Fluid Phase Equilibria, 73 (1992) 27-38 27

Elsevier Science Publishers B.V., Amsterdam

The Bender equation of state for describing thermodynamic

properties of krypton, neon, fluorine, sulfur dioxide
and water over a wide range of state

A. Polt ’ and G. Maurer

Lehrstuhl fir Technfiche Thermodynamik, Universit& Kaiserslautern,
D-W-6750 Kaiserslautem (Germany)
(Received June 19, 1991; accepted in final form October 28, 1991)

ABSTRACT

Polt, A. and Maurer, G., 1992. The Bender equation of state for describing thermodynamic
properties of krypton, neon, fluorine, sulfur dioxide and water over a wide range of state.
Fluid Phase Equilibria, 73: 27-38.

The parameters of the Bender equation of state for krypton, neon, fluorine, sulfur
dioxide and water were fitted to experimental pressure-density-temperature data and
saturation properties. The resulting equations cover the gaseous as well as the liquid region.
Calculated densities typically deviate from experimental results by about 0.4%; for vapor
pressure and coexisting (liquid and gaseous) densities the deviations typically are about
0.05%, 0.2% and 1% respectively.

INTRODUCTION

Thermodynamic properties of pure fluids are described either by a

fundamental equation or a combination of an equation of state and some
information on the ideal gas-state heat capacity. In recent years many
sophisticated equations have been proposed to describe the volumetric as
well as the thermal properties over a wide range of state including the
two-phase region. Describing precisely with a single equation several prop-
erties such as p-p-T data, vapour pressures, residual parts of the enthalpy

Correspondence to: Professor Dr.-Ing. G. Maurer, Lehrstuhl fiir Technische Chemie,

Universitat Kaiserslautem, Erwin Schriidinger Strasse, D-W-6750 Kaiserslautem, Germany.
’ Present address: BASF AG, Zentralbereich Technische Entwicklung W-6700 Lud-
wigshafen a. Rh., Germany.

0378-3812/92/$05.00 0 1992 Elsevier Science Publishers B.V. All rights reserved

28

and the heat capacity, requires expressions which have to incorporate a

large number of adjustable parameters. Usually a reliable equation of state
contains between ten and more than one hundred parameters. Structure
optimized equations especially developed for a single substance or a small
group of substances reduce the number of parameters while being able to
accurately reproduce experimental data, ‘but from an engineering point of
view these equations have some disadvantages. For each equation special
computer software has to be developed and the generalization of the
equations for predicting properties of other pure fluids or mixtures is
nearly impossible. From a more practical point of view it is more efficient
to use a somewhat less sophisticated yet sufficiently accurate single equa-
tion and determine the adjustable parameters for as many fluids as possi-
ble. This procedure was followed in the present work.
The Bender equation of state has been successfully applied to describe
the thermodynamic properties of argon, nitrogen, oxygen (Bender, 1973),
carbon dioxide (Bender, 1970), hydrogen (Bender, 1981), methane, ethane,
propane, ethylene and propylene (Biihner et al., 1981) as well as of 16
halogenated hydrocarbons (refrigerants) (Platzer et al., 1990). It is also
used here to describe the thermodynamic properties of further fluids,
provided enough experimental data are available for determining the total
19 parameters. This publication reports results for five monoatomic, di-
atomic and triatomic fluids including a polar substance (water).

BENDER EQUATION OF STATE

The Bender equation of state is an extended virial equation. It is a

modification of the Bendict-Webb-Rubin equation (Benedict et al., 1940)
as well as of the Starling equation (Starling, 1973):
P(P, T)
=pT[R+Bp +Cp2+Dp3+Ep4+Fp5+ (G +Hp2)p2 exp(-a,p2)]
(1)
with temperature functions
B = a, + a,/T + a3/T2 + a4/T3 + as/T4 (14
C = a6 + a,/T + a,/T2 (lb)
D = a, + a,,/T (14
E = alI + a,,/T w
F = a,,/T ue>
 29

