Journal of Colloid and Interface Science 304 (2006) 549–553

www.elsevier.com/locate/jcis

Correlation between surface tension and critical temperatures of

liquid metals
Sidney Blairs a,∗ , Mohammad Hassan Abbasi b
a School of Materials Science and Engineering, University of New South Wales, P.O. Box 1, Kensington 2030, Australia
b Faculty of Materials Engineering, Isfahan University of Technology, Isfahan, Islamic Republic of Iran

Received 3 May 2006; accepted 23 July 2006

Available online 1 August 2006

Abstract
The inter-relationship of surface tension σ , molar volume V , and critical temperature Tc has been examined using experimental values for
eighteen liquid metals. Hard-sphere diameters a correlate with the equation

a 5/2 = 8.9733 × 10−19 V (σ/Tc )1/4 − 1.0459 × 10−25 .

Unknown Tc may be estimated using surface tension and liquid density values.
© 2006 Elsevier Inc. All rights reserved.

Keywords: Liquid metals; Critical temperatures; Surface tension; Density

1. Introduction more accessible thermophysical properties. In the present com-

Measurement of the critical parameters of liquid metals by
conventional static techniques is limited by their generally high
melting and critical temperatures. Critical temperatures are at
low enough temperatures and pressures to allow their mea-
surement by static methods for only mercury and the heavier
alkali metals, although by reasonable extrapolation, values for
the lighter alkali metals may be obtained. To overcome these
limitations, dynamic pulse heating experimental techniques of
sub-millisecond duration have been developed [1–3]. While
rapid pulse heating techniques are of general experimental im-
portance, difficulties encountered include; uneven energy dis-
persion caused by the skin effect, electrical instabilities caused
by sample inhomogeneity, nonuniform expansion and magneto-
hydrodynamic instabilities. Notwithstanding significant devel-
opments in the technique of experimentation, directly deter-
mined critical parameters for the majority of liquid metals are
as yet unavailable. In their absence, several attempts have been
made to develop correlations between critical parameters and
* Corresponding author. Fax: +612 93851000.
E-mail address: blairs@netspace.net.au (S. Blairs).
0021-9797/$ – see front matter © 2006 Elsevier Inc. All rights reserved.
doi:10.1016/j.jcis.2006.07.072
munication, the inter-relationship between critical temperature,
surface tension and molar volume (density) of liquid metals is
examined.
2. Methods for estimating critical temperatures
Critical temperature Tc has been related to the normal boil-
ing point at atmospheric pressure Tb via the empirical Guldberg
rule [4]. Using the alkali metals as a normalising factor, the
proportionality constant of 1.5 in the original Guldberg rule
may be modified to (2.107 ± 0.054) [5]. As an alternative to
a direct proportionality between Tc and Tb , a power law re-
lationship Tc = 1.2574Tb1.0788 (correlation coefficient 0.9798)
may be derived [6]. These power law coefficients were obtained
using experimental Tc and Tb for both metallic and nonmetallic
liquids. Since the vaporisation entropy of metals is nominally
constant (Trouton’s rule), Tc may also be related to the enthalpy
of vaporisation Hv as in the Kopp–Lang rule [7,8].
Grosse [9] has outlined two essentially independent methods
whereby the critical constants of liquid metals may be esti-
mated. In one of these methods, experimental liquid density ρ
and vapour pressure data may be used to estimate critical tem-
550 S. Blairs, M.H. Abbasi / Journal of Colloid and Interface Science 304 (2006) 549–553

