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Calculating the dynamic viscosity of paraffins using the Lee-Kesler equation

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DOI: 10.1134/S0040579510040135

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ISSN 00405795, Theoretical Foundations of Chemical Engineering, 2010, Vol. 44, No. 4, pp. 448–453. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © I.V. Derevich, V.S. Ermolaev, N.V. Zolnikova, V.Z. Mordkovich, 2010, published in Teoreticheskie Osnovy Khimicheskoi Tekhnologii, 2010, Vol. 44, No. 4,
pp. 487–472.

Calculating the Dynamic Viscosity of Paraffins

Using the Lee–Kesler Equation
I. V. Derevicha, V. S. Ermolaevb, c, N. V. Zolnikovab,c, and V. Z. Mordkovichc
a
Bauman State Technical University, Moscow, Russia
b
Moscow State University of Engineering Ecology, Staraya Basmannaya ul. 21/4, Moscow, 105066 Russia
c
Technological Institute of Superhard and New Carbon Materials, Troitsk, Russia
email: DerevichIgor@gmail.com@
Received August 19, 2009; in final form, November 23, 2009

Abstract—A model for calculating the viscosity of individual paraffins that constitute the major
part of the products of the Fischer–Tropsch synthesis is developed on the basis of the fluctuation
hypothesis of the formation of vacancies in the liquid phase. All of the thermodynamic parameters
of a substance and the energy barrier of the formation of vacancies are calculated using the Lee–
Kesler equation of state. The results of the calculations of the viscosity of heavy paraffins are com
pared with the experimental data from published works.
DOI: 10.1134/S0040579510040135

INTRODUCTION Let us dwell upon the current promising methods for

The synthesis of liquid hydrocarbons by the Fischer–
Tropsch method is a promising technique for the recycling
of petroleum gas and the processing of biomass. In the
synthesis carried out in Fischer–Tropsch reactors, high
molecular hydrocarbons, the major part of which is paraf
fins, are produced from a mixture of carbon monoxide
and hydrogen. The number of carbon atoms in the mole
cules of synthesized paraffins can reach 30–50. The reac
tors developed for synthesis are ones with a fixed bed of a
dispersed catalyst. Hydrodynamic processes associated
with the removal of the liquid products of synthesis from a
reactor affect the stability and safety of the operation of
the setups. The dynamics of the flow of the liquid film of
highmolecular hydrocarbons in the fixed bed of a dis
persed catalyst is determined by dynamic viscosity. In
published works, experimental data on the thermophysi
cal properties, including viscosity, of heavy paraffins are
presented fragmentarily up to С15. These data cannot be
used in modeling the technological regimes of synthesis.
At present, the development of methods for modeling the
viscosity of liquids and gases is promising. A review of
popular methods for calculating the dynamic viscosity is
presented in [1]. However, the calculation procedures
described in [1] are valid for comparatively light hydrocar
bons and lead to unsatisfactory results when they are used
over a wide range of thermodynamic parameters, in par
ticular, on the line of the liquid–vapor equilibrium. The
scope of the present study does not allow us to perform a
complete analysis of the methods for modeling the viscos
ity of organic compounds. A brief review of the main
approaches to the calculation of the viscosity of liquids
and gases is presented in [2].
calculating the viscosities of liquid highmolecular com
pounds. The main idea used in constructing the calcula
tion procedures is based on the fluctuation mechanism of
momentum transport in a liquid [3, 4]. To calculate the
viscosity of the liquid, thermodynamic parameters such as
the density and a compressibility factor are necessary.
Therefore, methods that use the equations of state both
for calculating the thermodynamics of a substance and for
modeling viscosity are promising. In [5], viscosity is cal
culated using an equation of state derived within the lat
tice model. In this study, the compressibility factor deter
mined from an equation of state is used in an expression
for dynamic viscosity. In model [5], two empirical func
tions are determined on the basis of an analysis of experi
mental data. Model [5] is adjusted for calculating the vis
cosity at high pressures.
The popular cubic equations of state such as the
Peng–Robinson equation, the Soave equation, and the
Redlich–Kwong equation are used in [6] for calculating
the viscosity of paraffins at high pressures. The type of the
equation of state in [6] is the key limitation. The calcula
tion of the dynamic viscosity is based on the balance of
intermolecular repulsive and attractive forces, which can
be found only using cubic equations of state. In [6], sets
consisting of seven constants that are different for each
type of an equation of state are found on the basis of the
processing of experimental data. The results of the calcu
lations show a satisfactory agreement with the experimen
tal data up to reduced pressures of 70. However, for high
reduced pressures, cubic equations of state are unstable
and yield a considerable error. In addition, the results of
the calculations of the thermodynamic properties of high