G = a,,/T3 + a,,/T4 + a,,/T5 (19

H = a,,/T3 + a,,/T4 + a,,/T’ (lg)
coefficient azo is usually predicted from the critical density a, = l/p:, but
in some cases small variations in azo from that relation yield a considerable
improvement.
Several investigations have shown that the Bender equation can be
successfully applied to correlate thermodynamic properties of pure fluids in
the gaseous as well as in the liquid phase. It only fails like all analytical
equations in the immediate neighborhood of the critical point.
The 19 parameters of the equation are usually determined by fitting to
experimental pressure-density-temperature data in the gaseous and in the
liquid region as well as to precorrelated vapour pressures and other
saturation properties by means of applying the Maxwell criterion. Details
on that procedure are available in the literature (Bender, 1973; Polt, 1987).

IDEAL GAS-STATE HEAT CAPACITY

For completely describing the thermodynamic behavior of a fluid, be-

sides the equation of state, information on the ideal gas-state heat capacity
is needed. In the present work literature data on the isobaric heat capacity
at zero pressure, ci, are correlated by an empirical equation:

c; = t d,(T)‘-’ (2)
i=l

where ci is in J g- ’ K- ’ and T is in K.

RESULTS

Parameters aj for the Bender equation of state for krypton, neon,

fluorine, sulfur dioxide and water are given in Tables l-5 together with
information on the pressure, density and temperature ranges of the experi-
mental data on which the parameters are based and the references for that
data. Additionally, Figs. l-5 explain the region covered by the underlying
experimental data. The units of density are g cme3, and pressures and
temperatures are MPa and K respectively. As the equation fails in the
immediate neighborhood of the critical point one should not use it in the
temperature region
T*=T,-l.O<T<T,+l.O=T** at densities p”(T**)<ppp’(T*)
30

TABLE 1
ai for the Bender equation of state and experimental data for krypton

Critical properties and molecular weight: p&MPa) = 5.50222; p&g cme3) = 0.9090; T,(K) =
209.40; M = 83.70; R(J g-l K-l)= 9.93354x lo-‘.
Equation of state parameter: a, = 6.5938891690 X lo-*; a2 = -4.0571007860 x 10; a3 =
2.7849769770 x 103; a4 = -7.3606658440 X 10’; a5 = 3.4594724970 X 10’; a6 =
-7.6921567890x 10-3; a, = 1.6779773100x 10; as = 2.3157513400x lo*; a, = 2.9836283720
x lo-*; a,, = -1.7622483850x 10; al, = -3.7548214840x 10-3; aI = 4.9864458520; al3 =
2.8391097110 x 10-l; aI = -6.4894979130 X 10’; aI = 2.5062646360 x 10’; uI6 =
-2.8889378510 x lOlo; aI7 = -2.8926365220 x 10’; urs = 7.6705646720 x 10’; a,s =
1.2951380280 x 10”; a, = 1.2102420363.
Underlying experimental data:
Pressure-density-temperature (N = 1622): 0.25 < p(MPa) Q 373.78; 0.01716 $ p(g crne3)
< 2.80747; 120.00 < T(K) < 778.38.
Saturation properties (N = 40): T,,,,,,(K)= 116; p,,(MPa) = 0.073; &,(g crnm3) = 2.45;
p~i”(g cme3) = 0.0065.
References: Albuquerque et al. (1980); Barreiros et al. (1982); Beattie et al. (1952); Mathias
et al. (1937); Michels et al. (1952); Novikov et al. (1974); Rabinovich et al. (1973); Street and
Staveley (1971); Theeuwes and Bearman (1970); Trappeniers et al. (1966).