peratures, densities and volumes using the rule of rectilinear
diameters (between upper and lower bounds). Evidence ex-
ists [10] that this rule is not obeyed in the vicinity of the critical
point. In the second method, Tc values are obtained by appli-
cation of the principal of corresponding states to the entropy
of vaporisation Sv . Metallic liquids with identical reduced
temperatures T ∗ = T /Tc have identical molar entropies of va-
porisation. Use of these two methods is well-illustrated by the
construction of liquid range-temperature diagrams for lead and
silver [11]. Fortov et al. [12] have used the second method to-
gether with the experimental Sv vs T curve for caesium to
obtain Tc values for the metallic elements.
Tc values may also be estimated from experimental sound
velocities, isobaric heat capacities, and liquid densities using
an isochoric thermal pressure coefficient method [13].
Goldstein et al. [14] have related Tc to the free electron con-
centration ne,c at the critical point. Likalter [15] has related
the critical point parameters to the ionisation potential of the
undisturbed atom and the critical valence zc . Unfortunately, in
both of the latter approaches neither ne,c nor zc is well defined.
Hess [16] has developed a method whereby the requirement
for a knowledge of zc is removed. Tc is obtained by the in-
tersection of the Likalter [17] equation with the experimentally
determined vapour pressure curve for the metallic element.
Martynyuk and Tamanga [18] have calculated critical point
parameters of a series of refractory metals on the basis of a gen-
eralised van der Waals equation of state. Experimental vapori-
sation enthalpies Hv and liquid densities were used to derive
the coefficients in the generalised equation of state.
Hohenwarter and Schwarz–Bergkamf [19] have adapted
a critically standardised Plank–Riedel steam pressure equa-
tion to obtain Tc for metallic elements. The Hoch–Arpshofen
method [20] may be also employed to obtain critical constants.
In this latter method only the liquid density as a function of tem-
perature (but not necessarily close to Tc ) is required to obtain
the critical temperature and density.
in which ε and a are the parameters in the Lennard-Jones (6.12)
potential. For spherical nonpolar molecules obeying the Len-
nard-Jones (6.12) potential:
ε = 0.77kB Tc , (3)
where kB is the Boltzmann constant. By combining Eqs. (1)–
(3), the diameter of hard-sphere molecules may be expressed
as
a 5/2 = constant × V (σ/Tc )1/4 . (4)
Data necessary to compute hard-sphere diameters of mole-
cules are therefore liquid densities, surface tensions and critical
temperatures. Alternatively the hard-sphere diameter of a liquid
may be calculated from the commonly-used expression:
a = (6yV /πN0 )1/3 , (5)
where y is the dimensionless packing fraction and N0 is
the Avogadro number. In the Percus–Yevick [24] hard-sphere
model of a liquid, the long-wavelength limit of the static struc-
ture factor S(O) may be expressed solely in terms of y viz.:
S(O) = (1 − y)4 /(1 + 2y)2 . (6)
Hard-sphere diameters may thus be obtained from experi-
mental S(O) and liquid densities. Hard-sphere diameters ob-
tained in this manner were found to conform closely with the
relationship [25]
a 3 = (1.484 ± 0.025) × 10−24 V . (7)
Van Loeff [26] used experimental viscosities and Protopa-
pas and Parlee [27] self diffusion values to assign values of
1.514 × 10−24 and 1.506 × 10−24 , respectively to the factor in
Eq. (7). Equations analogous to Eqs. (3) and (4) are anticipated

3. Method of calculation

The parachor [P] relates the surface tension σ and the molar
volume V of a liquid and was expressed by Sugden [21] as

[P] = σ 1/4 V . (1)

The parachor is an additive and constitutive property of organic
and inorganic liquids and is almost independent of temperature.
Since σ appears in Eq. (1) to the exponent 1/4, its influence on
the parachor is damped and its influence on the additive nature
of the parachor is consequently less than V . Paquette and Gold-
sack [22] have proposed an anisotropic surface model for [P]
explaining these properties in terms of molecular parameters.
The anisotropic surface model gives a rational explanation to
various empirical relationships between [P] and other liquid
properties such as Tc . Lennard-Jones and Corner [23] have
shown that for simple molecules the parachor is given empir-
ically by Fig. 1. a 5/2 vs V (σ/Tc )1/4 for liquid metals. a is the hard-sphere diameter,
V the molar volume, and σ the surface tension at the melting temperature. Tc is
[P] = constant × ε 1/4 a 5/2 , (2) the critical temperature.
 S. Blairs, M.H. Abbasi / Journal of Colloid and Interface Science 304 (2006) 549–553 551

for metallic liquids differing only in their numeric factors. Us-
ing literature values for liquid densities, surface tensions and
critical temperatures, the quantity V (σ/Tc )1/4 has been cal-
culated and also the term a 5/2 using Eq. (7) at the respective
melting temperatures, see Table 1. Fig. 1 shows the resulting
plot of a 5/2 vs V (σ/Tc )1/4 . Data from Fig. 1 correlate with the
equation (correlation coefficient R = 0.9960):
a 5/2 = 8.9733 × 10−19 V (σ/Tc )1/4 − 1.0459 × 10−25 . (8)
Using liquid densities together with Eq. (7) to calculate a,
Eq. (8) may then be used together with literature surface
tensions and densities to calculate Tc values. Values ob-

