Chemical Physics Letters 383 (2004) 359–361

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The law of corresponding states for the entropy of rare gases

V.S. Vorob!ev *

Theoretical Department, Institute for High Energy Densities, Russian Academy of Sciences, Tzorskaya 13/19, 125412 Moscow, Russia
Received 22 September 2003; in final form 14 November 2003
Published online: 5 December 2003

Abstract

We show that the behavior of entropy along the phase co-existence curves for rare gases can be analyzed based on the corre-
sponding-states concept. To implement this concept, we consider dimensionless entropy Sl=R (R is the universal gas constant, l is
the atomic weight) +3 ln B, where B is the de Boer parameter. It is demonstrated that such reduced entropy expressed in terms of
reduced temperature T =D (D is the characteristic depth of the potential wells) is a universal function for all rare gases.
! 2003 Elsevier B.V. All rights reserved.

The thermodynamics of substances formed by atoms
(molecules) with short-range interactions and having
face-centered cubic crystal structure is characterized by
a number of common features [1,2]. Here, the term
"short-range interaction! means an interatomic (inter-
molecular) interaction significant only within a limited
range of interparticle distances. For condensed matter,
this implies a dominant role of the pairwise interaction
between neighboring particles. Parameters of this in-
teraction determine the main features of the thermo-
dynamic behavior of a system.
As a typical example of such systems, we consider
here rare gases having, face-centered cubic (fcc) crystal
lattice with close-packed atoms. It is well known [1,2]
that many thermodynamic functions of these systems
coincide being expressed in a dimensionless form. Thus,
to determine the main thermodynamical characteristics
of a substance with experimental accuracy, it is sufficient
to know only two parameters related to the potential
curve: depth D of the potential well and equilibrium
distance r (r is the "diameter! corresponding to the dis-
tance where the potential is equal to zero). These pa-
rameters determine in a natural manner the set of
dimensionless variables, which in its turn causes the
similarity of thermodynamic functions. Thus, tempera-
*
Fax: +70953620487.
E-mail address: vrbv@mail.ru (V.S. Vorob!ev).
ture dependence of the saturated vapor pressure pðT Þ for
all rare gases is expressed in a universal form
p# ¼ p=p0 ¼ /ðT =DÞ ¼ /ðT # Þ: ð1Þ
Here p0 ¼ D=r3 is a natural unit of pressure for the
system under study. As the natural unit of density for
such systems, one could use the expression q0 ¼ m=r3 ,
where m is the mass of a particle.
The parameters of the interaction potential for two
noble gas atoms can be found from analysis of physical
properties, which depend on this potential. For solidi-
fied and liquefied noble gases, these parameters could be
determined based on the differential and full scattering
cross section, the second virial coefficient, the diffusion
coefficient, the conductivity, the viscosity, the excitation
spectrum for two-atomic molecules of noble gases. The
reliable interaction potentials for two noble gas atoms
have been constructed in [3–6] as a result of measure-
ments and processing of these quantities. The resulting
parameters rmin and D for Ne, Ar, Kr and Xe are given
in Table 1.
For Ne, Ar, Kr and Xe, parameters at the critical and
triple points in dimensional and dimensionless units are
also presented in Table 1. The plots of (a) the pressure
and (b) the phase equilibrium densities versus tempera-
ture along the phase co-existence curves are presented in
Fig. 1. The values from in [7,8] are denoted by symbols.
For these plots, we use thermodynamic functions for
noble gases tabulated in [7,8] that are consistent with the

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doi:10.1016/j.cplett.2003.11.038
360 V.S. Vorob’ev / Chemical Physics Letters 383 (2004) 359–361

Table 1
Parameter Ne Ar Kr Xe
!)
rmin ¼ 21=6 r (A 3.09 3.76 4.01 4.36
D (meV) 3.64 12.3 17.3 24.4
D (K) 42 143 200 278
m (a.u.) 20.18 39.95 83.8 131.3
p0 ¼ D=r3 (atm) 286 525 608 666
q0 ¼ m=r3 (g/cm3 ) 1.61 1.76 3.05 3.72
Tc (K) 44.4 (1.05) 150.9 (1.06) 209.4 (1.04) 289.7 (1.02)
pc (atm) 27.6 (0.097) 49 (0.093) 55 (0.0905) 58.4 (0.087)
qc (g/cm3 ) 0.484 (0.30) 0.535 (0.304) .919 (0.301) 1.11 (0.298)
Ttr (K) 24.55 (0.584) 83.78 (0.586) 115.76 (0.579) 161.36 (.58)
ptr (atm) 0.433 (0.0013) 0.687 (0.0013) 0.73 (0.0013) 0.816 (0.0013)
vl (cm3 /g) 0.801 (1.28) 0.707 (1.25) 0.409 (1.25) 0.337 (1.25)
vs (cm3 /g) 0.70 (1.12) 0.618 (1.09) 0.358 (1.09) 0.301 (1.12)
vg (cm3 /g) 226.6 (363) 243.4 (430) 152.9 (466) 121.9 (453)
B 0.217 0.069 0.038 0.024
H0 (K) 45 92 72 64
In the table, notation a.u. means atomic units of mass. The values in parentheses are given in reduced units.

