V apour Pressure of Liquid Metals and Alloys

Y . Waseda and K . T. Ja co b
Department of Metallurgy and Materials Science University of Toronto,
Toronto, Canada, M 5 S 1 A4
Y . Tsuchiya and S. Tam aki
Departm ent of Physics, Facu lty of Science, Niigata University, Niigata, 950-21, Japan

Z. Naturforsch. 33a, 940—945 (1978); received May 3, 1978

The Gibbs-Bogoliubov formalism in conjunction with the pseudopotential theory is applied

to the calculation of the vapour pressure of eight liquid metals from Groups I to IV of the periodic
table and o f alloys (Na-K). The calculated vapour pressure o f the elements and their temperature
dependencies, the partial pressures, activities and boiling points of the alloys are all found to be
in reasonable agreement with measured data.

1. Introduction the number of ions and the ionization energy,

respectively.
The thermodynamics of liquid metals and alloys
An expression for the total energy -£7tot in liquid
from a viewpoint of microscopic theory has made
m etals and alloys based on the pseudopotential
significant progress in the last few years. The
theory has been discussed previously (for example,
success of the thermodynamical perturbation theory
H artm ann [6 ]) and is not repeated here. The basic
in conjunction with the Gibbs-Bogoliubov technique
equations which are necessary for discussion are:
(Jones [1]) has motivated several applications to
liquid metals and alloys (Hasegawa and W atabe [2 ], E tot E elec En E es E bS
Um ar et al. [3] and Hafner [4]). Recently, Minchin _1- E
W. cc _1_
' 3 | ^ (3)
et al. [5] have calculated the vapour pressure of
liquid sodium using this approach. This prompts us 2.21 0.916
E,elec —r s2 Z ----------
Z
to report our extensive calculations on the vapour rs
pressure of liquid metals and partial vapour - (0.115 — 0.031 ln rs) Z , (4)
pressure of liquid alloys, based on a method which
I 8 7i \Z
is similar in principle but differs in the evaluation E n = hm + — Z |— (5)
of input data. 9 ^o\ Q2 )Q
Eeft -- E es -(- E q
2. Basic Equations and Method of Calculation
E bs (6 )
The condition of equilibrium between a liquid 8 71 e(q)
m etal and its vapour is :

where fx\ and /ug are the chemical potentials of
liquid and gas state.
I f the hard sphere model is used as a reference
system in the perturbation theory of liquid metals,
then the chemical potential of a liquid m etal is
given by:
d { F vs + N I }
p i = r ihs + a »r— L
M
where F ps denotes the total free energy composed
o f electrons and ions in liquid metals, N and I are
Reprint requests to Professor Y . Waseda, Departm ent of
Metallurgy and Materials Science, University of Toronto,
Toronto, Canada, M 5 S 1 A4.
(1 ) = ~2 2 (?)[« (?) - 1 ]
J OO
= Y q J ^ etf d(r ) 4 Tr r 2 dr , ( 7)
where wbp is the bare pseudopotential, 0 eff means
the effective interionic potential, and g(r) and a(q)
are the pair distribution function and the structure
factor, respectively. The other symbols have the
(2 ) usual meaning, and have been described previously
(W aseda et al. [7]).
There have been several treatm ents for evaluat­
ing the pseudopotentials of bare ions in metals.
The em pty core potentials with the core radius
o f rc (Ashcroft [8 ]) were used in this work. E qu a­
tion (2 ) is valid for the systems in which the hard
Y . U'aseda et al. • Vapour Pressure of Liquid M etals and Alloys 941

sphere model is a good reference one. This fact

requires th at the hard sphere structure factors are qo <
m <n
used to fit the experimental ones and then to 1
ui if * ® e^ ti ®
n
« n h h «n a
determine the parameter o f rc in the bare pseudo-
potential by the zero pressure condition, dE tot/ o 'C ■
o oo o co
012 = 0 (see for example, Minchin et al. [5]). I t is g g, 23 ■-H CO « «3
>6 I oc I 50 I o si
also desirable to take into account the contribution W ” CO I I I 50

