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 Author's personal copy

Fluid Phase Equilibria 279 (2009) 41–46

Contents lists available at ScienceDirect

Fluid Phase Equilibria

journal homepage: www.elsevier.com/locate/fluid

Novel correlations between the critical constants of the noble gases

Philip Molyneux ∗
Macrophile Associates, 33 Shaftesbury Avenue, Radcliffe-on-Trent, Nottingham NG12 2NH, UK

a r t i c l e i n f o a b s t r a c t

Article history: For any particular fluid, the set of three critical constants (CC) – pressure Pc , temperature Tc and molar
Received 19 April 2008 volume Vc – has a central importance in defining the physical behaviour of the fluid in the gas and
Received in revised form 18 December 2008 liquid states. However, little attention seems to have been paid in the past to the relations between the
Accepted 20 January 2009
CC of different substances. In the present paper, some simple and apparently novel relations have been
Available online 30 January 2009
found between the three CC for the set of four noble gases: Ne, Ar, Kr, Xe. Defining the critical quotient
Qc ≡ RTc /Pc (where R is the Gas Constant) the correlations may be summarised by the dual equation:
Keywords:
(Vc /cm3 mol−1 ) = 27 + 0.31 (Tc /K) = 3.3 + 0.280 (Qc /cm3 mol−1 ), which describes the CC data for the quartet
Critical constants
Linear correlations between critical
Ne–Xe with an average uncertainty of 0.5%. Regarding the other two noble gases, the two isotopes of
constants the lightest member, 3 He and 4 He, show the deviations from these relations that are expected from
Noble gases quantal effects and their low molar masses; while for the heaviest member, Rn, the correlations enable
Quantal (quantum mechanical) effects a value of 145(5) cm3 mol−1 to be estimated for Vc that is not otherwise well defined in the literature. By
Residual Volume Effect contrast, and contrary to the general assumption, the second lightest member, Ne, apparently does not
Zeronium show appreciable quantal effects in the area, so that Ne–Xe may be considered together as a group. These
correlations are compared with the behaviour of a selection of polyatomic fluids; in these comparisons,
the NG dual correlation equation provides a reference line defining the presumed simplest behaviour. This
and related areas show a “Residual Volume Effect”, in that extrapolating the equivalent temperature and
energy parameters to zero for the state of zero-mass point particles, referred to here as the hypothetical
element zeronium (Ze), the system in each case still has a finite intercept; this intercept amounts to
essentially 34% of the average volume for the present quartet Ne–Xe, rather than the zero volume expected
for this condition.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction derived dimensionless quantity, the critical compressibility factor,

The set of the three critical constants (CC) for a fluid – the critical
pressure Pc , the critical temperature Tc and the critical molar vol-
ume Vc – plays a central role in defining the physical properties of
the fluid, particularly its behaviour in the gaseous (vapour) and the
liquid states.1 Primarily, this set defines the critical point for the
substance, that is, the point at which the vapour and liquid states
merge, and the vapourization enthalpy change becomes zero [1–4].
Furthermore, the corresponding three reduced quantities: Pr , Tr ,
Vr , which are obtained by division of these three properties (pres-
sure P, temperature T, and molar volume V) by their respective CC,
are found for simple-molecule fluids to give universal curves defin-
ing the deviations from the ideal gas laws, commonly referred to as
the Law of Corresponding States (LCS). Likewise, theories of equations
of state (EOS) such as the classic van der Waals equation focus on a
∗ Tel.: +44 115 933 4813; fax: +44 115 933 4813.
E-mail address: molyneux@easynet.co.uk.
1
Throughout this paper, the units used for critical constants and derived quanti-
ties are: pressure, MPa; temperature, K; molar volume, cm3 mol−1 .
Zc , defined by
Pc Vc
Zc ≡ (1)
RTc
where R is the Gas Constant (in the present customary units,
8.3145 cm3 MPa K−1 mol−1 ). The experimental values of Zc for
simple-molecule fluids range between about 0.29 and 0.26 [1,2],
whereas (for example) the simple van der Waals equation requires
Zc to have a value of 0.375; one criterion of a “good” EOS therefore is
if it yields values of Zc closer to these experimental ones [3,4]. The
parameter has also been used as a criterion of the molecular inter-
actions; for example, the term “perfect liquids” has been applied
to the four fluids: Ar, Kr, Xe and CH4 for which Zc = 0.292 [5]. In
all of these applications, there is the limitation that the value of Zc
depends upon all three critical parameters, and is subject to their
combined experimental uncertainties.
These CC are also important technically in chemical engineering,
both directly in relation to the behaviour of fluids, and indirectly for
the correlation and prediction of other physical properties [6,7].
As a preliminary to considering the correlations that are the spe-
cific topic of this paper, it is useful to introduce a new quantity, the