TABLE 2
a, for the Bender equation of state and experimental data for neon

Critical properties and molecular weight: p,(MPa) = 2.6664; p,(g crne3) = 0.484; T,(K) =
44.45; M = 20.179; R(J g-r K-‘) = 0.412031.
Equation of state parameter: a1 = 3.1862726390 X 10-l; a2 = - 2.9324312310 x 10; a3 =
- 1.6038518950 x 103; a4 = 2.8998165480 x 104; us = - 2.2593974260 x 10’; a6 =
7.1590441840 x 10-l; a7 = -3.6856589850 x 10; us = 4.2160233670 x lo*; us =
- 1.5351896140; a,, = 1.6862832570x lo*; aI, = 1.5893092460; a,, = -2.3177225280x lo*;
a 13 = 9.0405270090 x 10; aI = -3.2109957510 x 105; aI5 = 4.2313945130 x 10’; aI6 =
- 1.2736339620 x 109; al7 = 6.9363611510 x 106; ars = - 8.6799972950 x 108; aI9 =
2.5333184320 x lOlo; a2o = 2.0000000000 x 10.
Underlying experimental data:
Pressure-density-temperature (N = 1261): 0.09 Q p(MPa) Q 98.97; 0.00302 < p(g cme3)
< 1.26207; 27.00 c T(K) Q 723.15.
Saturation properties (N = 16): T,,(K) = 25.0; p,,(MPa) = 0.0509; &,(g cmW3>= 1.240;
&,(g cmp3> = 0.005.
References: Crommelin et al. (1918); Gladun (1966); Holborn and Otto (1926); Mathias et
al. (1922); McCarty and Stewart (1965); Michels and Gibson (1928); Michels et al. (1950);
Osnovskii and Moroz (1970); Osnovskii (1971); Rabinovich et al. (1970); Scott (1967); Street
(1971); Sullivan and Sonntag (1970).
 31

TABLE 3
a, for the Bender equation of state and experimental data for fluorine

Critical properties and molecular weight: p,(MPa) = 5.2153; p&g cm-? = 0.574; T,(K) =
144.31; A4 = 37.997; R(J g- ’ K- ‘) = 0.218815.
Equation of state parameter: a, = 2.3823775150 x lo- ‘; a2 = - 8.7424940580 x 10; a3 =
1.5494392790X 103; a4 = - 5.0231636610 X 105; a5 = 6.6495654510 X 106; a6 = 4.2430473630
x10-2; a7 = 3.1010978040; as = 6.3658026710 x 103; a9 = 2.8435129170 x 10-l; aI0 =
- 8.7028755450~ 10; aI1 = 1.1122078760 x lo- ‘; al2 = -5.2356492050; al3 = 1.9170068410
x 10; aI = 7.6869156680X 105; aI = - 1.5903010440 X log; a16 = 5.1098043990x 10’; al7 =
-2.0634314360 x 106; a18 = 6.8677007310 X 10’; aI9 = - 1.9218618160 X 10”; a2o =
2.8000000000.
Underlying experimental data:
Pressure-density-temperature (N = 1008): 0.02 < p(MPa) d 24.55; 0.00143 & p(g cm-3)
< 1.71515; 54.00 < T(K) < 300.0.
Saturation properties (N = 32): T,,(K) = 56.0; p,,,(MPa) = 0.0025; &,,(g cme3) = 1.690;
p~i,(g cmm3) = 0.00006.
References: Goodwin and Prydz (1970); Prydz (1970); Prydz and Goodwin (1970); Prydz and
Straty (1970); Prydz, Straty and Timmerhaus (1970); Straty and Prydz (1970).

Table 6 gives a comprehensive comparison between the experimental

p-p-T data and those calculated by the Bender equation for the gaseous,
the liquid and the near-critical regions which are defined in Fig. 6. The

TABLE 4
a, for the Bender equation of state and experimental data for sulfur dioxide

