l n( Ma v g) (7)
3 3 2
+ x I ln(M1) x 2 ln(M 2) + 3 x 2 x 2 ln(M12) 3 x l x 2 ln(M21)
where Mavg = x t M 1 + x2M2, M12 = (2M 1 + M2)/3 and M21 = (M 1 + 2M2)/3. Equat i on (7) has 2
adj ust abl e paramet ers, v~2 and v21 , and is a cubic equation which could have a maxi mum,
mi ni mum, nei t her or both, all of which can occur in viscosity-composition data. This met hod is
applicable at a given t emper at ur e and to correlate viscosities over a t emper at ur e range, paramet ers
v12 and v21 and component viscosities, v 1 and v2, are requi red at two or more t emperat ures.
Asfour et al. (1991) emphasi zed t hat t he major drawback of t he McAllister met hod is t he
presence of t he adj ust abl e bi nary paramet ers (v/j). Usi ng experi ment al data, paramet ers for 6 n-
al kane bi nary mi xt ures were correlated to mat ch t he dat a wi t hi n 1%. Wei and Rowley (1985)
proposed a met hod based on Equat i on (6) which requi res pure component viscosity data, NRTL
bi nary information and excess enthalpy. For toluene+n-C v and benzene+n-C 6 bi nary syst ems, t he
AADs were 0.8 and 1.0%, respectively. Predicted viscosities were sensitive to bi nary paramet ers
and to t he effect of composition on excess enthalpy.
Wu (1986) utilized t he group contribution approach of UNIFAC (Fredensl und et al., 1975)
to describe t he excess free energy of activation for flow in Eyring~s equat i on for viscosity. The
met hod correlated and predicted t he viscosity dat a for 18 hydrocarbon bi nary mi xt ures wi t hi n 3.0%.
Cao et al. (1992) derived t he following viscosity model based on Eyring' s theory, usi ng
st at i st i cal mechanical lattice t heory and local composition.
TI i = ( 2 ~ R T M i / V?) y2 e (zq~niUJ2RT) (8)
Wi t h regressed constants, this met hod correlated t he pure component viscosities wi t h a MSRD of
1.1%. For mi xt ure viscosity, bi nary interaction paramet ers were obtained by correlating t he
viscosities of 215 mixtures. Cao et al. (1993a) re-derived t hei r model for molecular segment s to
t ake into account molecular size/shape and, in following work, Cao et al. (1993b) i nt roduced group
contribution utilizing UNIFAC paramet ers. For 384 bi nary and t ernary syst ems from vari ous
organic families, t he overall average MSRD was 4.1%. These resul t s are i mpressi ve for a
generalized, predictive model.
H a r d s p h e r e ( E n s k o g ) mo d e l s
A theoretical met hod to predict t he effect of densi t y on t he viscosity of gases is due to
Enskog (Hirschfelder et al., 1954; Chapman and Cowling, 1970). Although t he statistical
mechani cal basis is complex, t he resul t i ng simple equation for t he viscosity of hard spheres is:
"qEl ~ o = l / g(a) + 0. 8bp + 0.761g((~)(bp) 2 (9)
where ~ o = (5/16~ 1z2)[(mkT)1Z 2/a2]" The model requi res two paramet ers, a and g(~), along wi t h t he
fluid densi t y and molar mass. No fluid is a hard sphere (repulsion only) fluid; hence, Enskog
suggest ed replacing pressure wi t h t hermal pressure, t hereby implicitly accounting for attraction.
The resul t i ng met hod is known as modified Enskog t heory (MET).
A. K. Me hr ot r a e t al. / Fl ui d Ph a s e Equi l i bri a 117 ( 1996) 3 4 4 - 3 5 5 349
Dymond (1974) applied t he Enskog theory to noble gases, by correcting for molecular chaos
and wi t h g(~) obtained from t he Carnahan-St arl i ng (1969) equation of state (EOS). Dymond
st at ed t hat t he hard sphere theory satisfactorily represent ed the dat a above T c from >2Pc to 1.2Pc.
Dymond also obtained t he hard sphere di amet er as a function of t emperat ure for each of t he fluids.