0378-3812/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2009.01.008
 Author's personal copy
42 P. Molyneux / Fluid Phase Equilibria 279 (2009) 41–46
critical quotient Qc defined by
RTc
Qc ≡ (2)
Pc
This is a volume-dimensioned quantity that is found to give linear
correlations when used in place of Pc alone.
2. Correlations between the critical constants
2.1. Critical constants for the noble gases
The above discussion of CC is of course part of the common
currency of physical chemistry. However, it is evident from the liter-
ature cited that the CC values for any specific fluid are considered by
the physicochemical community simply as a given set of parameters
that are characteristic (but otherwise unexplained or unrelated) for
that fluid. In particular, little if any interest seems to have been
shown in the literature as to whether or how these parameters for
different fluids might be related to one another.
The present paper points out some simple correlations that are
apparent between these parameters, specifically as applied to the
four noble gases (NG): Ne, Ar, Kr, Xe; the “outer” two NG, He and
Rn, are considered somewhat separately. This set of elements (still
commonly referred to either as the “rare gases” or the “inert gases”)
is ideal for testing such correlations, since they are monatomic with
spherical molecules (atoms) and with any interactions between the
atoms only of the van der Waals/London dispersion type. For these
reasons, any theory of molecular behaviour must first be shown to
be applicable to the NG before it is worthwhile testing with other
less simple fluids.
The literature values for the CC for the noble gases are sum-
marised in Table 1. To get the best consensus on these data, those
listed are the averages from six published data-sets [8–13]. The data
for Ne and Rn require special note.
In the case of Ne, it has been suggested that the relatively greater
uncertainty in the literature values of Pc may reflect contamination
by He in some of the samples used; on the other hand, the appar-
ently low uncertainty in Vc seems to reflect the use of a single early
value that has been copied from one listing to another. Neverthe-
less, the data for this NG seem to be sufficiently well defined to
behave consistently in the correlations observed.
In the case of Rn, the values listed for Pc and Tc are from the recent
re-evaluation by Ferreira and Lobo [14] of the early data (and still
apparently the only precise ones) that were obtained by Gray and
Ramsay [15]. From its format, the value for Vc of 140.00 cm3 mol−1
listed by Poling et al. [13] is evidently an estimate; the value given in
Table 1 is an extrapolation from the present Case C linear correlation
for the quartet Ne–Xe (Section 2.4). This Vc value is important for
example in connection with the diffusion of Rn from radiogenic
rocks into the environment.
In considering the correlations for the NG considered below in
Sections 2.2–2.4, the data are compared with those for two other
groups of fluids, both to put this behaviour in the wider context and
to show how it relates to that of fluids in general.
The first comparison group is a trio of related molecules: H2 ,
O2 , and H2 O. Here, H2 is a “light” gas that is expected, like the iso-
topes of He, to show quantal (quantum mechanical) effects (QE), as
discussed in Section 4; in this case, since the three isotopic forms:
H2 , HD, D2 , have very similar CC values (average range 14%) [13],
the latter two have been omitted in the comparisons. For O2 , its
CC values are coincidentally close to those for Ar, differing by only
3% on the average; this suggests that one may act as substitute for
the other in considering physical behaviour in particular applica-
tions. Lastly, with H2 O, at normal temperatures and pressures (for
example, 100 ◦ C, 0.1 MPa) the vapour (steam) shows no sign of the
association by hydrogen bonding that is prominent in the liquid
state [16]; however, such association would be expected to be sig-
nificant at the critical point because of the much higher density
(Vc = 56 cm3 mol−1 —compare molar volume Vm = 18 cm3 mol−1 for
the liquid at ambient temperatures).
This second comparison group comprises fluids with molecules
of the type MY4 (tetrahedral) and MY6 (octahedral, where Y = F in
all the examples used), which may be referred to as quasispheri-
cal molecules (QSM) since they would become effectively spherical
by rotation in these fluid states. For example, the tetrahalides MX4
have been studied by Hildebrand and co-workers as proposed heav-
ier analogues of the NG [17]. The intermolecular forces throughout
will again be of the van der Waals/London dispersion type, although
(unlike the situation with the NG) these forces will no longer be
central.
The present examination of the CC values for the NG group
Ne–Xe has revealed three linked linear correlations, listed here as
Cases A, B and C and discussed in Sections 2.2–2.4 respectively. It is
useful to present the equations for these at this initial stage before
they are discussed individually.
Case A : Vc = 27(2) + 0.31(1)Tc (3)
Case B : Qc = 86(2) + 1.12(2)Tc (4)
Case C : Vc = 3.3(4) + 0.280(1)Qc (5)
It will be noted that these are not three independent equations,
since they involve only three independent variables; however, it is
convenient to consider them all in turn, because each has distinctive
features.
In the above Eqs. (3)–(5), since all the cases refer specifically to
the quartet Ne–Xe, the coefficients are put only as their numerical
values, rather than being given symbols. In each case, the numerical
value given is the mean, with in parenthesis the estimated stan-
dard deviation in the last quoted decimal place. This usage will be
followed throughout this paper.
2.2. Case A: critical volume versus critical temperature
The plot of Vc against Tc for the noble gases and other comparison
molecules is shown in Fig. 1. In the case of Rn, the Vc value plotted
(filled circle) is that obtained by extrapolation from Case C below
(Table 1). Excepting the two helium isotopes, the plot is essentially
linear according to Eq. (3) above; the average deviation for the four
NGs in Fig. 1 is about 2%. The strong deviations for the two helium
isotopes may be attributed to the QE resulting from the low molar
mass, and the different character of the liquid/vapour equilibrium
in these cases [18]. With Ne, however, there is no marked deviation
for this fluid from the straight line in Fig. 1; this is surprising, since
similar although lesser QE are to be expected because of its low
molar mass (Section 4).
The finite intercept of Vc (27 cm3 mol−1 ) for Tc → 0 presumably
relates to the limiting condition of zero-mass point particles. The
occurrence of this finite intercept is reminiscent of the “covolumes”,
with values in the range 13–40 cm3 mol−1 , that arise for the limit
of zero molar mass in the additive group-contribution schemes for
molar volumes of pure substances [6], and for partial molar vol-
umes of solutes [19,20]. From the molecular viewpoint, Stillinger
has suggested this parameter may arise from the zero-point motion
for these limiting particles [19]. For concreteness of discussion, and
in view of the importance of this limiting state in the present and
the related correlations (Section 2.6), it is convenient to name this
hypothetical limiting situation (zero-mass point particles) as the
“element” zeronium (Ze), characterised from the present Cases by
the data in Table 1; this is accordingly so-plotted (asterisk) in Fig. 1.
It is convenient to quantify this intercept by reference to the NG
quartet, as 34(2)% of the average Vc value for the four gases. As
discussed below (Section 2.6), parallel behaviour is shown at the
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P. Molyneux / Fluid Phase Equilibria 279 (2009) 41–46 43