o f core-core repulsion potential between ions,

except for lighter elements. In this work, we used
the repulsive core part of the effective interionic
£ %
potential which was estimated from the experi­
05 50 05 X 50
mental pair distribution function (Waseda and o 05 x ‘ co’
CO
co’
CO
Tam aki [9]) by using the Johnson and March
scheme. The reliability o f the pair potential CO o O <N
Y i o> oa n Y
estimated by this scheme has been discussed in the
Ö o © © O © © o
literature (Gaskell [10], Kum aravadivel et al. [11],
X X X X X X X X
Ailawadi et al. [12], De Angeles and March [13]). T*
00
50 50 X
Tt; 50 © co 05
I t appears acceptable to use the repulsive part of the CO CO «5
pair potential as a first approximation since the CO o f—
i
05 Gi Ci CO N
results for Na, K and Al are in good agreement with © O o © O © © ©
H
those o f W allace [14] who determined the core-core X X X X X X X X
repulsion potential by fitting the experimental X CO o 05
Cvj uo 05 50 00 075 >o
phonon spectrum. 00 «5 l>

The experimental structure factors for the oc co 50 50 ©

00 o <N <N iq X
elements investigated in this work are well expressed I> <ri 05 Ö a> 1C ui CO
(M <N (M <N
by the hard sphere model (Waseda [15]). E xp eri­ «•!
£3 ci 1 1 1 1 1 1 1 1
mental structure factors are therefore used in the
calculation, although the condition of the Gibbs-
x 05 i-H co
Bogoliubov inequality is slightly obscure. The use CO o X >o X oo

C. J. Smithells [25].
i> I> 50 50 o ’ oc cc
of experimental structure factors is consistent with
the application of core-core repulsion potential
derived semi-empirically. This is also supported by
the close correspondence of the values for the
parameter re determined in this work (Table 1) and
those reported using the hard sphere model (H art­
R. E. Honing and D. A. Kramer [18]. — **

mann [6 ], Hasegawa and W atabe [2]).

« M n a a « T f n
lO *0 05 ^

3. Calculated Results and Discussion

3.1. Vapour Pressure

The entropy of electrons in simple liquid metals
is negligibly small (Umar et al. [4]) and therefore Tf x 50 t - io r-
O N N h C O» ^ WI NSOt O
LO 05 00 50
F ps can be approximated by the total energy i?tot • Ö Ö Ö - —I -rt -H ©
A diagram for the energy states o f a liquid m etal
and its gas phase is shown as Fig. 1 in which the &
origin of energy level corresponds to isolated ions so o o o o o
CO X O ■"♦
50 a co
and valence electrons. From this figure, it is easy
to understand th at the chemical potential o f the *
c3 -O _ 6C n
liquid m etal is given by Equation (2).
942 Y. Waseda et al. • Vapour Pressure of Liquid Metals and Alloys

GROUND LEVEL (ALL IONS AND VALENCE

ELECTRONS ARE ISOLATED)

•tot
ENERGY LEVEL OF ATOMIC GAS STATE

FREE ENERGY STATE OF LIQUID METAL (Fps)

Fig. 1. Diagram of energy state. Etot- total energy in the

liquid state, I : ionization energy of atoms.

The chemical potential of gas atoms which is in

therm al equilibrium with the liquid metal is simply
given by :
I 2 7ih2 \ w
= In [ p (8 )
kBT k B T Km k B T J

