secondary cells with lithium anodes and immobilized fused_salt

aa .
-
The rrost difficult rctionele is the formation of the AsF6 in the reaction.
Admittedly a multiplicity of diverse reertion seqaences could be proposed
rost of which k'oul? be difficlllt to experimentally verify. 3ne possible
path offerd involves the dissoci?tion of C10 AsF C1 into its cocponents
with :he suSsesuent reactions noted:
2 5
C102AsF5C1 __$ FC102 + AsFdC1 (6)
3AsF4C1- -> AaF?C12 + AsF
5
AsF + PC102 -* C102AsF6
5
.b?,Cl + Cl20 _j AsF,O + 2C1
, 2 2
(9)
'
It is rer.dily seen tnst the suc of eluztiong d through 9, suitably veishted,
.qivez equ?:io? 1.
The ide:itity of ASOF, w.97 t!ot estPSlished as n product since it is ti
non-volatile1° X-rs.v'nmor=hous s3lid. In addition. we did ~ o wish t to
further eo-nlicete nrtters by studying the renction of AsF C1 with Cl 0 QS
a test ox" sTyftion 8 inasmuch as AsF,Cl "Foes ionic" 2nd 1s ?ornulate$ as
+ - . Ve did feel, howeve$, ghat a suitrble test of equation 8
Ad14 AsF F.
woull be 'he re?ction of PF3C12 2nd C1 0. Indeed, the mpid conversion of
PF CI to KF : i r ~ ~1 ila in e;!urtion ?o:
3 7 3 2
: ?F,C12 + Cl20 ?OF + 2C12 (10)
3
stron&:ly suceestn t!wt "covRlent" AF' C1 would react sinilerly. The
3 2
re;:ction conditiohs "e s:ich th?t the reory:!nizstion of AsF C1, postulated
-9 rin interr.ediere in e.:uation 6, would Tive initially the 8ovzlent strwture.
The initinl resort on the prep?r-tions of "C
rerc:ion of NO -9 P proof of the rrlical ?resent
7
ClOAsF + 2LC2 ::C),i.sF + C11i07 (11)
5 L 5
T?,e Ftvistence of "0 As" h?s r.lresdy been ?uestioned Periously and apparently
disarovedt2: 'Fur?her. the formntion of soze ClNO? should be expected
f'r(;c ..i- ~~..,,-. :.--> , c. ..,- i NO in.-s-uc!: 2s thc r?oc:icn of C:07 2nd NO rives
~t
2
i? ~ uite likely thnt the reaction oSaerve3. by Scgmeisser &.
ciiio,
- - * - .
(7)
ia)
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