Table 1
Critical constants and derived quantities for the noble gases.a

Gas Atomic number, Z Relative atomic mass, Mr Pc (MPa) Tc (K) Vc (cm3 mol−1 ) Qc (cm3 mol−1 )b Zc
3
He 2 3.017 0.116(1) 3.32(1) 72.23(1) 239(2) 0.302(4)
4
He 2 4.003 0.228(1) 5.24(6) 57.5(3) 191(1) 0.301(1)
Ne 10 20.180 2.71(6) 44.5(2) 41.7(1) 137(3) 0.305(7)
Ar 18 39.950 4.89(2) 150.9(1) 74.9(3) 257(1) 0.292(2)
Kr 36 83.800 5.50(1) 209.40(1) 91.7(6) 317(1) 0.289(2)
Xe 54 131.300 5.84(1) 289.75(5) 119.0(8) 413(1) 0.288(2)
Rn 86 222.00 6.2(2)c 377.1(1)c 145(5)c 506c 0.287c
Zed 0 0 0 0 27(2)d 86(2)d 0.31(2)d
a
Tabulated values of the CC (except for Rn—see below) are averages from listings in the literature [8–13], except for the underlined values, which are either assigned zero
values, or estimates (see below and text). Numbers in brackets are estimated standard deviations in the quoted last decimal place.
b
Critical quotient—see Eq. (2).
c
Rn: the values of Pc and Tc are from the re-evaluation by Ferreira and Lobo [14] of the original data of Gray and Ramsay [15]. The value of Vc has then been estimated from
Eq. (5), as shown in Fig. 4—see also Section 2.1.
d
Hypothetical element “zeronium” as the limiting state of zero-mass point particles—see Eqs. (4) and (5), and Section 3.