Table 1
Experimental critical temperatures Tc , and the terms a 5/2 and (V σ/Tc )1/4 at the melting temperature Tm
Metal a 5/2 (m5/2 × 1024 ) (V σ/Tc )1/4 (m2 N K−1 mol−1 × 106 ) Tc (K)
Cs 5.0983 5.7553 1924 ± 10 [5]
Na 2.0204 2.3586 2485 ± 15 [5]
Li 1.2144 1.5161 3344 [5]
Pt 0.9672 1.1848 9825 [35]
In 1.4244 1.5449 7000 ± 490 [36]
Pb 1.6564 1.8741 5400 ± 400 [37]
K 3.4483 4.0173 2198 ± 30 [5]
Rb 4.0564 4.6303 2017 ± 10 [5]
Zn 0.9452 1.2246 3600 ± 360 [38]
Au 1.0653 1.2856 7400 ± 1100 [39]
Hg 1.3023 1.9033 1753 ± 15 [40]
Ir 0.9357 1.1946 10,335 [41]
V 0.9157 1.2584 6396 [41]
Co 0.7546 0.8888 10,384 ± 830 [42]
Fe 0.7806 0.9506 9250 ± 1110 [43]
W 1.0433 1.2763 13,400 ± 1400 [44]
W 1.0433 1.2344 16,000 ± 1000 [45]
Se 1.6778 1.7373 1863 ± 20 [46]
Mo 0.9859 1.3674 10,400 ± 267 [47]

Table 2
Critical temperatures estimated by various procedures
Metal Tc (K)a Tc (K)b Tc (K)c Tc (K)d Tc (K)e Tc (K)f Tc (K)g Tc (K)h
Li 3647 3223 3660 4176 – 4230 3875 –
Be 6432 8080 – 9195 – 8680 7650 2733
B 10,003 8200 – 12,300 – 14,990 – 2695
Na 2568 2573 2447 2535 – 2840 2628 –
Mg 3021 3590 2929 – – 3860 3385 4437
Al 6557 8000 5654 8960 – 8560 7543 5115
Si 8384 – 5964 – 12,910 10,453 4387
K 2260 2223 2286 – 2380 2249 –
Ca 3976 4180 3770 – 4630 3962 4894
Sc 7374 8350 – 7014 – 9670 8847 7868
Ti 8710 11,790 – 7964 9040 12,560 10,689 8888
V 8834 12,500 – 9141 9980 13,540 11,787 –
Cr 6941 9620 – 6482 – 10,400 8721 5024
Mn 5401 5940 4927 7051 – 6650 5984 5882
Fe 7426 9600 5874 4762 – 10,430 9264 –
Co 7595 10,460 5272 10,214 – 11,150 9753 –
Ni 7559 10,330 5807 6517 10,770 9784 6705
Cu 6690 8390 5518 7696 – 8990 7881 5183
Zn 2588 3190 2884 – – 3390 3028 –
Ga 5760 7210 4282 – – 7430 6690 4218
Ge 7354 9170 5742 – – 9600 8698 2668
Se 2183 1010 – −− – 2750 – –
Rb 2098 2093 2047 1969 1946 2220 1981 –
Sr 3806 3860 3640 – – 4320 3667 4918
Y 8648 10,800 3884 – – 11,300 9742 9035
Zr 11,513 16,250 – 10,872 10,720 15,740 14,586 11,571
Nb 12,335 19,040 – 11,809 12,320 19,580 17,267 11,499
Mo 12,242 16,140 7696 18,766 11,330 17,360 15,239 –
Ru 10,766 15,500 – 8990 – 17,010 15,115 10,377
Rh 9583 13,510 – 8948 10,590 14,950 11,787 8967
(continued on next page)
552 S. Blairs, M.H. Abbasi / Journal of Colloid and Interface Science 304 (2006) 549–553