(a) 100 entire body experimental data on thermal properties of

noble gases. We can see that the law of corresponding
10 states is valid.
There is a question regarding the possibility to use
1 such kind of presentation for the entropy of rare gases
along the phase co-existence curves. Here we shall dis-
Ne
cuss such a possibility.
p*

0.1 Ar
2
Kr Let us write the ideal gas entropy
Xe
! "
0.01 R 5 K3
S¼ % ln ; ð2Þ
l 2 ga mv
1E-3
where R is the universal gas constant, l is the atomic
0.5 1.0 1.5 2.0 2.5 3.0
weight, ga is the inner statistical sum of p
anffiffiffiffiffiffiffiffiffiffiffiffi
atom in va-
T* por, v is the specific volume, K ¼ h= 2pmT is the
thermal wavelength. Rewriting Eq. (2) using dimen-
(b) sional units and equation of state for ideal gas in the
1.2
2 form p ¼ RT =lv, we obtain
1.0
1 l 5
S# ¼ S % þ 3 ln B ¼ p# =T #5=2 ¼ uðT # Þ; ð3Þ
0.8 R 2
Ne
h
0.6 3 Ar where B ¼ pffiffiffiffiffiffiffiffi is the de Boer parameter. The values of
ρ*

Kr 2pmDr
Xe this parameter are given in the table. For heavy noble
0.4 gases, B is quite small. In Eq. (3), we introduce the
function uðT # Þ ¼ p# ðT # Þ=T #5=2 , which is valid along the
0.2 liquid–gas co-existence curve. Let us write also the ex-
4 pression for entropy of a crystal state in the Debye ap-
0.5 1.0 1.5 2.0 2.5 3.0 proximation
$ ! " % ! "&'
T* R H H
S¼ 4D % 3 ln 1 % exp % ; ð4Þ
l T T
Fig. 1. (a) Reduced pressure and (b) equilibrium densities versus re- R x 3 dy
duced temperature along the phase co-existence curves. Symbols cor- where DðxÞ ¼ x33 0 eyy %1 is the Debye function, H is the
respond to the values of pressure and equilibrium phase densities Debye temperature. The dependence of the latter pa-
tabulated in [7,8] for Ar, Ne, Kr and Xe. In Fig. 1a, plots 1 and 2 rameter on volume is given by the expression
correspond to the solid–liquid co-existence curve and liquid–gas co-
existence curve, respectively. In Fig. 1b, plots 1, 2, 3 and 4 correspond ! Z m "
to the solidification curve, melting curve, vaporization curve and H ¼ H0 exp % Cd ln m ; ð5Þ
condensation curve, respectively. m0
 V.S. Vorob’ev / Chemical Physics Letters 383 (2004) 359–361 361

where C is the Gruneisen parameter, H0 is the Debye

-Ar
temperature at T ¼ 0 when m ¼ m0 . The values of H0 are -Ne
4 4 -Kr
given in Table 1.
-Xe
We see that in the latter case the entropy depends
only on ratio H=T . As it is known, the energy corre-
sponding to the Debye temperature is equal to vibration 0
energy hm of the unit cell typical of the crystal state. The 3

only quantity having dimension of frequency that can be
constructed using parameters D, r, and m is mD ¼
p ffiffiffiffiffiffiffiffiffiffi
D=m=r. Then the dimensionless frequency is m# ¼
m=mD . The Debye temperature must be proportional to
this frequency, which is, in fact, a natural unit in this
case. Thus, dimensionless ratio H=T can be written as
follows:
pffiffiffiffiffiffi #
2pm
H=T ¼ B ¼ B/ðT # Þ:
T#
Along the phase co-existence curves, the relationship
m# =T # ¼ /ðT # Þ depends on the reduced temperature
only. We see that in two limiting cases considered above,
the entropy depends on factor Bf ðT # Þ.
This suggests that entropy of rare gases along all
phase co-existence curves can be presented in reduced
form as
Sl 5
S # ðT # Þ ¼ % þ 3 ln B: ð7Þ
R 2
To check this assumption, we present in Fig. 2 the plot
of the reduced rare gas entropy S # ðT # Þ versus the re-
duced temperature. To draw this plot, we used the val-
ues of entropy along the phase co-existence curves for
noble gases tabulated in [7,8]. Tabulated data for Ne,
Ar, Kr and Xe have been transferred to the form pre-
sented by to Eq. (7) and shown by symbols in Fig. 2. As
is seen, the curves for entropy of heavy noble gases Ar,
Kr and Xe plotted using these variables coincide with
each other. The curve for Ne slightly deviates from this
common dependence because this substance has the
largest value of de Boer parameter.
S*
2
-4
1
-8
0.5 0.6 0.7 0.8 0.9 1.0 1.1
T*
ð6Þ
Fig. 2. Reduced entropy (Eq. (7)) along the phase co-existence curves
versus reduced temperature. Symbols correspond to the values of en-
tropy tabulated in [7,8] for Ar, Ne, Kr and Xe. Plots 1, 2, 3 and 4
correspond to the solidification curve, melting curve, vaporization
curve and condensation curve, respectively.
This study was supported by the Russian Foundation
for Basic Research, projects No. 02-02-17255, 02-02-
17376 and NSh-1953-2003.2.
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