448
 CALCULATING THE DYNAMIC VISCOSITY OF PARAFFINS 449

molecular compounds with the use of cubic equations of tum diffusion; the number density of vacancies is pro
state noticeably differ from experimental data. portional to the density of a substance. Being guided
The present study is the generalization of the approach by these considerations, from (1)–(3), we write the
proposed earlier in [2]. Here, the fluctuation hypothesis of functional form of the dynamic viscosity of a liquid:
the formation of vacancies in a liquid is used. A closed id
model for calculating the dynamic viscosity of individual δΔH +σZ
hydrocarbons is proposed that does not depend on the ηl ∝ ρe R°T
. (4)
form of an equation of state. The model includes two Here, Z = PV ( R °T ) is the compressibility factor
empirical constants, the values of which for normal paraf that is independently determined from the equation of
fins are constant. The Lee–Kesler equation of state [7], state and ρ is the density.
which describes the thermodynamics of paraffins, includ
ing heavy ones, with a satisfactory accuracy, is used in the At the critical point (T = Tc, P = Pc, and Z = Z c the
model. The results of the calculations are compared with viscosity is identical to the critical value:
the experimental data. id
ΔH c
δ +σZ c
ηc ∝ ρce R°T
. (5)
DESCRIPTION OF THE MODEL A comparison of (4) and (5) leads to a simple formula
The reasoning given below is not a rigorous theory of for calculating the viscosity of a liquid:
the viscosity of a liquid or a compressed gas. The formulas
derived in the study are semiempirical, and the descrip ⎡ ΔH id − ΔH cid ⎤
tion of the theoretical constructions mainly serves as an ηl = ηcρ rexp ⎢δ + σ ( Z − Z c )⎥ , (6)
⎣ R°T ⎦
illustration of the proposed functional relationships. The
model of viscosity is based on the hypothesis of momen where ρ r = ρ ρ c is the reduced density.
tum transport due to the formation of an excited macro In (6), there are only two empirical constants, and all
scopic region with a reduced concentration of molecules of the other parameters are determined from the equation
in the liquid [3, 4]. The probability of the formation of a of state. The equation of state makes it possible, in partic
vacancy within an isobaric–isothermal ensemble (see, for ular, to calculate the line of the liquid–vapor phase
example, [8]) is approximated by the formula equilibrium. The value of dynamic viscosity at the criti

( ) (
w ∝ exp −σ PV exp −δ min ,
R°T
A
R°T ) (1)
where R° is the universal gas constant, T is the absolute
temperature of the medium, P is the pressure in the
medium, V is the molar volume, and δ and σ are
empirical constants that are chosen on the basis of an
analysis of experimental data.
In formula (1), Amin is the minimum work that is
necessary for the formation of an excited region in the
isothermal approximation:
Amin = Δ U + P Δ V , (2)
where Δ U , and Δ V are the local variation of internal
energy and the volume of the medium in the place of
the formation of the excited region, respectively.
We assume that the thermodynamic state of the region
with a reduced concentration of molecules can be
approximated by the ideal gas state. The minimum value
of work in (2) that is necessary for the formation of a
vacancy is equal to the deviation of the enthalpy of a sub
stance from the ideal gas approximation:
Amin = H id − H = ΔH id. (3)
The value of ΔH in (3) is calculated using the
id
chosen equation of state. The role of vacancies that
arise in a random manner is twofold. On one hand, a
decrease in the probability of the formation of vacan
cies leads to an increase in the friction coefficient. On
the other hand, vacancies are the centers of momen
cal point is estimated using the empirical approxima
tion [1, 6]
ηc = 7.7 Tc−1 6μ1 2Pc2 3.
Here, the critical temperature is in Kelvin, the molec
ular weight is in grams per mole, and the critical pressure
is in bars. As a result, the dynamic viscosity at the critical
point has a dimension of a micropoise (1 μP = 10–7 Pa s).
It should be noted that the critical temperature is unat
tainable for heavy paraffins with the number of carbon
atoms of more than 20, since thermal decomposition
begins at lower temperatures. The critical parameters of
such compounds are estimated using approximations
available in published works.
The formula given below for the viscosity of a com
pressed gas is a purely intuitive construction that is based
on wellknown tendencies of the behavior of the viscosity
of a gas at elevated temperatures. For a gas, momentum
diffusion is associated with the random motion of mole
cules, the intensity of which is proportional to the temper
ature of the gas. Using the hypothesis of residual viscosity
[1], we approximate the viscosity of the gas as
(
ηv = ηv + ηc − ηv
id id
) × Tr exp
(7)
⎡ ΔH id − ΔH cid ⎤
⎢δ  + σ ( Z − Z c )⎥ ,
⎣ RT ⎦
where ηvid is the viscosity of a rarefied gas and Tr = T Tc
is the reduced temperature.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