Critical properties and molecular weight: p,(MPa) = 7.880; p,(g cmp3) = 0.525; T,(K) =
430.65; M = 64.066; R(J g-l K-l) = 0.129777.
Equation of state parameter: a, = -1.4246011930X 10-l; a2 = 2.6532381870x102; a3 =
-2.3752778330 X 105; u4 = 6.3328699860 X 107; u5 = - 1.0511913090 X lOlo; a6 =
1.3599896740 x 10-2; u7 = - 6.2374945420 x 10; a, = 6.7469951870 x 104; ug = 7.8712189540
x10-l; uro=-4.3154734320x102; al,=-4.3521985580x10-‘; a,,=2.9019874830x102;
1113 = - 1.5203490660 x lo; al4 = 2.3204990930 x 107; aI5 = - 1.7942299080 X 10’; $6 =
- 2.4935183040 x 1012; al7 = 1.3121923010 X log; a18 = - 1.9379200850 X loll; al9 =
6.7743465870 X 1013; aZo = 3.6281179138.
Underlying experimental data:
Pressure-density-temperature (N = 897): 0.10 < p(MPa) < 31.853; 0.00238 < p(g cmm3)
Q 1.36818; 283.15 Q T(K) < 523.15.
Saturation properties (N = 18): T,i,(K) = 323; Pmln(MPa) = 0.860; &,,(g cmT3) = 1.297;
p~i,(g cmp3) = 0.0234.
References: Hirth (1958); Kang (1960); Kang et al. (1961).
32

TABLE 5
ai for the Bender equation of state and experimental data for water

Critical properties and molecular weight: p,(MPa) = 22.0932; p,(g cme3) = 0.317; T,(K) =
647.25; M = 18.015; R(J g-l K- ‘I= 0.461521.
Bender equation parameter: aI = - 1.3002084070 x 10-l; a2 = 7.6533762730 x 102; a3 =
- 9.0745855500 x 105; a4 = -2.9984514510 x 10s; a5 = -1.6148196450 X 10”; a6 =
4.4890768230; u7 = -6.3451282300x 103; us = 3.6353975160x 106; a, = -8.1460085550; uIo
= 6.0971223530 x 103; uIl = 1.0426877550 x 10; uI2 = - 1.0516986730 x 104; uI3 =
2.7385365060 x 103; uI4 = -2.2453231530 X 109; uI5 = 2.1342907950 X 1012; uI6 =
-3.1262434070 x 1014; uI7 = 4.9365926510 X 109; u1s = -5.7492854100 X 1012; a,, =
1.1440257530x 1015; u2o = 4.0000000000.
Underlying experimental data:
Pressure-density-temperature (N = 837): 0.53 4 p(MPa) Q 79.47; 0.01164 d p(g cmp3) Q
1.03681; 273.15 < Z’(K) Q 923.91.
Saturation properties (N = 38): T&K) = 273.16; p,i,,(MPa) = 0.061; &,,(g cme3) =
1.000; &,(g cmm3) = 0.000005.
References: Holser and Kennedy (1958); Kell and Whalley (1965); Osborne et al. (1933);
Osborne et al. (1939); Rivkin and Achundoff (1963); Rivkin and Achundoff (1966); Stimson
(1969); Wukalowitsch et al. (1961).

averaged deviations given in Table 6 are defined as follows:

100 250 400 550 700 0 200 400 600

temperature T/K temperature T/K
Fig. 1. Krypton: an overview of experimental data used to determine the parameters of the
Bender equation.

Fig. 2. Neon: an overview of experimental data used to determine the parameters of the
Bender equation.
 33

lo'

g loo
ZE
h
E lo"
3
E ICP
h
IO3
II I
IOh
100 200 300
temperature T/K
Fig. 3. Fluorine: an overview of experimental data used to determine the parameters of the
Bender equation.

Fig. 4. Sulfur dioxide: an overview of experimental data used to determine the parameters
of the Bender equation.

Pexp - Pcalc(T7 P> 2

Ap= 100
P ew

In the gaseous regions both deviations (Ap and Ap) are about the same
and amount to between 0.1 and 0.65%. As in the liquid region the
influence of density on pressure is much larger than the influence of
pressure on density, the average deviations Ap and Ap differ by a factor of
about 10. But generally liquid-phase densities calculated with the Bender
equation agree with experimental data as well as gaseous densities.
In Table 7 experimental results for the vapor pressure, the saturated
liquid density and the dew-point density are compared with results calcu-
lated from the Bender equation of state by applying the Maxwell criterion.