Assael et al. (1992a) established universal curves for the t ransport properties of dense hard sphere
fluids, and gave predictions t hat were typically within 3%. Assael et al. (1992b) correlated t he
dense fluid t ransport properties of aromatic hydrocarbons within 3-5%. Assael et al. (1992c)
correlated t he dense fluid t ransport properties of 32 binary mixtures, 2 t ernary mi xt ures and 3
quat ernary mi xt ures of n-alkanes.
Sheng and Lu (1990) utilized t he Peng-Robinson (1976) EOS to obtain b and bpg(c), and
made t he const ant 0.8 in Equation (9) an adjustable parameter, although only substance-dependent.
With t he regressed adjustable parameter, they correlated liquid, vapour and dense phase viscosities
of met hane, ethane, propane and ethylene with AADs of 2-3%.
Squar e wel l model s
Davis et al. (1961) developed t he following equation for t he viscosity of square well fluids:
_- [1 +0.4bpg(q 1)+0.4R3bpg((~2)~/1 ]2 + 48 [ bpg(~l)+R4bpg(c2)~2] (10)
TlobP bpg(gl) + R 2bpg(~ 2)[~ 2 + (1/ 6)(e/ kT) 2] 25n
where W1 and ~2 are t emperat ure-dependent parameters. The model requires five paramet ers, gl,
e, R, g(~l) and g(g2), along with t he fluid density and molar mass. Collings and McLaughlin
(1980) used t he square well model to calculate t he t ransport properties for 14 polyatomic fluids.
They set R = 1.5, and regressed ~1 and e to mat ch t he second virial coefficients and critical
properties, wi t h t he AADs rangi ng from 2% for C 3 to 70% for cyclohexane.
Du and Guo (1991) empirically modified the Davis et al. (1961) square well theory and
applied it to 26 nonpolar fluids. The met hod correlated t he dat a with an overall AAD of 9.3%
al t hough deviations for met hane, n-butane, cyclohexane and toluene were 24-30%.
Le n n a r d - J o n e s model s
The Lennar d- J ones (LJ ) 6-12 intermolecular potential function is a well-known simple
potential energy model. Heyes (1988) t reat ed LJ molecules as effective hard spheres and correlated
t he viscosity by t he following equation.
o/ ~ = [1 -exp(-0.2195(V/V o- 1.384))] 1"75 (11)
For given values of p~j and kT/ e, this model correlated LJ molecular dynamics si mul at ed
viscosities to wi t hi n 10% over a wide range of conditions.
Sun et al. (1994) proposed a combination of t he rough sphere theory, with TILJ obtained from
Equat i on (11), by regressing e, ~LJ and t he effective hard sphere di amet er usi ng a pert urbat i on
theory. The rough sphere factor was regressed to mat ch t he viscosities of C2-C16 , and generalized
as a function of carbon number and kT&. The viscosity of n-Cx6H34 was predicted with an error
of 1.9%. The above met hods have not been extended to mixtures.
Modi f i ed Ch a p ma n - E n s k o g theory
Chung et al. (1988) extended t hei r earlier model based on t he Chapman- Enskog theory for
dilute gases to dense fluids and mixtures by introducing empirically correlated density and
t emper at ur e dependent functions into Enskog hard sphere theory. For 25 hydrocarbons, t he model
resul t ed in AADs of 3-4%. They extended t he met hod to mixtures with mixing and combining
rules, and t est ed t he met hod on 80 dense gas/liquid binary mixtures with an AAD about 9%.
Brul~ and Starling (1984) modified one of t he paramet ers in t he Chung et al. met hod to
model t he viscosity of polycyclic aromatic hydrocarbons. The met hod correlated viscosities wi t hi n
350 A. K. Me hr ot r a et al. / Fl ui d Phas e Equi l i bri a 117 ( 1996) 3 4 4 - 3 5 5
10%. The met hod became i naccurat e for viscosities above 10 mPa. s, which corresponds to T r < 0.35
for hydrocarbons. Reid et al. (1987) did not recommend t he met hod at T r < 0.5.
