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1492 THE DISTRIBUTION EQUILIBRIUM OF SODIUM

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T H E DISTRIBUTION EQUILIBRIUM O F SODIUM

BETWEEN MOLTEN SODIUM HALIDES (NaBr,
NaI) AND A MOLTEN METAL PHASE (Cd, Pb,
T1, Sn, Bi, Sb, Au).
AND H. P. WEBER.
BY E. HEYMANN
Received 9th September, 1938.

The investigation of the distribution equilibrium of cadmium between

molten cadmium chloride (as a salt phase) and molten bismuth (as a
metal phase), and the application of Nernst’s distribution law to this
equilibrium, has shown that solutions of cadmium in cadmium chloride
are true atomic so1utions.l Moreover these systems proved to be dia-
magnetic, thus excluding the existence of a unimolecular subchlsride.2
It is desirable to apply the distribution equilibrium method to solu-
tions of other metals in their molten salts (e.g., sodium in molten sodium
halides), since no reliable information about the molecular state of such
solutions has been available.
Great experimental difficulties are encountered in these systems,
containing molten sodium and molten sodium halides, partly because
of the chemical reactivity of the metal (attack on the glass container)
and partly because of the high melting-points of the salts. However,
although these difficulties render impossible a high degree of accuracy
in these systems, i t will be seen that not only is information obtained
about the molecular state of solutions of sodium in molten sodium
halides, but also qualitative information about the stability in the
molten state of intermetallic compounds of sodium with the respective
metallic components of the system.
Solutions of sodium in molten sodium chloride have been d e ~ c r i b e d . ~
The systems are very intensely coloured, dilute solutions appearing
violet, whereas the more concentrated ones are almost black, Molten
1 E. Heymann and E. Friedlaender, 2. p h y s i k . Chemie., A , 1930, 190, 148.
2 J . Farquharson and E. Heymann, Trans. Faraday Soc., 1935, 31, 1004.
R. Lorenz and R. Winzer, 2. anorg. Chemie, 1929, 183, 121.
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E. HEYMANN AND H. P. WEBER I493

sodium chloride is, however, not very suitable as a solvent, since, apart
from silica, there is no glass available which does not soften at its melting
temperature (800" C.). For this rea5on molten sodium bromide and
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molten sodium iodide were chosen, the melting-points of which (755"

and 655") are sufficiently below the softening point (800")of the Supremax
glass (Jena) employed in these experiments.

Experimental.
The salts and metals used were the purest products commercially
obtainable, the salts being of Analar standard.
" "

Immediately prior to use the salt was dried at 400" to 500" in a stream
of nitrogen. It was then placed together with an alloy of Na with the
respective metal (e.g., Cd, Pb, Bi, etc.) in a Supremax glass tube of about
1 2 mm. internal diameter and the air thoroughly displaced by introducing,
a stream of pure dry N from the bottom of the tube. This was prepared
by passing commercial N through a furnace containing hot reduced Cu
metal. The tube was afterwards formed to a capillary at the end, evacu-
ated and sealed. Finally a hook for suspension purposes was sealed on
to the end of the tube.
A heat resisting steel tube furnace was used. The steel tube, of 3 cm.
diameter, was wound in such a way that over a distance of 26 cm. the
temperature, measured by a calibrated chromel-alumel thermocouple
and a Hoskins indicator, did not vary by more than 4" at 760". The
furnace was mounted so that it could either be set vertically or rocked
about a horizontal position by means of a lever resting on a slowly rotating
crank.
The sealed tube was placed in the cold furnace and brought to the
experimental temperature. The furnace was rocked for 60 minutes and
afterwards the system allowed to settle vertically for 20 to 30 minutes.*
The tube was then removed and quenched in a blast of compressed air.
I n order to ensure that no appreciable shift in the equilibrium occurred
during the quenching operation, the experiments were carried out only
about zoo above the melting-point of the salt phase, thus ensuring quick
solidification on cooling.
The tube, on opening, was quickly analysed. With alloys below
70 atom yo Na, clean separation of the metal phase from the salt phase
occurs. Above this concentration, however, and also with pure Na, the
separation presented great difficulties, the metal phase which, a t these
concentrations, is less dense than the salt phase, adhering strongly to the
salt ; moreover, a considerable amount of Na condensed on any otherwise
free salt surface because of high vapour pressure of Na. Because of this
the tubes containing Na a t high concentrations on being removed from
the furnace were treated thus : the lower portion of the tube, containing
the salt phase, was quickly cooled, and when this had solidified, the tube
was inverted to allow the still molten alloy to run to the other end of the
tube away from the salt. Next the end containing the alloy was sub-
jected to a cooling air blast in order to bring about condensation of the
Na vapour in this portion of the tube, and not on the salt surface which
was still at about 400". But even when this procedure was adopted the
experiments with metal phases of high Na content still gave irregular
results as can be seen from Figs. 4 and 5. Therefore, measurements at
high Na concentrations were only carried out with certain systems. The
main evidence was furnished by the investigation of distribution equilibria
in which the Na content of the alloy did not exceed 30 atom yo.
The inside wall of the tube, after the experiment, was covered with
a black adhering layer of Si formed by the reduction of the 50, of the
* In systems containiug Na in high concentrations these times were shortened,
because of the attack of the Na on the glass, to 2 0 and 15 minutes respectively.
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1494 THE DISTRIBUTION EQUILIBRIUM O F SODIUM

