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LETTERS TO THE EDITOR

A note o n t h e h e a t s o f f u s i o n o f C a l c i u m , the nominal melting points. Therefore we con-
Strontium and Barium Nitrate clude that the process of fusion must have a rather
(Received 16 February 1962) different character in the calcium salt and in the
strontium and barium salts. The "extra" entropy
IT IS well known that the nitrates of the divalent of fusion in these latter compounds is about
metals are thermally "unstable": i.e. they undergo 2"4 cal/degree per nitrate ion. This is sufficiently
thermal decomposition under formation of nitric close to R In 3 (2-18 cal/degree) to suggest that
oxides and oxygen when heated to certain tem- the nitrate ions in strontium and barium nitrate
peratures under ordinary pressure conditions. (but not in calcium nitrate) undergo a disordering
Although the stability of these salts differs con- process which is associated with fusion. It seems
siderably from one salt to the other, it generally likely that this disordering process consists in the
is found that decomposition is of significant mag- onset of "rotation" of the nitrate ions around the
nitude even before the melting temperature is trigonal axis. It is suggested that in the process of
reached. Therefore, it is rather difficult to obtain fusion the nitrate ions in the barium and strontium
good data on the heats of fusion of these com- salts gain access to three essentially equivalent
pounds by the usual techniques of drop calori- equilibrium configurations, while these states are
metry and/or cryoscopic measurements. inaccessible in the liquid calcium salt. This inter-
Recently we have obtained reasonably reliable pretation is consistent with recent views regarding
values for the heats of fusion of calcium, stron- the "free rotation" of multiatomic groups in
tium and barium nitrate by extrapolation of heat solids.t3)
of solution data for these solid salts measured at It is significant that we do not find this "extra"
temperatures where they are still thermally entropy of fusion in calcium nitrate. This, first
stable.(1, 2) of all, correlates with the fact that the calcium ion
In this manner we arrived at the following heat is smaller than the strontium and barium ions.
data: Thus, it produces a stronger electric field acting
on the oxygens of the neighboring nitrate groups.
Secondly, it is found that calcium nitrate, alone
Nominal m.p. AHfuston AStuslon among the salts considered here, is an excellent
Salt (°C) (kcal/mole) (cal/degree-
mole) glass-former in some of its (liquid) mixtures with
other nitrates.(4)
Ca(NO3)2 561 5.7 (at 350°) 6"8 Clearly the development of the three-dimen-
Sr(NOa)~ 645 10.65 (at 450°) 11.6 sional network characteristic of a glass structure
Ba(NO3)2 592 9"95 (at 450 °) 11"5
will be possible only if the rotational freedom of
the nitrate ions is severely restricted.
The entropies given in this table are based on the Institute for the Study of Metals
O. J. KLEPPA
rather crude assumption that AC~ for the process and Department of Chemistry,
of fusion is zero, and they should be considered University of Chicago,
as approximate only. In fact, AC~ is believed to Chicago, Illinois
be positive. However, even a quite significant
temperature dependence of the quoted heat data References
cannot materially influence the rather striking
1. KLEPPAO. J. and HERSHL. S., Disc. Faraday Soc.,
difference between the entropy of fusion of in press (1961).
calcium nitrate, on the one hand, and that of 2. KLEPPAO. J., unpublished work.
strontium and barium nitrate on the other. 3. See e.g. Symposium on Plastic Crystals and Rotation
The three salts considered here all have iso- in the Solid State J. Phys. Chem. Solids 18, 1-92
(1961).
morphous fluorite-like structures, and show no 4. BEROMANNA. G., Dokl. Aead. Nauk. S.S.S.R. 38,
evidence of any solid state transformations below 304 (1943).
3G* 819