450 DEREVICH et al.

For a rarefied gas, Δ H id R T ≈ 0,the contribu

( ) B (Tr ) , C (Tr ) , and D (Tr ) .. The empirical functions in
tion of the second term in the righthand side of (7) is (9) are as follows:
small, and the viscosity is close to the viscosity of an
b2 b3 b4 c c
ideal gas. In approaching the critical point, as is seen B = b1 − − − , C = c1 − 2 + 33 ,
from (6) and (7), we have the values of ηl, ηl, ηv → ηc. T r Tr2 Tr3 Tr Tr
The viscosity of an ideal gas is calculated by the formu d
D = d1 + 2 .
las recommended in [1]. Tr
The calculation of dynamic viscosity in the entire The reduced molar volumes of simple and refer
region of thermodynamic parameters is performed as fol ence substances V r and V rR. respectively, are deter
lows. mined as a result of the double solution of the Lee–
At a temperature below the critical temperature, Kesler equation of state (9). The reduced volume of
T < Tc , the existence of a liquid and a vapor is possible. the substance being modeled is calculated by the for
If the pressure is lower than the saturated vapor pres mula that follows from (8):
sure, P < Ps (T ) , we have η = ηv(7) (see Eq. (7)). At
Vr = Vr + ωR VrR − Vr .
( )
P ≥ Ps (T ), the viscosity of a substance is identical to ω
the viscosity of a liquid η = ηl (see Eq. (6)). For super The compressibility factors for simple and reference
heated steam and subcritical pressures, T ≥ Tc and substances are
P ≤ Pc , viscosity is calculated by the formula for a
PV  PV R
vapor η = ηv (Eq. (7)). For the supercritical fluid, Z = r r , ZR = r r .
P > Pc , the approximation η = max (ηl, ηv ) . is used in Tr Tr
the entire temperature range. The compressibility factor of the substance being
modeled appears as

EQUATION OF STATE Z = Z° + ωR Z R − Z° .
( )
ω
The Lee–Kesler equation of state is based on the rep In accordance with procedure (8), for example, the
resentation of the thermodynamic property of the sub enthalpy and fugacity of the substance being modeled are
stance being modeled Ω as a combination of the proper found:
ties of simple and reference substances Ω° and ΩR,
respectively, and Pitzer’s acentric factor: H = H° + ωR H R − H° , φ = φ° + ωR φR − φ° ,
( ) ( )
ω ω