glass by the Na a t high temperature. Although this attack was con-
siderable, the Na,O which must be formed in the reaction was obviously
bound by the glass and did not pass into the salt phase, as the total alkali
there, as determined by titration ‘with N . / I O HCl, was seldom more than
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0.2-0-4 weight yo of Na greater than the amount of free Na as determined

by the volume of H , evolved on solution of the salt in water. The glass
thus absorbed alkali oxide from the molten salt, a behaviour which is
consistent with a high acid content in the Supremax glass.
Alloys of Na with metallic “ solvents ” were prepared in separate
Pyrex glass tubes. The Na and the other metal, e.g., Pb, Cd or Bi, etc.,
were placed in a bent tube, the tube evacuated and sealed, the sodium
melted in one arm of the bend, and the other metal, e.g., Pb, tipped over
into it and dissolved, and the resulting alloy poured over into the clean
arm of the tube, the alloys thus obtained being free from oxide.
The analysis of the metal phase was simple. It was decomposed under
water, the complete decomposition being effected by alloying it with Hg
and boiling with H,O until all action had ceased. The solution was then
titrated with ~ . / HC1.
2 Alloys higher in Na content were decomposed
first by alcohol and later by water. In the case of
Bi-Na alloys, the alloy had to be ground up with
Hg under water until no further alkali could be ex-
tracted, as Bi does not so readily alloy with Hg a s
do other metals.
For the analysis of the Na content of the salt
phase, based on the evolution of H, when the salt
was dissolved in water, an apparatus as shown in
Fig. I was constructed. A glass bulb ( a ) of about
j cm. diameter was fitted with a ground glass
stopper (b) from which a short delivery tube (c)
led to a gas burette of small capacity. To the
stopper was attached a glass hook (d) from which
could be suspended a glass capsule (e) containing
--u the salt sample (up to 12 grams of salt). A known
volume of water was placed in the bulb, the sample
capsule and stopper placed in position, and the
whole allowed t o come to the temperature of a
FIG. I. surrounding water bath, the temperature of which
was adjusted to room temperature.
The pressure in the apparatus was then adjusted to atmospheric pres-
sure, and the apparatus inclined so that the capsule fell into the water.
When the salt was completely dissolved, the volume of the hydrogen
evolved was measured in the gas burette.
The volume of the whole apparatus was about IOO ml., and the tem-
perature of the apparatus and the gas burette during any determination
was kept constant within o-1-0.2~ ; hence the volume errors due to any
temperature fluctuations in the apparatus were not greater than 0.1ml.,
this representing an error in the Na value of 2-3 yo a t nfost, which is less
than the experimental error.
The volume of H, measured must be corrected for the solubility of
the H, in the salt solution, and the contraction of volume which occurs
on solution of the salt in water. From the densities of solid NaBr and
NaI and of their solutions, curves may be constructed expressing the
volume contractions per 10 ml. water as a function of the concentration
of the salt solution. From the data on the solubility of H, in NaCl
solutions a curve may be constructed for the solubility correction, assum-
ing that the solubilities in NaBr and NaI solution are approximately the
same. This correction is rather uncertain, but since i t is very small
(about 0.05 ml.), compared with the volume of H, measured (2-15ml.)
4 A. Seidel, Solubilities, New York, 1919.
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E. HEYMANN AND H. P. WEBER I495

and the volume contraction correction, it is not sufficient to impair the
experimental accuracy, which for other reasons (cf. the discussion) is not
high, The addition of these two curves gives then a correction curve
which represents the total volume contraction per 10ml. water as a function
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of the concentration of the salt solution. From the corrected volume of

H,, the temperature, pressure and the mass of the sample, the concentra-
tion of the free Na in the salt may be calculated.*
The solid salt phase (Na-NaBr) after quenching was of light blue colour
when the free Na content was almost below the limit of analytical accuracy
(analogous to the blue rock salt). A t slightly higher concentrations the
solid salt phase was yellow, whereas it had a greyish white appearance
when the Na content was above 0.3 atom yo. The solid salt phase Na-NaI
also exhibited a definite colour only a t low Na contents. The colour
was here lemon yellow to orange yellow.