macroscopic (molar) level for the crystal state, and at the molecu-
lar level with the Lennard–Jones (LJ) parameters; it may therefore
be referred to collectively as the Residual Volume Effect (RVE) as
discussed specifically in Section 3.
With the first comparison group, the point for H2 deviates above
the correlation line because of the QE for this light gas, as seen
with the He isotopes. The point for H2 O lies far to the right (off
scale) because of the high Tc value, evidently related to the strong
hydrogen bonding as already discussed. For O2 , as already noted,
here and in other plots the point lies (coincidentally) close to Ar.
2.3. Case B: critical quotient Qc versus critical temperature Tc
It is useful to preface this Case by considering firstly the simple
plot of critical pressure Pc (MPa) against critical temperature Tc (K)
for the noble gases as shown in Fig. 2. The curve for Ne–Xe may be
fitted by a rectangular hyperbola
7.4(1)Tc
Pc =
[77(3) + Tc ]
Although the data for Rn are available (Table 1), they have been
omitted in deriving the above coefficients for conformity with the
other Cases; however, it is notable that its plotted point lies very
close to the correlation curve. The average deviation for the four NG
in Fig. 2 is 0.6%. The form of the curve of Eq. (6) indicates that the
origin, that is, for the hypothetical limiting “element” Ze (asterisk
in Fig. 2) lies on the curve, so that this corresponds both to Tc → 0
and to Pc → 0.
The points for 3 He and 4 He lie close to the curve, but evidently,
this is only because both parameters are small and the points are
therefore close to the origin. The point for Ne lies close to the curve,
indicating again that QE do not have an important effect on the CC
for this gas, which is contrary to a common expectation (Section 4).
The form of Eq. (6) suggests that for these NG, at the limit
of indefinitely large Tc (presumably, indefinitely large molar
mass), the critical pressure should approach a limiting value of
Pc∝ = 7.4 MPa.
One method of testing the hyperbolic form of Eq. (6) is to plot the
ratio Tc /Pc against Tc , which should be linear. However, it is more
(6)

Fig. 2. Critical pressure Pc versus critical temperature Tc . Symbols as Fig. 1—point

Fig. 1. Critical volume Vc versus critical temperature Tc . Symbols: () noble gases for Rn from experimental values (Table 1). The continuous trend curve and its bro-
as labeled – the continuous trend line and its broken extrapolation relates only to ken extrapolation (rectangular hyperbola) relate only to the data for the NG quartet
the NG quartet Ne–Xe (Eq. (3); (䊉) (estimated value of Vc – Table 1); () H2 , O2 and Ne–Xe (Eq. (6)); the horizontal broken line is the extrapolated limiting critical pres-
H2 O; () sym-MY4 as labelled; (∗) Ze—see text and Table 1. sure Pc∞ = 7.4 MPa.
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44 P. Molyneux / Fluid Phase Equilibria 279 (2009) 41–46

Fig. 3. Critical quotient Qc versus critical temperature Tc . Symbols as Figs. 1 and 2.
The continuous trend line and its broken extrapolation (Eq. (4)) relate only to the
data for the NG quartet Ne–Xe.
fruitful to use the quantity RTc /Pc , that is, the volume-dimensioned
critical quotient Qc as already defined by Eq. (2). This plot of Qc
against Tc is shown in Fig. 3. For the NG set Ne–Xe the plot is essen-
tially linear according to Eq. (4) above; the average deviation for the
four NG is about 0.5%. As with Fig. 2, the data for Rn have been omit-
ted from fitting the line, but its point nevertheless lies close to this
line. The marked positive deviations for the two He isotopes may
again be attributed to the QE resulting from the low molar mass,
the lower mass isotope as expected showing the greater deviations.
However, with Ne, as with Case A, there is again no marked devi-
ation from the straight line than seen with the other NG in Fig. 3,
despite the QE commonly expected for this “light” gas (Section 4).
The finite intercept (Qc = 86 cm3 mol−1 ) for Tc → 0 in Fig. 3 again
presumably relates to the limiting condition of point mass particles,
i.e., zeronium (Ze) as introduced in Section 2.2, and defines the Qc
value for this state (Table 1). This is discussed further in Section 3.
For the first comparison group, H2 is strongly deviant upward
like the He isotopes presumably again because of QE (Section 4).
The point for H2 O deviates in the other direction, again presum-
ably because the hydrogen bonding gives a high Tc value, as already
discussed.
Fig. 4. Critical volume Vc versus the critical quotient Qc . Symbols as Figs. 1 and 2.
The continuous trend line and its broken extrapolation relate only to the data for
the NG quartet Ne–Xe (Eq. (5)). The dotted line indicates the critical compressibility
factor Zc = 0.292 for “perfect” fluids (see Section 1).
stage further, Fig. 5 shows the same plot with extended axes to
include the heavier QSM; the 13 compounds shown now fit the line
with an average deviation of about 3%, although there seems to be
some downward deviation from the line at the upper end. The plot
is particularly interesting as it contains a number of compounds of
technical importance, such as SF6 and UF6 .
To obviate further crowding at the upper end of this plot, the
data available [8] for the Group 4 tetrachlorides – TiCl4 , ZrCl4 , HfCl4
– have been omitted; in fact these data are anomalous, showing a
decrease in the values plotted with increase in molar mass, which
requires further investigation.