The hard sphere term in the chemical potential of

liquid m etal is written as follows:
/hs 2 n h 2 \ 3/2
= In (9)
kBT m kBT ]
Fig. 2. Temperature dependence of the saturation vapour
where the packing fraction rj is given by rj = j i n a sl&, pressure for sodium and potassium. T b : boiling point.
n being the number d e n s i t j ^ and a the hard sphere
diameter. W ith respect to the quantity of S (rj), an Consequently, the term — (dF/dN - f I) corresponds
empirical but a better expression for the entropy to the laten t heat of vaporization. This inference is
of the hard sphere system is the result of averaging supported by the close agreement between values
the two Percus-Yevick pressures (Silbert et al. [16]), for the quantities given in Table 1. The temperature
as given by the Carnahan-Starling equation: dependence o f the vapour pressure, calculated
S csiy ) 1 using E q. (11), is compared with experimental
= 3 (10 ) information for Na and K in Figure 2.
kB (1 — rj) (1 — rj)2 '

A t thermodynamic equilibrium, the following 3.2. Entropy of Vaporization

relation is obtained.
Using the relation of E q. (11), the entropy of
Scsitj) vaporization a t the boiling point (where p = 1 atm )
ln p = ln n k B T —
kB is given by :
1 ps
+ / (11 ) 1 \l^F i
+ kBT

This expression is essentially equivalent to those 2

= k\\ ln wb k B T b 3 -
obtained by Minchin et al. [5] and Reiss et al. [17]. (1 - »7b)
The details of the calculation of vapour pressures 1
of eight metals at their melting points based on (1 2 )
(1 — rjb)2
E q . (11) are summarized in Table 1, together with
the experimental data (Honig and K ram er [18]). where T b , Wb and rjn are the boiling temperature,
The calculated vapour pressures are in reasonable the number density, and packing fraction, respec­
agreement with experimental inforamtion. As seen tively, of the liquid m etal at the boiling point.
in Fig. 1, the binding energy in metals is approxi­ I f there is no significant change in the electronic
mately expressed by the latent heat of vaporization. structure of liquid metals from their melting point
Y . W aseda et al. • Vapour Pressure of Liquid Metals and Alloys 943

Table 2. Comparison o f calculated entropy of vaporization with experimental data.

a TJm — ($Cs/&B)Tb In kß Tb Entropy of vaporization

( X 10~4 deg-1 ) (cal •deg-1 m o h 1)
calc. exp. *

Li 1.80 0.46 0.38 2.83 8.87 23.3 20.26

Na 2.75 0.46 0.38 2.83 8.10 21.7 20.27
K 2.90 0.46 0.38 2.83 7.29 20.1 18.60
Rb 3.38 0.43 0.35 2.44 6.92 18.6 18.79
Cs 3.95 0.43 0.35 2.44 6.64 18.0 20.32
Mg 1.90 0.46 0.42 3.42 8.83 24.3 23.56
Al 1.16 0.45 0.37 2.70 9.71 24.7 25.11
Pb 1.17 0.46 0.39 2.97 9.04 23.9 21.01

m : melting point; b : boiling point; * C. J . Smithells (1962) [25],

to the boiling point, the hard sphere model might /ha is given by the following expression:
n ot be less applicable with the increase in tem pera­
ture. The change in the packing fraction with
tem perature can be estimated from thermal expan­ (16)
sion coefficient a v :
where N a + -^b = N.
As mentioned before, F ps can be approximated
^ > = i r r J r a r (13) by the to tal energy. The derivation of the total
where the suffix m denotes the melting point. energy of liquid metals and alloys based on the
Using the observed values for rjm (Waseda [15]) pseudopotential method is well described in the
and av (Willson [19]), the entropies of vaporization
a t the boiling point are obtained, as shown in
T able 2. The agreement between theory and
experiments is satisfactory. I t should be noted
th a t the Trouton’s rule suggests an average value
o f about 2 0 cal.deg . - 1 mol- 1 for entropy o f vapor­
ization for metals.