Ω = Ω + ωR ΩR − Ω ,
( )
R
(8) where H , H are the enthalpies of simple and refer
ω ence substances, respectively, and φ° , φ R are the
fugacity coefficients of simple and reference sub
where ω and ω are the acentric factors of the sub
R
stances, respectively. The coefficients of the Lee–
stance being modeled and the reference substance, Kesler equation and expressions for calculating the
respectively. enthalpy and fugacity coefficients are given in the
The idea of the Lee–Kesler approach is as follows. Appendix.
Transcendental equation of state (9) is solved individually
for simple and reference substances. As a reference sub RESULTS OF CALCULATIONS
stance, noctane is chosen. The Lee–Kesler equation of
state has the form The results of the calculations of the density of a liquid
using the Lee–Kesler equation have a substantially higher
Tr B (Tr )Tr C (Tr )Tr D (Tr )Tr accuracy than the cubic equations of state (Fig. 1). This
Pr = + + + + fact is illustrated in Fig. 1a. The accuracy of the calcula
Vr Vr2 Vr3 Vr6 tion of the thermodynamic potentials using the Lee–
(9)
c ⎛ γ⎞ ⎛ γ⎞ Kesler equation of state and the cubic equations is compa
+ 24 3 ⎜β + 2 ⎟ exp ⎜ − 2 ⎟ , rable (see Fig. 1b). It should be noted that the error in the
Tr Vr ⎝ Vr ⎠ ⎝ Vr ⎠ calculations of the density of heavy hydrocarbons
where γ , β , and c4 are empirical constants, which are increases with an increase in the number of carbon atoms
different for simple and reference substances. in a molecule. This leads to considerable errors in the
determination of the dynamic viscosity of heavy liquid
The equations of state for simple and reference paraffins. To improve the results of modeling the viscosity
substances are the same, but differ in the values of the of heavy hydrocarbons, we use a more complex equation
constants that are included into the functions of state.

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 CALCULATING THE DYNAMIC VISCOSITY OF PARAFFINS 451

ρ, kg/m3 The model for calculating the viscosity of paraffinic

(а) hydrocarbons was tested using a representative body of
750 experimental data. Experimental values on the satura
tion line and at high pressures are taken from [9], and
720
experimental data at pressures that substantially
690 exceed the thermodynamic critical value are taken
from [10]. For all normal paraffinic hydrocarbons, the
660 constants δ = 0.19 and σ = 1.5 did not change.
630 Figure 2 illustrates the dependence of the viscosity of
methane on the pressure on isotherms. It can be seen that
600 together with the calculation of the phase equilibrium
line, we obtain satisfactory data on the viscosity of both a
– 30 0 30 60 90 120 150
T, °C vapor and a liquid. Data in the supercritical region are also
described satisfactorily. The average relative error does not
ΔHlv, kJ/kg
exceed 6%.
360 (b)
A comparison of the viscosity of noctane on the iso
300 therms that correspond to the supercooled liquid state and
the twophase state, as well as on the critical isotherm,
240 with experimental data is presented in Fig. 3. The average
relative error for these experimental data does not exceed
180 2% (a formula for calculating the relative error is given in
120 the Appendix).

60
Figures 4 and 5 illustrate the dependence of the
dynamic viscosity of ndecane and npentadecane on the
0 reduced pressure. It can be seen that the results of the cal
0 60 120 180 240 300 culations are in satisfactory agreement with the experi
T,°C mental data [10]. The average relative error for these two
substances does not exceed 5%.
Fig. 1. (a) Density of liquid ndecane and (b) the enthalpy of The average relative error for the dynamic viscosity
the evaporation of ndecane. The dashed curve represents the of normal paraffins from methane to npentadecane
calculation by the Peng–Robinson equation of state, the solid
curve represents the calculation by the Lee–Kesler equation of on the saturation line and at high pressures (Pr ≤ 20 )
state, and the points represent experimental data [9]. does not exceed 8%.

η × 10 7, Pa s
η ×106, Pa s
104 1
1
10 2 2
10 3
4 3
10 4
10 5
103 5
6
10
10 7

10 6
10 102
0 100 101
100 101 102 Pr
P, bar

Fig. 2. Viscosity of methane on isotherms. The points repre Fig. 3. Influence of pressure on the dynamic viscosity of
sent the experimental data [9], and the lines represent the cal noctane. The points represent the experimental data [9], and
culations: T = (1) 100, (2) 110, (3) 130, (4) 150, (5) 180, the curves represent the calculations: Tr = (1) 0.5, (2) 0.6,
(6) 200, and (7) 220 K. (3) 0.7, (4) 0.8, (5) 0.9, and (6) 1.

THEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 452 DEREVICH et al.