Table 2 (continued)
Metal Tc (K)a Tc (K)b Tc (K)c Tc (K)d Tc (K)e Tc (K)f Tc (K)g Tc (K)h
Pd 7687 10,760 – 9142 – 10,190 9255 7624
Ag 5655 7040 3852 – – 7400 6612 5609
Cd 2258 2790 2318 – – 3010 2620 4510
In 5430 6420 3520 – – 6590 5972 –
Sn 6766 8200 4536 – – 8070 7605 4956
Sb 4309 2570 4390 – – 4970 – 3755
Te 2940 – – – – 3450 2972 2543
Cs 2046 2057 2026 1941 1884 2000 2002 –
Ba 4991 4100 4506 – – 4520 3993 4879
La 8956 11,060 5698 – – 11,370 10,276 8200
Hf 11,958 18,270 – – 11,030 17,770 14,526 11,936
Ta 14,238 20,570 10,177 12,791 13,680 21,600 19051 13,284
W 14,788 21,010 7650 12,466 14,700 22,920 20,447 –
Re 14,608 19,600 – – 13,070 20,660 17,949 13,398
Os 13,048 17,110 – 12,450 – 20,290 16,929 11,961
Ir 11,498 15,380 – 10,636 12,120 17,760 15,650 –
Pt 9919 14,330 – 16,850 10,450 14,450 13,093 –
Au 7413 8970 4048 – – 9950 8644 –
Hg 1315 1753 1982 – 1720 1710 1542 –
Tl 3949 4470 3249 – – 4800 4322 4176
Pb 4624 4980 5573 – – 5150 4670 –
Bi 4415 4200 – – – 5250 4537 3958
Ce 8876 8860 4190 – – 11,430 9271 7363
Pr 9096 9160 5028 – – 9620 – 7269
Nd 7952 7920 – – – 8370 7410 6998
Sm 4728 5340 – – – 5800 4507 4274
Eu 7426 4680 – – – 4680 – 3921
Gd 8462 8670 – – – 10,080 – 6571
Tb 8351 8060 – – – 9893 – 6492
Dy 6659 7240 – – – 8530 – 6195
Ho 6997 7240 – – – 8460 – 6159
Er 7462 8250 – – – 9380 – 5940
Tm 5115 5910 – – – 6600 – –
Yb 3272 4280 – – – 4310 3272 3907
Lu 8796 7060 – – – 11,000 8796 8375
Th 12,449 14,950 – – 10,890 15,490 12,449 10,777
U 10,721 11,630 – 9000 9900 12,820 10,721 10,456
a From T , this study. b From S [12]. c From sound velocities [13]. d From Likalter method [16,17,34]. e From H and ρ [18].
b v v
f From H [7,8]. g From Plank–Riedel method [19]. h Present study from ρ and σ using Eqs. (7) and (8).
v

tained in this manner are summarised in Table 2 and com-
pared with the results of earlier critical temperature estima-
tions.
4. Results and discussion
In Table 2 critical temperatures are listed for the metallic el-
ements from different literature sources and methods together
the present values. Selenium is essentially a molecular liquid
in the vicinity of the critical point [28] rather than a metallic
one but is included because of the availability of its experi-
mental Tc . Literature surface tensions were taken from the re-
view by Keene [29] except for the liquid rare earth elements
where both densities and surface tensions are those reported
by Kononenko et al. [30]. Other liquid densities used were ob-
tained from the reviews by Crawley [31] and by Lucas [32].
Boiling temperatures used to calculate Tc using the power law
relationship reported earlier were taken from the compilation
by Barin [33].
With the exceptions of boron and beryllium, critical tem-
peratures reported in the present work fall close to or within
the range of values reported in the literature. Low Tc values
for beryllium and boron is suggested to result from inadequate
surface tension data. Literature data for these two refractory
and reactive metals comprise data at only a single measure-
ment temperature. In particular, Tc values for the transition and
refractory metals are close to those values obtained by appli-
cation of the Likalter approach [34] or by use of the gener-
alised van der Waals equation of state [18]. For the liquid rare
earth elements a double periodicity in the variation of Tc with
atomic number is observed. This mirrors the similar periodic-
ity observed by Kononenko et al. [30] for other thermophysical
properties of this group of elements. The observed variation is
a probable consequence of the well-known lanthanide contrac-
tion. For this group of metals, the present Tc values are closer to
those obtained by Fortov et al. [12] from vaporisation entropies
than to those obtained via the Kopp–Lang approach [7,8] using
vaporisation enthalpies.
 S. Blairs, M.H. Abbasi / Journal of Colloid and Interface Science 304 (2006) 549–553 553

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