3.3. P artial Vapour Pressures Over Alloys

The equilibrium partial vapour pressures over
liquid binary alloys is given b y :
vx = v\ ax, (14)
where p°x is the vapour pressure of component A
in its pure state and a\ is the activity of com­
ponent A in liquid alloys.
A calculation o f activities in liquid alloys based
on the electron theory of metals has already been
attem pted by the present authors (Waseda et al.
[7]). The essential features are summarized below:
The activity aa in a binary A -B alloy is given b y :

a a — exp (15)
Jcb T
where [jla and [i\ are the chemical potentials of
elem ent A in the alloy and in the pure standard Fig. 3. P artial structure factors obtained experimentally
state. for liquid N a-K alloys.
944 Y. Waseda et al. • Vapour Pressure of Liquid M etals and Alloys

literature (Heine and Weaire [20], Stroud and Table 3. Comparison of calculated partial vapour pressure
of liquid N a-K alloys with experimental data.
Ashcroft [21], Harrison [22], Hafner [3]). In the
case of liquid alloys, the parameters required to
Atomic PNa ( X 10“9 atm.) P k ( X 10~9 atm.)
determine the to tal energy are the bare pseudo­ fraction
potentials o f the elements, the dielectric function of Na calc. exp. * calc. exp. *
and the partial structure factors. The partial
0.0 0.00 0.00 4.98 1.46
differentiation ( d F vsldN A) can be easily obtained 0.1 0.044 0.03i 4.50 1.32
from the plot of i^ps versus 2VA (Waseda et al. [7]). 0.2 O.O81 0.054 4.02 1.21
0.3 0.11 0.071 3.62 1.10
Following the method described in our previous 0.4 0.13 O.O85 3.22 1.01
work (Waseda et al. [7]), the activity of liquid 0.5 0.15 0.09s 2.87 0.91
0.6 0.17 0.11 2.53 0.81
N a-K alloys a t 110°C was estim ated. However, in 0.7 0.19 0.11 2.07 0.70
this calculation, we used the partial structure 0.8 0.21 0.12 1.60 0.55
factors of Fig. 3 obtained experimental!}". A more 0.9 0.23 0.13 0.95 0.33
1.0 0.26 0.15 0.00 0.00
detailed information on the partial structure
factors will be published elsewhere. Other param ­ * F . A. Cafasso, V. M. Khanna and H. Feder (1967) [23].
eters were almost identical to the previous ones.
Namely, we used the empty core potentials which
— ~ " Table 4. Comparison of
are fitted to satisfy the equilibrium condition in the K Tb ( C) calculated boiling point of
pure state, and the Habbard-Sham dielectric
/a t o / \ ZÜ exn * H q u id N a "K a ll° yS W ith
function. As shown in Fig. 4. the estim ated activity ' ' '° ' ________ experimental data.
curve reasonably reproduces the observed one 0 865 892
(Cafasso et al. [23]). 32 802 825
68 775 784
The partial vapour pressures estim ated from the 100 733 760
calculated activities using E q. (14) are shown in
Table 3. There is fair agreement between the * C. B . Jackson (1955) [24].
calculated and experimental values.
The total pressure P over a binary alloy is given Consequently, we could estimate the boiling point
by the following relation: of a binary alloy from Equation (17). The boiling
point of a binary alloy corresponds to the tem ­
P = P a “ a + J> B ° b • (17) perature which satisfies the condition of P = 1 atm .
The estimated values are in good agreement with
experimental data (Jackson [24]) as shown in
Table 4.
As stressed in the work of Michin et al. [5], the
present theory is adequate only for the systems in
which the hard sphere reference is applicable and
at pressures below one atmosphere. However, the
results obtained in this extensive work suggest th a t
the first order variational method of Gibbs-
Bogoliubov is one way to discuss th e vapour
pressure of liquid metals and alloys in the pressure
range amenable to experimental investigation.

Na N k K
Fig. 4. Calculated and experimental curves of the activ ity
of liquid N a-K alloys at 110°C. Solid dotts: present
calculation; dotted line: previous calculation with the hard
sphere model (Waseda et al., 1977).
A cknowledgements
The authors are indebted to Professor J . M.
Toguri for his encouragement in this study. One of
the authors (YW ) is grateful for financial assistance
from the National Research Council of Canada.
Y . Waseda et al. • Vapour Pressure of Liquid Metals and Alloys
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