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1 Introduction
Liquid densities are needed in many engineering problems such as process calculations, simulations, equipment
and pipe design, and liquid metering calculations. A good liquid density correlation should be accurate and
reliable over the whole liquid region from the freezing point to the critical point. In most practical cases, the
fluids of interest are mixtures.
Liquid densities can be calculated from equations of state (EOS). Normally, the accuracy of liquid density
predictions with EOS is not sufficient, and therefore special correlations for liquid density are used. Many
accurate correlations are available for saturated liquid densities of pure fluids. The accuracy of many models is
not good enough for mixtures, mainly due to problems in formulating the mixing rules.
A good discussion of saturated and compressed liquid density calculation methods can be found in Poling et al.
[14]. For density of saturated pure liquids, they recommend the Daubert et al. [8] version of the (modified
Rackett) equation proposed by Spencer and Danner [16]. That model is applicable only for pure compounds.
Reid et al. [15] recommend Spencer and Danner [16] and Hankinson-Thomson [9] (HT) models. They also
recommend compressed liquid densities to be calculated using the Hankinson-Brobst-Thomson (HBT) model
[17], in which HT is used for saturated liquid density. Poling et al. [14] recommend the model by Aalto et al. [1,
2, 3] for accurate compressed liquid density; the model is applicable from triple point up to the critical point for
pure compounds. The model by Aalto et al. [1,2,3] uses the HT model as basis and is applicable both for pure
compounds and mixtures to predict compressed liquid densities. The data used in general model parameter
fitting of that model was limited to 20 MPa as maximum pressure, and therefore systematic errors at extremely
high pressures are obtained. Later, Aalto and Keskinen [5,6] published an improved version of Aalto et al.
[1,2,3] model. The new model is applicable for pure components and liquid mixtures also for extremely high
pressures and gives better density prediction near critical temperature. The Aalto and Keskinen [5,6] model also
uses the HT model as the basis for saturated liquid density.
The saturated liquid density models available in literature for refrigerant systems were reviewed by Nasrifar and
Mosfeghian [12] and they found that the HT model was the most accurate among 18 methods tested. They state
that Iglesias-Silva and Hall [10] model is better for polar compounds and non-hydrocarbons than the HT model.
Later, Nasrifar et al. [11] have published a compressed liquid density calculation model which is based on the
use of the HT model as the basis for saturated liquid density.
Based on the above discussion it can be stated that one of the most successful saturated liquid density calculation
models is the Hankinson-Thomson model. We will review the HT model, what general and pure-component
model parameters are needed, where they are already available and how to the fit the parameters from
experimental data. Then we will review shortly some of the above mentioned compressed liquid calculation
methods based on the HT model.
Our aim is to determine the HT model parameters for as many pure compounds as possible, as well as some
parameters needed by the compressed liquid calculation methods based on the HT model. We give a listing of a
few new HT parameters determined this far. The necessary data for the parameter fitting, data treatment, factors
to be taken into account and the fitting procedure is discussed. Also, we will review some of HT model
deficiencies that might need improvement. Carrying out a large study of parameter fitting would point out some
problem areas and hints for the HT model improvement. Our HT model parameter collection will be available on
a web-site.
Vs
= VR(0 ) 1 SRKVR( )
*
V
V R( 0) = 1 + a (1 Tr )
1/ 3
+ b(1 Tr )
(1)
2/ 3
+ c(1 Tr ) + d (1 Tr )
4/ 3
< 1.0
(2)
(3)
Tr =
(4)
Tc , HBT
For equations (2) - (3) the general parameters are the following:
a = -1.52816
b = 1.43907
c = -0.81446
d = 0.190454
e = -0.296123
f = 0.386914
g = -0.0427258 h = -0.0480645
The pure-component specific parameters are the following: characteristic volume V*, slightly adjusted critical
temperature Tc,HBT and the SRK-acentric factor SRK. These are tabulated for many compounds in Reid et al.
[15]. Reid et al. [15] recommended the use of these special parameters to get best accuracy. Hankinson and
Thomson [9] also give their original parameter collection. For refrigerant systems Aalto [4] has determined a set
of these parameters.
Although equation (2) was originally stated to apply only at range 0.25< Tr < 0.95, Aalto et al. [1,2,3], Aalto and
Keskinen [5,6] and also Nasrifar et al. [11] and Nasrifar and Mosfeghian [12] found it to hold reasonably well up
to the critical temperature.