Results and Discussion.

of Na in the salt phase (NaBr)

is plotted against the atomic
fraction of Na in the metal .CW$
' *
c --
_--
phase. Up to 20 atom yo a .o.7.s c
c
c

straight line is obtained. -

I
0
Nernst's distribution law pos- .0-5-
tulates in this case that the
Na in both phases is in the -0.3$
same molecular state. It is
almost certain that the solu- .
I

' relation leads to the assumption

that the solution of Na in molten
NaBr is atomic. The deviation of
the curve from a straight line a t
concentrations above 20 atom yo
merely indicates that the system
is no longer ideal a t higher concen-
trations.
An analogous result is obtained
for the distribution equilibrium of
Na between molten Cd and molten
NaI a t 770" (Fig. 3 ) . Here, too,
a t low concentrations a linear re-
lation is found between the atomic
fractions of Na in the metal phase
and in the salt phase. Hence i t
may be concluded that solutions
FIG. 3 . Cd-Na-NqI. of Na in NaI are also atomic.
0 770:c. Also a t 690" a linear curve is ob-
690 C. tained a t low concentrations, but
* The concentration of Na in the salt phase is expressed as atom per cent.
.loo,where nxa is the number of gram atoms Na and nsalt the number
"Na + "salt
of gram molecules of the salt.
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1496 T H E DISTRIBUTION EQUILIBRIUM OF SODIUM

the solubility of Na in the molten NaI is only about one half of that at
7 7 0 ~ . At higher concentrations the curve becomes concave upwards. It
1s possible that this curvature is the result of interatomic forces between
Na and Cd in the metal phase which make themselves felt more strongly
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a t lower than a t higher temperatures (cf. discussion below).

The first deviation from the simple type was encountered in the dis-
tribution equilibrium of Na between a sodium halide phase and P b as a
metal phase. At low atomic fractions of Na in the metal phase (up to
15 atom yo in the equilibrium with NaBr a t 770" and up to 25 atom yo
with NaI a t 690"), the concentration of Na in the salt phase is zero (Figs.
4 and 5 ) . Only a t higher atomic fractions in the metal phase does the
sodiu content in the salt phase rise slowly, the curves being concave to
the afscissa. The curves in Figs. 4 and 5 can only be regarded as ap-
proximate representations of the respective distribution equilibria. The
experimental accuracy decreases very considerably with increasing Na
content of the systems. One reason for this is the attack of the Na on
the glass, which is unimportant so long as the equilibrium between the
molten phases is continuously maintained by shaking ; afterwards, how-
ever, when the phases are allowed to separate, the reaction with the glass
affects the concentration in the salt phase more than that in the metal
phase, since the former is much lower than the latter. Moreover, as men-
tioned above, the separation of the salt phase from the metal phase be-
comes more difficult with increasing concentration of Na.
However, the curves are clearly concave, rising from zero only at 15
t o 25 atom yo Na in the metal phase, and considerably below the straight
dotted line which would be expected -if the mixtures of Na and Pb were
ideal mixtures. On the other hand, the previously mentionediequilibria
with Cd as metal phase show linear distribution and, therefore, solutions
of Na in molten NaBr and NaI must be regarded as atomic. Thus the
concave shape of the distribution curve in the case of equilibria with P b
as solvent'' (the curve lying always below the "ideal" curve), must
"