η × 107, Pa s CONCLUSIONS
18000 In the present study, a closed procedure for calculating
the dynamic viscosity of normal paraffins in a wide range
15000
of thermodynamic parameters is developed. The thermo
dynamic parameters and dynamic viscosity of individual
1 highmolecular paraffins that are the products of the Fis
12000 cher–Tropsch synthesis are modeled using the Lee–
Kesler threeparameter equation of state with an accuracy
9000 2 sufficient for engineering applications. The model of vis
cosity does not depend on the type of an equation of state
6000 3 and is distinguished by simplicity and universality.
4 The results of the study can also be used in modeling
3000 the viscosity of the components of reservoir oil.
5 6 7 The main idea of the study about the modeling of vis
0 cosity on the basis of the activation mechanism of
0.1 1 10 momentum transport in a liquid is used in the modeling of
Pr
the viscosity of the solutions of paraffinic hydrocarbons.
Fig. 4. Dynamic viscosity of ndecane. The points represent
experimental the data [10], and the curves represent the calcu
lations: Tr = (1) 0.45, (2) 0.55, (3) 0.60, (4) 0.65, (5) 0.70,
(6) 0.70, and (7) 0.76. APPENDIX
The constants of the Lee–Kesler equation of state
are given in the table. The deviation of the enthalpy of
simple and reference substances H° and H R , respec
η × 107, Pa s tively, from the ideal gas approximation is calculated
by the formulas
25000
H − H id = T ⎧Z − 1 − b2 + 2 b3 Tr + 3 b4 Tr −
2

1  r⎨
20000 R Tc ⎩ TrV r
c2 − 3 c3 Tr2 d2 ⎫
2 − 2 + 5 + 3E ⎬,
15000 2 TrV r 5 TrV r ⎭
3
c4 ⎡ ⎛ λ⎞ ⎛ γ ⎞⎤
3 ⎢(1 + β) − ⎜1 + β + 2 ⎟ exp ⎜ − 2 ⎟⎥ .
10000 4 E=
5 2Tr γ ⎣ ⎝ Vr ⎠ ⎝ Vr ⎠⎦
5000 6 The logarithm of the fugacity coefficient of simple and
reference substances φ° and φR, respectively, is deter
0 mined as
0.1 1 10
Pr
ln (φ) = Z − 1 − ln ( Z ) + B + C 2 + D 5 + E.
Fig. 5. Dynamic viscosity of npentadecane. The points repre Vr 2Vr 5Vr
sent the experimental data [10], and the curves represent the
calculations: Tr = (1) 0.44, (2) 0.47, (3) 0.50, (4) 0.525, The saturated vapor pressure Ps (T ) of the substance
(5) 0.55, and (6) 0.575. being modeled is calculated from the condition of the

Values of constants in the Lee–Kesler equation of state

Constant Simple substance Reference substance Constant Simple substance Reference substance
b1 0.1181193 0.2026579 c1 0.0236744 0.0313385
b2 0.265728 0.331511 c2 0.0186984 0.0503618
b3 0.154790 0.027655 c3 0.0 0.016901
b4 0.030323 0.203488 c4 0.042724 0.041577
d1 × 104 0.155488 0.48736 β 0.65392 1.226
d2 × 104 0.623689 0.0740336 γ 0.060167 0.03754
Zc 0.2901 0.259 ωR – 0.3978

JOURNAL OF CTHEORETICAL FOUNDATIONS OF CHEMICAL ENGINEERING Vol. 44 No. 4 2010

 CALCULATING THE DYNAMIC VISCOSITY OF PARAFFINS 453

equality of the fugacity coefficients of the liquid and SUBSCRIPTS AND SUPERSCRIPTS
the vapor at a given temperature. c—value at the thermodynamic critical point;
The relative error is determined by the formula
id—ideal gas state;
Nexp η − ηexpi l—liquid state;
ε = 1 ∑ modi ,
N exp i =1 ηexpi o—thermodynamic parameters of the simple sub
stance;
whereηmod, ηexp are the dynamic viscosity calculated R—thermodynamic parameters of the reference sub
by the model and the experimental one taken from stance;
published data, respectively, and N exp is the number of r—reduced thermodynamic parameters;
experimental values. s—saturation line;
v—vapor state.
NOTATION
Amin —minimum work that is necessary for the for REFERENCES
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