Poling et al. [14] discuss the need for the special parameters V*, Tc,HBT and SRK. They state that real Tc can be
used in place of special Tc,HBT. We agree on this, but remind that the same value of Tc should be used with the
model that was used in the fitting of the V* and SRK. Poling et al. [14] also state that with a little loss of accuracy
V* can be set equal to Vc and correspondingly SRK can be set to the normal Riedel acentric factor . Later in this
paper we will see how this simplification affects on the error of density prediction.
A + C ( D Tr ) ( p r p s ,r )
B
V = Vs
A + C ( p r p s ,r )
(5)
where
b1
b2 + SRK
(7)
C = c1 (1 Tr ) 2 + 1 (1 Tr ) 2 exp[c3 + c4 ( pr p s ,r )]
c
(6)
(8)
pr =
ps
p
and p r , s =
.
pc
pc
(9),(10)
The AK model uses the same pure component parameters as the HT model: V*, Tc,HBT and SRK. In addition to
that the critical pressure and saturated liquid vapor pressure are needed.
available. Therefore we have chosen to use the real critical temperature Tc instead of Tc,HBT. It should be noted
that there is wide variation in the critical temperature values reported in the literature, especially for heavier
compounds. Thus, the same Tc value that is used in other parameter (V* and SRK) fitting should be used also
when applying the HT model.
Table 1: Some of the new HT parameters already determined in this project. Critical values from other sources.
Tc, K
V*, cm3/mol SRK
pc, MPa
Notes
Component
Argon, Ar
150.8
75.471
-3.5E-05
4.874
Revised
Boron trichloride, BCl3
455.0
229.84
0.1651
3.871
New
260.8
80.232
0.4258
4.99
New
Bromine, Br2
588.0
141.75
0.1024
10.3
New
440.0
134.15
0.2608
9.119
New
Chlorine, Cl2
416.9
123.21
0.0851
7.98
New
563.0
249.60
0.1937
5.67
New
508.1
318.72
0.2206
3.59
New
Deuterium, D2
38.4
61.457
-0.1609
1.66
New
Fluorine, F2
144.3
66.752
0.0506
5.22
Revised
234.0
120.34
0.1252
4.53
New
259.0
165.22
0.4160
3.72
New
318.7
200.05
0.2057
3.76
New
Hydrogen iodide, HI
424.0
124.77
0.0788
8.31
New
373.2
405.5
97.922
69.572
0.0970
0.2441
8.94
11.35
Revised
Revised
Hydrazine, N2H4
653.0
97.246
0.3047
14.7
Revised
Helium, He
5.19
61.479
-0.4086
0.227
Revised
Iodine, I2
819.0
184.79
0.1058
11.65
New
n-Decane, C10H22
617.7
619.03
0.4918
2.11
Revised
Example 1: The saturated liquid molar volume of n-decane at temperature 25 C is 195.95 cm3/mol (Poling et
al. [14]). The saturated liquid molar volume is calculated using the values from a) Poling et al. [14] as Tc,HBT = Tc
= 617.70 K, V* = Vc = 624.00 cm3/mol, and SRK = = 0.490, b) Reid et al. [15] Tc,HBT = 617.65 K, V* = 619.20
cm3/mol, and SRK = 0.4916, and c) new values in table 1 above Tc,HBT = Tc = 617.70 K, V* = 619.03 cm3/mol,
and SRK = 0.4918.
Results: Using equations (1) - (4) we get
Case
a)
b)
c)
T, K
298.15
298.15
298.15
Tr
0.48267768
0.48271675
0.48267768
VR( 0)
VR( )
0.3583816
0.3583969
0.3583816
0.24109728
0.24109192
0.24109728
Vs, cm3/mol
197.21
195.62
195.55
Error, %
+0.64
-0.17
-0.20
Based on the example, it is justified to eliminate the use of separate Tc,HBT value since the use of real Tc gives
nearly identical values. Also, the Poling et al. [14] approximation is useful if separate V* and SRK values are not
available, but some accuracy is then lost, which is clearly seen by example 2.