be due to the fact that the activity * of Na in the metal phase is con-
siderably smaller than its atomic fraction and sinks to zero a t an atomic
fraction of about 0 . 2 . From the curve i t may be estimated that the
activity coefficient * of Na in these mixtures, defined as unity for pure
Na, is of the order of 0.5 a t an atomic fraction of 0.4 and falls to zero a t
a n atomic fraction of 0.15 to 0 - 2 . t This low activity coefficient of Na is
most probably due t o interatomic forces between Na and Pb. At low
temperature, especially in the solid state, these forces lead to compound
formation, indicated by several maxima in the phase diagram, corre-
sponding, e.g., to Na,Pb (m.p. 405") and NaPb (m.p. 367"). At the experi-
mental temperature, which is about 400' higher, these compounds are
most probably decomposed (see below), but the forces between Na and
Pb atoms are obviously strong enough to cause a considerable decrease
of the activity of the sodium in the molten mixture.
The activity of the Na is reduced to zero in a metal phase of atomic
fraction 0.15 Na at 770" (equilibrium with NaBr), and in a metal phase
of atomic fraction 0.25 Na a t 690' (equilibrium with NaI). The inter-
metallic forces obviously make themselves more strongly felt a t the lower
temperature than at the higher one. The distribution equilibrium
Na-Cd-NaI leads to similar conclusions.
That van der Waals' attraction or compound formation can pro-
duce such a decrease of the activity of one component of a system is
shown for instance by the vapour pressure curves of the binary

* Cf. definitions of activity and activity coefficient in Lewis and Randall,

Thermodynamics, and Hildebrand, SoZubiZity (1936).
t.The experimental accuracy is not sufficient for decision whether, a t high
atomic fractions of Na, the experimental curve approaches asymptotically the
dotted line corresponding to Raoult's law.
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E. HEYMANN AND H. P. WEBER I497

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found that a d -
dition of Sb to ,2.0 ,

the metal phase 8

caused a shift in Ba
the equilibrium, ./.5
indicating a re- 8
duced activity of .S
the Cd, in con- ./-o$
formity with the w
phase diagram F
Cd-Sb, whi ch d.5:
shows the exist-
ence of a com- ,.*'

other hand, Bi
which forms no
compounds with
Cd or Pb, had no
influence on the
equilibrium. A
number of other
observations on
chemical equili -
bria between
molten m e t a l s
and molten
salts 6~ 7 may be
explained on
similar lines.
The reason for
the difference in
behaviour as sol- FIG. 5. Pb-Na-NaI (690' C.).
vent between Cd
and Pb, however, still remains unexplained. The behaviour of a molten
mixture Na-Cd approaches that of an ideal mixture a t 770" (cf. Fig. 3),
whereas the molten mixture Na-Pb shows at the same temperature
a very strong depression of the activity coefficient of the Na, and yet
the melting-points of the respective solid compounds are not very far
apart (385" and 405"). However, a similarity of the melting-points
4a Cf. Hildebrand, Solubility (1936),p. 39.
R.Lorenz, W. Fraenkel and J . Silberstein, 2. anorg. Chemie, 1923, 131, 247.
' G. Jellinek and J. Czerwinski, 2. p h y s i k . Chemie, 1924, 110, 212.
' R. Lorenz and R. Winzer, 2. anorg. Chemie, 1929,183, 127.
52
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1498 T H E DISTRIBUTION EQUILIBRIUM O F SODIUM

of two solid intermetallic compounds does not necessarily indicate the

degree of decomposition in the molten state a t tHe experimental tem-
perature which is almost 400" higher. Moreover, the molten Na-Cd
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alloys have a distinct bright metallic appearance, while the molten

Na-Pb alloys have lost this to a considerable extent, suggesting a lower
activity coefficient of Na in the latter system.* Finally, the heat of
formation, which according to W. Biltz does not differ considerably
from the free energy in these cases, of the solid compound Cd,Na (2800
cal.) is considerably smaller lo than that of the compound PbNa,
99