2.4. Case C: critical volume Vc versus critical quotient Qc

The plot of Vc versus Qc is shown in Fig. 4. In this Case, the straight

line fit for Ne–Xe is given for Eq. (5) above. The average deviation
here for the four NG is only about 0.4%. The closeness of the fit
is in this case remarkable in view of the fact that all three CC are
involved in this type of plot. In particular, it gives more confidence in
extrapolating to obtain an estimate of the value of 145(5) cm3 mol−1
for Vc of Rn as given in Table 1 (see also Section 2.1).
The close fit of the helium isotopes to the trend line in Fig. 4 is
quite remarkable because of the QE which show up in the previous
plots (Figs. 1–3); even the small deviation seen with 3 He could be
ascribed to uncertainties in the small values of Tc and Pc along with
the propagation of errors in taking their ratio.
For the first comparison group, H2 also lies close to the line, while
Fig. 5. Critical volume Vc versus the critical quotient Qc —extended ranges. Symbols:
H2 O is relatively closer than with the other plots.
(♦) sym-MF6 (octahedral); other symbols as Figs. 1 and 2. The continuous trend line
Likewise, for the second comparison group, the data for the QSM and its broken extrapolation relate only to the data for the NG quartet Ne–Xe (Eq.
also lie on or remarkably close to the line of Eq. (6). Taking this a (5)).
 Author's personal copy
P. Molyneux / Fluid Phase Equilibria 279 (2009) 41–46
It is evident that this Case C plot promises to be useful for fluids
in general, involving as it does all three values of the CC, where it
may be applied for the purposes of display, discussion and interpre-
tation; the NG linear correlation then provides a reference line for
this purpose. This should reveal aspects of the CC data not evident
from the conventional listings in tabular form [8–13].
Taking this a stage further, the use of the three parameters Tc ,
Vc and Qc in the three linear plots in Figs. 1, 3 and 4 indicates the
possibility of using 3D plots to display all three parameters. Going
beyond the 2D representation by stereo-optic pairs, this requires
the use of a computer display with software to allow the rotation
of the 3D plot.
The correlation line in Figs. 4 and 5 also explains the fact that
the values of the critical compressibility factor Zc in most cases drift
downwards with increasing molar mass, as seen from the data in
Table 1 for the noble gases—from 0.305 for Ne down to 0.288 for Xe.
This arises because the correlation plot has a small but finite posi-
tive intercept (3.3 cm3 mol−1 —Eq. (5)), and since lines of constant Zc
radiate from the origin in this type of plot, then these sweep across
the plots with lower slope in traversing from lower to higher molar
mass. The drift in Zc values is therefore an artefact of this finite ordi-
nate intercept, leading to Ne having a markedly different value of Zc
from Ar–Xe, which has customarily ascribed to QE with this “light”
NG (Section 4). It seems that these types of effects have not been
noted previously because such data have usually been treated on a
piecemeal basis and presented at most in tabular form, rather than
using plots of the present type.
It should be noted that although the line in Figs. 4 and 5 is
extended back to meet the ordinate axis, the actual extreme lower
limit is the Ze (zeronium) point as plotted (asterisk), which also lies
close to the correlation line.
2.5. The Law of Corresponding States
Experience during the preparation of this paper has shown that
the present correlations may be confused with, or may be taken
to be a special form of, the Law of Corresponding States (LCS). It is
therefore necessary to point out the distinctions between the two
forms of behaviour.
The LCS relates to the three reduced parameters Pr , Tr , and Vr , as
obtained by dividing the actual value of the specified quantity by
the corresponding critical value. The Law then specifies that for a
range of simple fluids, if two of these parameters are the same for
the different fluids, then the third parameter will also be the same;
in addition, plots for fixed values of Tr of the reduced compressibil-
ity factor Zr against the reduced pressure Pr are the same for the
different fluids. This applies more or less exactly to molecules of
complexity at least up to pentane [1,2].
However, by contrast, the present correlations are concerned