2.2. Empi ri cal met hods
A n d r a d e e q u a t i o n a n d i t s mo d i f i c a t i o n s
The following equation for t he variation of liquid viscosity with t emper at ur e was first
proposed by de Guzman (1913), t hough it is known as t he Andrade (1934) equation.
lnT1 = A + B / T (12)
For many liquids, Equat i on (12) has been successful from t he freezing to boiling points. It does not,
however, include t he effect of pressure, which has resul t ed in several modifications, most l y in t he
form density-dependence. A t hi rd paramet er, C, was added to obtain t he Vogel (1921) equation.
ln~ = A + B / ( T + C ) (13)
Reid et al. (1987) and Vi swanat h and Nat ar aj an (1989) have publ i shed values of A, B and
C in Equat i ons (12) and (13) for liquid hydrocarbons along wi t h t he recommended t emper at ur e
range. The discussion here will focus on studies in which t he const ant s in Equat i ons (12) or (13)
are listed for a large number of compounds or where an at t empt has been made to generalize t he
const ant s to i mpart predictive capabilities to t hese equations. Four met hods which at t empt to
predict t he const ant s by group contributions are t he met hods of Thomas, J oback, Orrick and Erbar
(Reid et al., 1977, 1987), and van Velzen et al. (1972a, b). Orrick and Erbar report ed an overall
AAD of 15% for 188 organic liquids, van Velzen et al. (1972) t est ed t hei r met hod wi t h 314 liquids,
of whi ch 272 had an average error of 15% or less. For 36 compounds in Reid et al. (1977), J oback' s
met hod had a mean deviation of 18%, compared to 16% and 15% for t he Or r i ck- Er bar and van
Velzen et al. methods, respectively. Reid et al. (1987) t est ed t he Or r i ck- Er bar and van Velzen et
al. met hods wi t h dat a for 35 compounds wi t h AADs of 14.8 and 10.8%, respectively. The deviations
vari ed significantly wi t h maxi mum deviations up to 60-70%.
Allan and Teja (1991) generalized t he const ant s in Equat i on (13) as functions of carbon
number for pure n-al kanes from C 2 to C20. With one val ue of liquid viscosity, t hey regressed
effective carbon numbers ( E C N s ) for 50 other hydrocarbons with an overall AAD of 2.3%. The
met hod was ext ended to mi xt ures usi ng a simple mixing rule for t he E C N . For bi nary mixtures,
t he met hod predicted viscosities wi t h an overall AAD of 5.8%. However, Gregory (1992) showed
t hat t he met hod gives an incorrect vi scosi t y-t emperat ure t rend for E C N > 22.
Orbey and Sandl er (1993) proposed t he following equation for liquid hydrocarbon viscosity:
l n(T1/ qref) = k [ -1. 6866 + 1 . 4 0 1 0 ( T b / T ) + 0 . 2 4 0 6 ( T b / T ) 2] (14)
where ~ r ef a n d k a r e paramet ers det ermi ned from experi ment al data. Wi t h regressed par amet er s
for 50 hydrocarbons, Equat i on (14) correlated t he dat a wi t h an overall AAD of 1.3%. Wi t h
generalized paramet ers, AADs for al kanes from C 3 to C2o were typically less t han 3%, except for
n-Cs, n-C 6 and n-Cz4 which had AADs of 9.6, 6.0 and 5.8%, respectively. For most alkenes, AADs
were also most l y less t han 3%. The model was ext ended to correlate viscosities at high pressures.
They ext ended t hei r model to alkane mixtures usi ng two approaches, a mi xt ure equat i on and a one-
fluid model for t he boiling point. Both approaches gave overall AADs of 2.4%.
A ST M o r Wa l t h e r e q u a t i o n
Anot her t wo-paramet er viscosity equation is t he ASTM (1981) or Wal t her (1931) equation.
