secondary cells with lithium anodes and immobilized fused_salt

102.
volume and then by pumping to a few microns pressure; this treatment would also
remove F20. The sample was then warmed cautiously to decompose the F2@4 to
F2@2; the O2 released was measured gasometrically. This oreration was carried
out most successfully by removing the liquid nitrogen bath until a small increase
in pressure was observed, replacing the liquid nitrogen, and repeating
the process until the F202 could be melted (113°K) without further oxygen
evolution. The oxygen thus evolved i.as mass spectrometrically free of F2
(hsiever, this was not a very sensitive test because the mass spectrometer
inlet system vas somewhat reactive with small uantities of fluorine). The
blood-red liquid F202 was then frozen at 77°K ?orange solid) and the residual
O2 was pumped away. Subsequent remelting at 113°K resulted in no further re-
' lease of OP. The sample was then warmed slowly to room temperature to decompose
the F202 and measure the F2 + 02.
This procedure was occasionally unsuccessful in cases with the initial
mole ratio F2/02 of 1.0 or 3.0, because a minor explosion ("pop") would be heard
dwing the decomposition of F2O4, accompanied by a sudden rise in pressure.
The gasmetric data indicated that in these cases some of the F202 was decom-
posed during the sudden decomposition of F204. Because of this, the apparent
yields of F& and F202 reported in Table 1 are taken only from experiments in
vhich there vas no audible evidence of explosion. Nevertheless, the reported
yields of F204 may be slightly too high in some cases because of sane decomposi-
tion of F202 during the decomposition of F204.
The data reported in Table 1 show several unusual features. First,
in the mixtures Containing only F2 and 02, the number of millimoles of oxygen
converted to F202 ard F204 remain nearly constant despite a large variation in
the initial ratio of F2 to 02, even when the major part of the oxygen was
consumed. The G-value for products also remained constant at a value that is
several-fol higher than the values that are usually found for non-chain
conditions involves a short chain process that is initiated with approximately
equal efficiency whether the initial absorption of energy is done by oxygen or
by fluorine.
These observations suggest that the formation of F202 under these
,
Another observation is that the ratio of F20 to F202 in the products
displays no obvious trend vith the initial ratio of F2f02. The possible chain
L F. 1 F2 1 F2 1 F2
F2 F202 + F. F204 + F. F2@o + Fa
'muld not lead to these results in a hcmogeneous system, but the kinetics are
probably conplicated by the fact that the products precipitate as solids.
The experiments in which the reactants were diluted with argon show
that the presence of argon ha6 a small positive effect on the total conversion
of oxygen, whereas dilution with citrogen does not appear to effect the yield.
Some energy transfer from argon seems icdicated.
a) G for ion pair formation is'expected to be about 4; for radicals it often
ranges fran 6-10.