directly with the critical values, whereas in the LCS these have
already been absorbed into the reduced values. In addition, in the
present case the correlation plots are straight lines (Figs. 1, 3 and 4),
whereas in the case of the LCS the specified plots of plots of reduced
compressibility factor Zr versus Pr (fixed Tr ) are nonlinear. A further
point of distinction from the latter plots is that the third parame-
ter is not kept fixed in the present plots—for example, in Fig. 1, the
value of Pc varies along the linear plot of Vc against Tc .
It should be evident, therefore, that the present correlations
represent a quite distinct form of behaviour from the LCS.
2.6. Links with other areas
These three correlations: Cases A, B, and C, are surprising both in
their simplicity and in the fact do not seem to have been noted previ-
ously in the literature, either in theoretical treatments [1–5,10,11],
or in the prediction methods that are currently used in chemical
45
engineering [6,7]. They are evidently important from the practical
viewpoint for the noble gases in three ways: (a) they confirm the
internal consistency of the CC data-set (Table 1), (b) they show that
with Ne any QE are not significant in this area, so that this element
can be considered on a par with Ar, Kr, and Xe (Section 4); and (c)
they enable a rational estimate to be made of Vc for Rn which is not
otherwise well defined in the literature (Table 1).
Although these correlations between experimental data are
therefore evidently both significant and useful, experience during
the preparation of this paper showed that they tended to be viewed
as purely “empirical” and liable to be dismissed as such by the
scientific community. In fact, the correlations may be viewed as
a quantitative example of the Periodic Law, which initially was of
course only “empirical” and without any theoretical background. It
can be shown [21] that similar correlations for the NG apply to the
comparable data for the solid (crystal) state [22,23], and the param-
eters controlling the Lennard–Jones (6–12) potential [24], but this
is outside the scope of the present paper.
3. Residual Volume Effect
This anomaly has already been discussed for considered CC (Sec-
tion 2), where it is seen that the joint limits Pc → 0, Tc → 0, referred
to as zeronium (Ze), there is still a finite value for Vc . As already
noted, such an effect also applies [21] to the crystal data [22,23]
and to the Lennard–Jones parameters [24]. It then amounts to an
overall average of 34% of the mean volume for the NG set Ne–Xe.
From the molecular viewpoint, the volume parameter Vc (relat-
ing to repulsions between the molecules in close proximity) and
the temperature parameter Tc (which may be taken to be an
energy parameter relating to attractions between the molecules)
are dependent on the number of electrons in the molecule, increas-
ing as this number increases; in the case of the volume parameter
this is mitigated by the contraction effect because of increasing
nuclear charge. Thus in each case, the limiting situation corresponds
to zero-mass point particles, where with zero number of electrons
there ought to be zero energy and zero volume; thus the zeronium
state does have a finite volume, and indeed without this anomaly
the state would not be noteworthy.
It is perhaps surprising that this RVE has apparently not been
noted before, or not been commented on before. For its seems even
from a cursory examination of the data for the noble gases that
the volume values for the lighter elements are much higher than
they should be, judged from the values for the heavier members. A
similar general effect may be readily seen with the sizes of atoms
and monatomic ions in the solid state [25].
4. Quantal (quantum mechanical) effects (QE)
As already noted, the present phenomena are influenced by
quantal (quantum mechanical effects (QE)), which are expected to
occur most markedly with the lightest gases such as the He isotopes
and to a much lesser extent Ne; they would also be expected to
occur with dihydrogen and its isotopic forms (H2 , HD, D2 ) [5,10,26].
Such effects could be the reason for the deviations from normal
behaviour seen for the CC data in Figs. 1–3, although they appar-
ently disappear in the plot of Vc versus Qc in Fig. 4. In general terms,
the QE add a repulsive contribution to the EOS, leading the high
