Vapour Pressure of Liquid Metals and Alloys
Vapour Pressure of Liquid Metals and Alloys
Vapour 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
(1 ) = ~2 2 (?)[« (?) - 1 ]
J OO
where fx\ and /ug are the chemical potentials of
= Y q J ^ etf d(r ) 4 Tr r 2 dr , ( 7)
liquid and gas state.
I f the hard sphere model is used as a reference
system in the perturbation theory of liquid metals, where wbp is the bare pseudopotential, 0 eff means
the effective interionic potential, and g(r) and a(q)
then the chemical potential of a liquid m etal is
are the pair distribution function and the structure
given by:
d { F vs + N I } factor, respectively. The other symbols have the
p i = r ihs + a »r— L (2 ) usual meaning, and have been described previously
M
(W aseda et al. [7]).
where F ps denotes the total free energy composed There have been several treatm ents for evaluat
o f electrons and ions in liquid metals, N and I are ing the pseudopotentials of bare ions in metals.
The em pty core potentials with the core radius
Reprint requests to Professor Y . Waseda, Departm ent of
o f rc (Ashcroft [8 ]) were used in this work. E qu a
Metallurgy and Materials Science, University of Toronto,
Toronto, Canada, M 5 S 1 A4. 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
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]. — **
•tot
ENERGY LEVEL OF ATOMIC GAS STATE
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.
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.
A cknowledgements
Na N k K
The authors are indebted to Professor J . M.
Fig. 4. Calculated and experimental curves of the activ ity Toguri for his encouragement in this study. One of
of liquid N a-K alloys at 110°C. Solid dotts: present
calculation; dotted line: previous calculation with the hard the authors (YW ) is grateful for financial assistance
sphere model (Waseda et al., 1977). from the National Research Council of Canada.
Y . Waseda et al. • Vapour Pressure of Liquid Metals and Alloys 945
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