(5800 cal.).
I t was to be expected that the activity coefficient of Na would be
still further decreased, i e . , the equilibrium curves still further depressed
below the ideal curve, if as solvents, those metals were used which
form even more stable compounds with Na in the solid state. Bismuth
is such a metal, the melting-point of the compound Na,Bi being 775"
and the heat of formation being 11400 cal. A low activity coefficient
of' Na in molten Na-Bi alloys was first indicated by a much weaker
attack on the glass in systems containing Bi.
An interesting effect was found in these systems. Bismuth, like P b and
Cd, is not soluble in NaBr. However, in the equilibria of molten Na-Bi
alloys with molten NaBr, a considerable quantity of Bi always passed
into the salt phase together with the Na.? Moreover, in this case, the
concentration of Na in the salt phase was considerably higher than in
the systems discussed previously. $ The simplest explanation for this
Isehaviour is that the compound Na,Bi, which is obviously stable in the
molten state a t 770°, is soluble in the salt phase, owing to the fact that
it is more " salt like " in nature than a simple alloy of two molten metals.
If this explanation is correct, then we should expect that metallic
solvents which form stable solid compounds with Na a t or not far below
the experimental temperature (770") and which show a high heat of
formation, will pass into the metal phase together with the Na. On
the other hand, metallic solvents, whose Na compounds possess only a
low heat of formation and whose phase diagrams with Na have maxima
much below the experimental temperature, would not be expected to
show such an effect, because their compounds, which may be stable in
the molten state in the immediate neighbourhood of the melting-point,
will be decomposed a t the experimental temperature. These expectations
were fully borne out by experiment, as Table I shows.
Tin, Bi, Sb and Au, normally inert with respect to molten NaBr,
pass, nevertheless, into the molten salt phase (NaBr) when alloyed
with Na. The high melting-points and the large heats of formation
indicate that these metals form stable compounds with Na. On the
other hand, T1, Cd and Pb, when alloyed with Na, are not soluble in
the metal phase. These alloys show maxima in the phase diagram
many hundred degrees below the experimental temperature and their
* The Na-Pb alloys wet the glass surface better than the Na-Cd alloys.
This, also, suggests that the nature of the former is less metallic than t h a t of the
latter.
* W. Biltz, 2.anovg. Chemie, 1934, 134, 37.
W. Seith and 0. Kubaschewski, 2. Elektrochemie, 1937, 43, 743.
l o W. Biltz and C. Haase, 2. anovg. Chemie, 1923, 129,141.
t The solidified salt phase is black.
2 The concentration of Na and Bi in the salt phase passed through a maximum
at about 60 atom "I, Na in the metal phase. The concentration a t this point is
about 3.6 atom "I, Bi and about 10 atom "I, Na.
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E. HEYMANN AND H. P. WEBER I499

TABLE EXPERIMENTAL TEMPERATURE
( T M ): 770' C.

Maximum ix Heat of
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Behaviour in Distribution Phase Formation9

System. Experiment. Diagram in cal./Mol.
VM.)

T1-Na-NaBr No T1 in salt phase . 305 O +465O -

(NaTI)
Cd-Na-NaBr No Col ,, 385O +385' 2 700
(NaCd2)
Pb-Na-NaBr No P b ,, 405O +365' 5800
(Na,Pb)
367O +405O
(NaPb)
Sn-Na-NaBr 580' +190°
(NaSn)
Bi-Na-NaBr 775" -5" I I 400
(Na,Bi)
Sb-Na-NaBr 856" * -86' >12000)t
(Na,Sb)
Au-Na-NaBr 989' * -219~
(NaAu)

* I n systems in which the maxima of the phase diagrams are a t temperatures

above the experimental temperature, experiments were carried out only a t com-
positions a t which the systems are liquid.
t The heat of formation of Na,Sb is certainly greater than that of Na,Bi.
Difficulties were encountered in preparing the Na-Sb alloys as a consequence of
the large amount of heat evolved.

heats of formation are only small. Obviously the Na compounds of

these metals have been decomposed at the experimental temperature.
These experiments are still in a qualitative state, but there seems to
be no doubt that compounds of Na with other metals are stable in the
molten state a t temperatures not too far above their melting-point,
but may be decomposed at temperatures several hundred degrees above
this temperature (cf. Heymann and Weber) .ll
Evidence for the stability of intermetallic compounds in the molten
state is not abundant. The considerable positive heat effects on mixing
of molten metal pairs,g,l2 like Mg-Pb and Mg-Bi, which are often of the
order of the heat of formation of the solid compounds and sometimes
even larger, suggest that these compounds are stable in the molten state.
The distribution equilibrium method, described in this paper, allows
an estimation of the stability of intermetallic compounds in the molten
state. The solubility of such compounds in molten salts suggests that
they are salt-like " in character. The electrolysis effects on passing
a current through molten binary alloys,13 are noteworthy in this con-
nection; but it is doubtful whether they can be regarded as a proof
of the existence of salt-like compounds in such mixtures, because such
effects are not only found in systems in which, according to the phase
diagram, compounds are formed in the solid state, but also in many
systems which give no indication of any compound formation a t all.
l1 E. Heymann and H. P. Weber, Nature, 1938,141, 1059.
l2 F. Korber, Stahl und Eisen, 1936, 56, 1401 ; cf. also A. Magnus and M.
Mannheimer, 2. Physik. Chemie, 1926,121,267, and F.Weibke, 2. Elehtrochemie,
193% 44, 263.
l 3 R. Kremann and R. G. v. Rehenburg, 2. physik. Chemie, 1924, I 10, 559 ;
R. Kremann and A. Kapaun, 2. anorg. Clzemie, 1924,140,183.
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1500 T H E DISTRIBUTION EQUILIBRIUM O F SODIUM