loglog(xl + 0.7) = b 1 + b21ogT (15)
A. K. Me hr ot r a e t al. / Fl ui d Phas e Equi l i br i a 117 ( 1996) 3 4 4 - 3 5 5 351
Mehrotra (1991a) fitted experimental data for 273 pure heavy hydrocarbons from API
Research Project 42 (1966) to Equation (15), with the constant changed from 0.7 to 0.8 to extend
the range of the equation. With regressed values ofb 1 and b2, overall AADs ranged from 0.8% for
n-paraffins and olefins to 1.4% for nonfused aromatics. A linear correlation between the two
parameters was observed and used to derive the following one-parameter equation:
log(~ +0.8) = O ( O T ) b (16)
where b - b 2. By regressing the data for all compounds with Equation (16), the best values of O
and were found to be 100 and 0.01, respectively. The optimum values of paramet er b were
regressed for each compound, and the overall AADs ranged from 2.3% for branched paraffins and
olefins to 10.3% for fused-ring aromatics and 10.6% for fused-ring naphthenes. Finally, paramet er
b was generalized for each family of heavy hydrocarbons with molar mass and boiling point (at 10
mmHg). In a similar manner, Mehrotra (1991b) correlated data for 89 light and medium
hydrocarbons. With regressed values of b 1 and b2, AADs ranged from 1.7% for 1-olefins to 4.3% for
n-paraffins. With Equation (16) and the regressed values of parameter b, the overall AADs ranged
from 6.6% for aromatics to 12.5% for n-alkylcyclopentanes. Again, parameter b was generalized
for each hydrocarbon family in terms of molar mass, Tb, T c or acentric factor. Equation (16) is not
recommended for very light hydrocarbons at low temperatures.
Mehrotra (1994a) combined the E C N approach of Allan and Teja (1991) with Equation (16)
to provide a simple relationship between E C N and parameter b, which can be extrapolated reliably
to E C N > 22. Chhabra (1992) proposed a binary mixing rule without an adjustable interaction
paramet er based on Equation (16). For 135 binary mixtures involving 57 different nonpolar and
polar compounds, the overall AAD was 7%.
V i s c o s i t y e q u a t i o n s o f s t a t e
This approach is based on the phenomenological similarity between the P - V - T and P - ~ - T
surfaces resulting in a viscosity correlation which is an explicit function of T and P. Based on a
cubic EOS, Lawal (1986) proposed a viscosity EOS with the positions of T and P reversed and
viscosity replacing the volume (or density). The EOS involves 4 constants and 2 temperature-
dependent parameters. Mixing rules for the 6 parameters were also provided. The results were
correlated within 6% of the data. Heckenberger and Stephan (1990, 1991) also proposed a viscosity
EOS, based on their conclusion t hat a residual transport property (TP) surface P- ATP- T
corresponded better t han the P - p - T thermal surface. For alkanes up to C8, ethylene and
propylene, the AAD was 4.7%; however, maximum errors were up to 32.9%.
Li q u i d mi x t u r e v i s c o s i t y e q u a t i o n s
The viscosity of liquid mixtures is calculated either with parameter(s) mixing rules or
correlated with mixture-viscosity equations. The simplest mixture-viscosity equation is additive
in form: l ~ m) = E Y f l q i ) , where f(~) = viscosity function (-= rl, ln(~), or 1/rl). A common equation
for liquid hydrocarbons is: qm = (Exi~Y 3)3, which gives reasonably good results for mixtures whose
constituents do not differ much in structure.
Irving (1977) presented an excellent review of various mixture equations and tested their
effectiveness with 318 sets ofnonpolar+nonpolar, nonpolar+polar and polar+polar binary data. The
most effective equations for correlating viscosity data are of the parabolic type with one adjustable
or interaction parameter. The Grunberg equation is such an equation:
ln~ r~ --" ~ . x i ln(rl i) + ~_, ~_, x i x j G i j (17)
where G i j is an interaction parameter (with Gii = 0) . A familiar form of the Grunberg equation for
a binary mixture is: ln~ m = Xllnq 1 + x21nTI2 + Xl X2 G 1 2 . Irving reported t hat the Grunberg equation,
352 A. K. Mehr ot r a e t al. / Fl ui d Phas e Equi l i bri a 117 ( 1996) 3 4 4 - 3 5 5
with optimized G12 , gave RMS errors from 2.3% for nonpolar+nonpolar mixtures to 8.9% for polar+
polar mixtures. Generally, G12 is system-dependent and sometimes temperature-dependent,
making their generalization difficult.
3. PETROLEUM FRACTIONS, CRUDE OILS AND BITUMENS
3.1. Semi - t heoret i cal met hods
Most semi-theoretical methods for petroleum fractions are based on either the corresponding
states approach or the modified Chapman-Enskog theory.
