secondary cells with lithium anodes and immobilized fused_salt

,
86.
Zeections of Cl30 and AsF5. Measured iuantities of C120 (117 cc,
5.22 anoles) and A s F 5 - W , 3.79 mmoles) were seperately condensed
into the reactor (glass or Teflon tubes) at -195O. The temperature wes
changed to -78’ and it wes ojserved that the nixed reactants gradually
developed a dark red color. Pun?ing on the mixture after e few hours at
-78’ resulted in the recovery of sone of the starting materials and much
C12. Subsequent werning of the reaction to arbient temperature gave additiowl
small amounts of enseous materials End a white solid. Little or no
-196O non-condenseble qases were observed throughout the reection. In all,
111 cc of volatile products were obtained. Infrared and p s chromatographic
analysis indicated these products to be a mixture of AsF (17.5 cc, 0.78
5
mole)
and C12 (93.5 cc, 4.17 mmoles) with e trace of C102 and no C1 0. The
observed reactant-product ratio of C1 0:AsF :C1 was 5.00:2.86:4.01. Similar
2 5
reaction ratios were obtained when C1 0 WRS use$ as the excess reagent. The
solid product showed two infrared bcn& 1280 cm” (m, doublet) and 690 to
700 cm-’ (8. broad). Based on the observed stoichi netry of the reaction
and the known infrered frequencies of C1-06 and AaF 7 compounds, it appeared
.
the solid night be principally C102AsF6.
w8s prepared.
\
Accordingly, en authentic sample
PreparRtion of C103AsF . Chloryl fluoride (lil cc, 4.96 molaa) and
AsFg (63.7 cc, 2.04 rnmol*were seperately condensed intc a Teflon ampoule
at -196O. After 1 hour at room tempersture, the unreacted gases were
removed snd meqsured (48.0 cc, 2.14 mnoles). An infrared spectrum showed
only CC102. The white solid product had an infrered spectrum identical to
that of the solid from the C120-AsF reaction. In addition, both solids
fumed in air and exploded on contac? with water. Powder X-ray patterns of
both sclids were obtained and were identical.
relative intensities are given ir. Table 1.
The observed spacings and
Reaction of C10 .AsF5 and NO2. Weiahed amcunts of C102AsF6 and excess
NO? PRS were reactedLfor 1 hour at 0’.
WRS ac.”,ieved but in poor yield; 20;6 for the solid from the C1
2
0 renction
nnd 3516 for the z3lii from the FC102 reaction.
The exr,ected displacement’ of C102
. , ..
-------------_-_---_------------------
(5) V. H. hyen md 3. C. lieale, Advances in Chemistry Series, No. 54,
kerican Cherical Society, Wsshincton, D. C., 1966, p. 223.
(6) E. A. aobinson, Can. J. Chem., fi, 3021 (1963).
(7) B. Peacock end D. Sharp, J. Chem. Soc.,_1766 (1959).
(8) H. Scbeisser and ’d. Fink, Anaew. Chem., a, 780 (1957).