TABLE 6
Comprehensive comparison between the Bender equation of state and experimental p-p-T
data
Substance Region
Gaseous Liquid Near-critical
N Ap Ap N Ap Ap N Ap Ap
Kr 584 0.16 0.17 865 3.17 0.13 173 0.20 2.14
Ne 943 0.41 0.47 276 3.65 0.91 42 3.03 3.23
F, 480 0.10 0.18 427 4.46 0.11 101 0.18 0.54
8% 598 0.23 0.35 142 5.33 0.42 157 0.56 6.76
f%G 161 0.41 0.65 484 9.26 0.31 192 0.47 2.91
34

102

d
0
$16
CL
:
z 10’
0
h 10-Z

400 600 800 1000

temperature T/K
Fig. 5. Water: an overview of experimental data used to determine the parameters of the
Bender equation.

Fig 6. Definition of liquid, critical and gaseous regions.

TABLE 7
Comprehensive comparison between the Bender equation of state and experimental satura-
tion properties (I in K)

Property Substance
Kr Ne F2 SO* Hz0
PS Tmin 116.0 25.0 66.0 323.15 313.15
T 209.0 43.0 136.5 430.65 647.23
lo”o”;AP’/P’ I max 0.14 = 0.80 a 0.10 0.13 0.10

0.049 0.20 0.025 0.046 0.034

P’ Tmin 127.0 25.2 67.7 323.15 303.14

Tmax 208.1 43.1 142.0 428.15 647.23
100 I AP’/P’I max 1.34 a 2.0 = 0.33 1.83 = 5.0 =

0.17 0.42 0.04 0.24 0.27

P” Gin 144.0 25.2 70.0 323.15 303.14

T 142.2 423.15 640.23
1;; A,“,,“, ,,,= 208.2
2.5 = 43.0
3.5 1.42 a 5.11 a 3.37 a

0.81 1.56 0.63 1.24 0.48

a Maximum deviation at T,,.

 35

TABLE 8
Parameters of the ideal gas-state heat capacity equation

Sub- Parameter
stance
d, d, d, d, d,
Kr 0.24834 - - -
Ne 1.03007 - - -
F2 7.5934-lo- l 2.8837)~10-~ -4.1929x1O-6 2.3098 x 1O-8 -3.2916x10-”
so2 4.0211 x10-l 8.7349x 1O-4 -4.5969x 1O-7 -1.3328x lo-” 2.3785 x lo- I4
Hz0 1.94077 -9.6766x10-4 3.0885 x lo+ - 2.6314 x 1O-9 8.6095 x lo- l3

Average deviations amount to about 0.05% for the vapor pressure, to about
0.2% for the saturated liquid density and to about 1% for the dew-point
density. Maximum deviations are about four times larger than the average
deviations and often occur at the upper temperature limit of the experi-
mental data.
Parameters di for the ideal gas-state equation (eqn. (2)) as compiled by
Polt (1987) are given in Table 8. The temperature region covered by that
equation at least corresponds to that of the equation of state. Ideal
gas-state heat capacities are represented with an accuracy of a few tenths
per cent.
Computer software for applying the Bender equation of state is available
from the authors on request.

LIST OF SYMBOLS

a1420 coefficients of Bender equation of state

B, C, 0, E, F, G, Htemperature functions
c: ideal gas-state heat capacity (J g-’ K-‘1
4-4 coefficients of the ideal gas-state heat capacity equa-
tion
M molecular weight
N number of data points
P pressure (MPa)
R gas constant (J gg’ K-‘1
T temperature (IQ
P density (g cmp3)
Subscripts

talc calculated from the Bender equation of state

C critical
exp experimental
max maximum
min minimum

Superscripts

S saturation
I
saturated liquid
I, dew point

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 37

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