values of Vc observed for 3 He and 4 He (Figs. 1 and 3).
These QE may be quantified in the present context in terms of
the thermal de Broglie wavelength at the critical temperature, c
[27]
1/2
c ≡ h/(2mkB Tc ) (7)
where h is the Planck constant, kB is the Boltzmann constant, and
m is the molecular (atomic) mass. Putting this on a volume basis,
 Author's personal copy
46 P. Molyneux / Fluid Phase Equilibria 279 (2009) 41–46
the cube of this wavelength must be compared with the critical
molecular volume Vc /NA (where NA is the Avogadro constant), with
their ratio giving a dimensionless quantal effect parameter ˚ defined
by:
3/2
˚ ≡ NA h3 /(2mkB Tc ) Vc
For QE to be negligible, ˚
1 (27). Using the values of Tc and Vc Qc critical quotient—Eq. (2) (cm3 mol−1 )
from Table 1 gives the values of ˚ for the NG: 3 He, 1.3; 4 He, 0.56; Ne,
0.03; Ar, 0.0001, with correspondingly smaller values for the higher
NG. The values for the two He isotopes are in line with the deviations
seen in the CC plots (Figs. 1–3). However, with Ne the small value
of ˚ indicates [27] that the QE are not expected to be appreciable,
which accords with the absence of any marked deviation for this NG
in the correlation plots (Figs. 1–4). In this respect therefore, QE do
not have as great an influence on the CC behaviour of Ne as has often
been assumed [5,10,26], and this supports the present observation
that the quartet Ne–Xe behaves as a single group.
5. Conclusions
• From the personal viewpoint, the present investigations started
out simply to try to clear up some anomalies in the literature
values for the sizes of gas molecules. This then became focussed
on the NG as the simplest fluids for which the molecular (i.e.,
atomic) size might be expected to be best established. This in
turn led to the linear correlations between the critical constants
for the NG presented here.
• For the CC area, the NG quartet: Ne, Ar, Kr, Xe, shows good lin-
ear correlations between the three critical parameters Tc , Vc and
Qc . These correlations are surprising in their simplicity and their
apparent novelty.
• The linear correlation between Vc and Qc has the immediate prac-
tical application of enabling the Vc of Rn to be estimated by
extrapolation.
• The positive intercept on this same plot is the cause of the
observed downward drift in the critical compressibility factor Zc
for the group Ne–Xe.
• The helium isotopes 4 He and 3 He show the deviations in that
order from these correlations that may be ascribed to the
expected quantal effects (QE) from such “light” gases.
• The absence of such deviations with the next lightest member, Ne,
indicates that the QE are not important in these CC correlations
and that the group Ne–Xe may be considered as coherent a group;
this is contrary to a common perception.
• The correlation equations for Ne–Xe provide a rational basis for
the display, comparison and correlation of the three CC values for
fluids in general.
• An important limiting case in these correlations is the extrap-
olation to limiting state of zero-mass point particles; this state
is made concrete by naming it as the “element” zeronium (Ze).
This is expectedly the zero limit for the temperature and volume
parameters. However, in this extrapolation the volume parameter
shows a finite intercept; this is referred to as the “Residual Volume
Effect”. It leads to the paradox that the limiting state zeronium,
although it lacks any electrons, is still able to exert a repulsive
force at sufficiently small distances. This remains to be clarified
from the theoretical viewpoint.
List of symbols
CC critical constant(s)
h Planck constant (6.626 × 10−34 J s)
kB Boltzmann constant (1.381 × 10−23 J K−1 )
LCS Law of Corresponding States
Me methyl group (CH3 )
NA Avogadro constant (6.022 × 1023 mol−1 )
NG noble (rare, inert) gas(es)
(8)
Pc critical pressure (Pa)
QE quantal (quantum mechanical) effects (Section 4)
QSM quasispherical molecule(s)
R gas constant (8.3145 cm3 MPa K−1 mol−1 )
RVE “Residual Volume Effect” (Section 3)
Tc critical temperature (K)
Vc critical molar volume (cm3 mol−1 )
Zc critical compressibility ratio—Eq. (1)
Ze zeronium—hypothetical limiting state of zero-mass point
particles
Greek letters
 thermal de Broglie wavelength—Eq. (7) (m)
˚ quantal effect parameter—Eq. (8)
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