The solubility of molten intermetallic compounds in molten salts

is remarkable also from another point of view. E. Zintl and his co-
workers l4 found that, of the compounds of Na with other elements,
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those with metals of group IV-VII of the periodic system are soluble
in liquid ammonia and form conducting solutions, i.e., are salt-like in
character (increasingly with increasing group number) whereas the
compounds with elements of group 1-111 are not soluble as a whole in
liquid ammonia, but are decomposed by this solvent, whereby only
the Na goes into solution. The last-mentioned group of compounds is
obviously " metallic " in character. Solubility of the solid compounds
at low temperature in liquid ammonia docs not seem to go always par-
allel with the solubility at high temperatures of the molten compounds
in molten salts. Thus Pb-Na compounds which are soluble in liquid
ammonia are not soluble in molten NaBr. This, however, is due prob-
ably to the high experimental temperature, 400" above the melting-
point, which may cause dissociation of the compounds. Unfortunately,
no sodium halide melts below 650" C., so that the stability of N a P b
compounds just above their melting-point cannot be tested. On the
other hand, whereas solid Na-Au compounds are not soluble in liquid
ammonia, and are regarded by Zintl as typical " alloy phases," yet,
in the molten system Na-Au-NaBr, gold is carried into solution in the
salt phase by the sodium. Thus, the Na-Au compound behaves in
this respect as a " salt-like " compound.
Apart from these discrepancies the similarity of the two groups of
Na compounds (" salt-like " or " polyionic " and " metallic ") with
regard to their solubility in liquid ammonia and in molten salts cannot
be overlooked. Further investigation may clear up the relation between
these two phenomena.
The colour of the solutions of metals in molten salts was in the case
of the bivalent metals attributed either to solvation of the dissolved
atom, whereby the atom is polarised by the surrounding ions of the
molten salt, or perhaps t o the existence of a diamagnetic, bimolecular
subchloride, e.g., Cd,Cl,. In the case of solutions of alkali metals in
their molten salts, the intense colour can only be explained by polarisa-
tion (solvation), since subchloride formation is highly improbable with
univalent metals. No further explanation can a t present be given,
since too little is known about the optical properties of such systems,
and even about the constitution of the molten salts themselves. The
latter are probably completely dissociated (high electric conductivity),
but the activity coefficient may be much smaller than unity as a con-
sequence of the strong interionic forces between ions a t very small
distances (strong apparent " association " according to the Eotvos-
Ram say - S hi eId s r u le).

Summary.
I . A linear relation is found in the distribution equilibrium (at low
concentration) of Na between molten NaBr or NaI as a salt phase and
molten Cd as a metal phase. Thus solutions of Na in molten sodium
halides are atomic in nature.
1 4 E. Zintl, J . Goubcau and W. Dullenkopf, 2.physik. Chemie, A , 1931, 154,
47 : E. Zintl and A . Harder, Z . pliysik. Chemie, A , 1931, 154, 47 ; E.Zintl and
W. Dullcnkopf, 2.physik. Chemie, B , 1932, 16, 183 ; cf. also F. Weibkc, Z . Eiektro-
chemie, 1938, 44, 263.
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E. HEYMANN AND H. P. WEBER 1501

2 . The distribution curves of Na between molten sodium halide and
molten P b as a metal phase reveal the existence of strong interatomic
forces between sodium and lead.
3 . When Sn, Bi, Sb and Au are used as metallic solvents, these metals
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pass into the salt phase together with the Na, while in the absence of Na
they are inert with respect t o the molten salt. These phenomena suggest
t h a t the intermetallic compounds of these metals with Na are stable in
the molten state a t 770° C. and soluble in the molten salt. Lead, Cd and
TI, on the other hand, do not show this phenomenon when used as
metallic solvents. This is obviously due t o the decomposition of the
compounds of the last-mentioned metals with Na at the experimental
temperature, which is 350" t o 400' above their melting-point. These
conclusions are in general accordance with the available thermochemical
data on intermetallic compounds.
4. The solubility of intermetallic compounds in molten salts is dis-
cussed in relation t o their solubility in liquid ammonia.

University of Melbourne,
Chemistry Department.