Example 2: The saturated liquid molar volume of liquid iodine (I2) at temperature 453.2 K is 67.86 cm3/mol
(Poling et al. [14]). Using values Tc,HBT = Tc = 819.00 K, V* = Vc = 155.00 cm3/mol, and SRK = = 0.1115
(from vapor pressure correlation) from Poling et al. [14] we get Vs = 56.47 cm3/mol, which is -16.78 % in error!
The values from table 1 above (Tc,HBT = Tc = 819.00 K, V* = 184.79 cm3/mol, and SRK = 0.1058) yield Vs =
67.42 cm3/mol, which is only -0.65 % in error.
7 Discussion
The Hankinson-Thomson model is one of the most accurate and most general models for saturated liquid density
prediction. This method is used as a basis in many compressed liquid density calculation methods; saturated
liquid density is obtained first and then the effect of pressure is taken into account. Both the HankinsonThomson model and the compressed liquid density models require a set of special pure-component parameters:
V*, Tc,HBT and SRK. We have chosen to use the real critical temperature instead of Tc,HBT. The parametersSRK and
V* are fitted for each pure compound using pure component vapor pressure data (or vapor pressure correlation
equation like Antoine) and saturated liquid density data, respectively. For mixtures, the models use
pseudocomponent method with suitable mixing rules requiring pure component critical pressure also. No binary
interaction parameters are used. When the compressed liquid density is calculated, one should also have the pure
component vapor pressure available.
In our project, we have started to determine these parameters for a collection of pure compounds. The
determination of a large collection of pure-component parameters will probably point out problems in the HT
model and thus give us hints where the model can be improved. The parameter collection will be available at the
web-site (note small and capital letters):
http://www.hut.fi/Units/ChemEng/Research/Density/index.html
8 References
[1] Aalto, M., Keskinen, K.I., Aittamaa, J., Liukkonen, S., Proceedings, The 4th Asian Thermophysical
Properties Conference (ATPC95), September 5-8, 1995, Tokyo, Japan.
[2] Aalto, M., Keskinen, K.I., Aittamaa, J., Liukkonen, S., Fluid Phase Equilibria 114 (1996) 1-19.
[3] Aalto, M., Keskinen, K.I., Aittamaa, J., Liukkonen, S., Fluid Phase Equilibria 114 (1996) 21-35.
[4] Aalto, M., Fluid Phase Equilibria 141 (1997) 1-11.
[5] Aalto, M., Keskinen, K.I., Proceedings, The 5th Asian Thermophysical Properties Conference (ATPC 98),
August 30 - September 2, 1998, Kim, M.S., Ro, S.T. (eds.), Seoul, Korea, 1998, 179-182.
[6] Aalto, M., Keskinen, K.I., Fluid Phase Equilibria 166 (1999) 183-205.
[7] Chang, C.-H., Zhao, X., Fluid Phase Equilibria 58 (1990) 231-238.
[8] Daubert, T.E., Danner, R.P., Sibel, H.M., Stebbins, C.C., Physical and Thermodynamic Properties of Pure
Chemicals: Data Compilation, Taylor&Francis, Washington, D.C., 1997.
[9] Hankinson, R.W., Thomson, G.H., AIChE J. 25 (1979) 653-663.
[10] Iglesias-Silva, G.A., Hall, K.R., Fluid Phase Equilibria 131 (1997) 97-105.
[11] Nasrifar, Kh., Ayatollahi, Sh., Mosfeghian, M., Fluid Phase Equilibria 168 (2000) 149-163.
[12] Nasrifar, Kh., Mosfeghian, M., Fluid Phase Equilibria 158-160 (1999) 437-445.
[13] Pokki, J.-P., Aalto, M., Keskinen, K.I., Remarks on computing the density of dense fluid, Paper presented in
the 9th International Conference of Properties and Phase Equilibria for Product and Process Design, PPEPPD
2001, May 20-25, 2001, Kurashiki, Japan, to be published.
[14] Poling, B.E., Prausnitz, J.M., O'Connell, J.P., The Properties of Gases and Liquids, 5th edition, McGrawHill, New York, 2000.
[15] Reid, R.C., Prausnitz, J.M., Poling, B.E., The Properties of Gases and Liquids, 4th edition, McGraw-Hill,
New York, 1987.
[16] Spencer, C.F., Danner, R.P., J.Chem.Eng.Data 17 (1972) 236-241.
[17] Thomson, G.H., Brobst, K.R., Hankinson, R.W., AIChE J. 28 (1982) 671-676.