Cor r e s pondi ng s t at es
Baltatu (1982) applied the method of Ely and Hanley (1981a) to predict the viscosity of
petroleum fractions data compiled by Amin and Maddox (1980). The overall AAD for 4 American
crude oil fractions was 6.6%, with maximum deviations of-18. 7 to -32.7%. As given in Table 2,
the overall AAD for 4 " other" crude oil fractions was 6.0%, with a maximum deviation of-30.2%.
J ohnson et al. (1987) modified the Ely-Hanley corresponding states method in applying it
to Athabasca (Canada) bitumen. The reference fluid was changed from CH 4 to a more conformal
heavy hydrocarbon, and empirical factors were introduced into the shape factor expressions to
match densities. With a new reference fluid EOS and viscosity correlations, bitumen viscosities
were predicted within about 6%. Mehrotra and Svrcek (1987) applied this method to predict the
viscosities of several Alberta (Canada) bitumens with AADs of 10-20%.
Using a characterization procedure, Pedersen et al. (1984) evaluated the rotation coupling
coefficient to match the viscosities of several North Sea crude oil samples within 6.5%. The modi-
fications by Pedersen and Fredenslund (1987) decreased the AADs from 6-14% to 3-8% for 14
crude oil mixtures and from 9-13% to 6-10% for crude oil fractions. Aasberg-Petersen et al. (1991)
applied their version of Teja-Rice (1981) method to crude oil viscosity with an overall AAD of 6.4%.
Mo d i f i e d Ch a p ma n - E n s k o g me t h o d
Chung (1989) modified his previously-presented method for the viscosity of petroleum
fractions by using a " characterization parameter" as opposed to the acentric factor. The
characterization parameter was determined by regression to match the boiling point and specific
gravity of petroleum fractions with an equation of state. The method was tested with the data
compiled by Amin and Maddox (1980); the overall AADs for the American and " other" crude oil
fractions were 8.3% and 3.7%, respectively.
3.2. Empi ri cal me t hods
A n d r a d e or de G u z ma n a n d Vogel equat i ons
Amin and Maddox (1980) compiled viscosity data for 4 American crude oil fractions and 4
" other" crude oil fractions and applied Equation (12) to model the kinematic viscosity as a function
of temperature by fitting the two parameters empirically. With generalized parameters, the overall
AADs for the American and other crude oil fractions were about 10%. Beg et al. (1988) applied the
Amin-Maddox approach to 4 fractions of Arabian crude oils. With generalized parameters, the
overall AAD for the Arabian crude oil fractions was 7.0%. For the American and other crude oil
fractions, the overall AADs were 11.1% and 5.5%, respectively.
Dutt (1990) used Equation (13) for crude oil fractions. Parameter C was obtained as per
Goletz and Tassios (1977), and parameters A and B were regressed to match viscosity data for 104
hydrocarbons, and then generalized. With the generalized parameters, overall AADs were 6.8, 5.3
and 3.8% for the American, Arabian and " other" crude oil fractions, respectively. Allan and Teja
(1991) applied their E C N approach to calculate the viscosity of Arabian Light, Mid Continent and
A.K. Mehrotra et a l . / Fluid Phase Equilibria 117 (1996) 344-355 353
Nort h Sea crude oil fractions wi t h t he AADs of 10-15%, 8-11% and 5-11%, respectively. Orbey
and Sandl er (1993) applied Equat i on (14) to pet rol eum fractions. The overall AADs for t he
American, Arabi an and ot her crude oil fractions were 4.7, 6.1 and 5.9%, respectively.
A ST M or Wa l t h e r e q u a t i o n
Mehr ot r a (1990a) applied Equat i on (15) to t he Middle-East crude oil and mi xt ure dat a of
Al -Besharah et al. (1989). To correlate t he effect of t emperat ure, par amet er s b 1 and b 2 were
regressed and it was found t hat b 2 fell in a narrow range such t hat it could be set to a const ant
value. Wi t h one paramet er, bl, for t he crude oils and mixtures, AADs were wi t hi n about 6%. To
correlate t he effect of pressure, t he t erm b3P* , where P* = ( P/ Pat m- 1) , was added. Both b 1 and b 3
were correl at ed wi t h crude oil mi xt ure densi t y at 25 C.
Mehrot ra (1995) used Equat i on (15) for t he ki nemat i c viscosity of crude oil fractions, wi t h
t he two par amet er s regressed usi ng t he dat a of Amin and Maddox (1980) and Beg et al. (1988).
An exami nat i on of t he par amet er s reveal ed t hat nei t her showed any t rend wi t h T b. However, t he
val ue of b 2 did not vary much; hence, it was set to -3.7. Par amet er b 1 was t hen expressed in t erms
of t he average boiling point (Tb): b 1 = 5.489 + 0.148 T '5. For t he Ameri can and Arabi an crude oil
fractions, t he overall AADs were 3.5% and 2.5%, respectively.
The viscosity of several Al bert a bi t umens was correlated also wi t h Equat i on (15) by Svrcek
and Mehr ot r a (1988), wi t h overall AADs typically wi t hi n 6%. It has also been applied to correlate
(with some at t empt s to generalize t he paramet ers) t he viscosity of Cold Lake bi t umen and its
fractions di l ut ed wi t h t ol uene (Mehrot ra et al., 1989; Mehrotra, 1990b, 1992a), di l ut ed-bi t umens
(Mehrotra, 1992b), and bi t umens sat ur at ed wi t h gases (Mehrotra, 1992c).
Put t agunt a et al. (1992) provided a viscosity correlation which, as shown by Mehrot ra
(1994b), is essent i al l y t he Wal t her equation. The correlation requi res one viscosity dat a point and
t he par amet er is not generalized, as pointed out by Orbey and Sandl er (1994). The crude oil
fraction dat a given in Ami n and Maddox (1980) and Beg et al. (1988) were correlated wi t h an
overall AAD of 2.1%. Singh et al. (1993) applied a similar correlation to t he dat a of Al -Besharah
et al. (1989); however, as pointed out by Mehrot ra (1994b), t here are errors in t he publication since
t he liquid viscosity is predicted to i nc r e as e wi t h t emperat ure. Furt hermore, no compositional
dependence or mixing rule was provided, implying t hat one viscosity dat um is requi red for every
new mixture.
Vi s c o s i t y e q u a t i o n s o f s t a t e
Lawal (1986) applied his viscosity EOS to various condensate, nat ural gas and crude oils
wi t h AADs of 19.7, 16.7 and 27.7%, respectively. However, resul t s vari ed significantly wi t h
maxi mum deviations of 40.9, 28.9 and 85.5%, respectively.
T wu ' s me t h o d
Twu (1985) developed a met hod for calculating t he ki nemat i c viscosity of hydrocarbons and
pet rol eum fractions at 100 and 210 F based on a pert urbat i on model, in whi ch n-paraffins are used
as a reference fluid. The overall AADs for calculation of ki nemat i c viscosities at 100 and 210 F of
pure hydrocarbons and pet rol eum fractions were 6.8% and 8.5%, respectively. To obt ai n viscosity
at any ot her t emperat ure, Twu recommended t he ASTM equation, wi t h t he par amet er s fitted from
t he viscosities at 100 and 210 F.
4. CONCLUSI ONS
There is an abundance of viscosity prediction/correlation methods. Most of t he existing
met hods are not t rul y predictive, requi ri ng viscosity dat a to det ermi ne adj ust abl e par amet er s or,
for mi xt ures, i nt eract i on paramet ers. It is difficult to st at e t he accuracy and reliability wi t h much
354 A. K. Me hr ot r a e t al. / Fl ui d Phas e Equi l i br i a 117 ( I 996) 3 4 4 - 3 5 5
cert ai nt y because the t est i ng of most methods by t he respective authors, wi t hout a common
database, has been limited. Tables 1 and 2 may provide some prel i mi nary guidance.
In fut ure viscosity modelling attempts, more emphasis should be placed on reducing t he
number of paramet ers followed by t hei r generalization for a wide array of compounds to improve
t hei r predictability. According to Ely and Hanl ey (1981a), the accuracy of most viscosity dat a is
in t he order of 5-15%; al t hough more recent dat a appear to be within about 5%. Thus, once the
AAD is less t han 5%, t here is little justification for improving the AAD by insignificant i ncrement s
at t he cost of additional parameters. Since such additional paramet ers usual l y require empirical
evaluation, t hei r generalization becomes increasingly difficult.
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