Piette. metie +.

18

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SEPARATION OF CESIUM AND RUBIDIUM BY THE FERROCYANIDES OF

COPPER, ZINC, AND ZIRCONIUM

DN, Edgington, M.A. Thommes, and L. £. Harrison*
The suitability of several metal ferrocyanides for ion exchange separation of cesium and rubidium has been studied.
Both cesium and rubidium are satisfactorily absorbed on zine
ferrocyanides and could be recovered in separate fractions by
elution with solutions of nitrate jon. Zirconium ferrocvanide
absorbs cesium strongly and is well suited to concentrate ce-

sium when subsequent clution is not required, e.g., to separate
fallout *"Cs from sea water. Copper ferrocyanide absorbs both
cesium and rubidium strongly. but is of little value in analysis
becauseof difficulties in elution of adsorbed species.

Extensive measurements of the concentration of
radioactive *'Cs in the biosphere have been made in
order to understand more fully the behavior of this

fission product in terrestrial and aquatic environ-

ments, as well as in man. While most elements are
discriminated against with incrcasing trophic level,

Gustafson has shown that the ratio of *7Cs to potas-

sium increases in the aquatic environment.” Folsom
has measured the concentration of this radionuclide
and stable cesium in salt water fish@) and sea
water.) Recently, Edgington and Lucas have shown
that there is also an increase in rubidium concentration with increasing trophic level in freshwater fish.“
It would be interesting to know whetherstable cesium
exhibits the same inerease in coneentration with

trophic level as its radioactive isotope.

In order to determine the concentration of cesium
in water and biota, its separation by ion exchange
and solvent extraction has been extensively studied.) On the other hand, very little has been published concerning the separation of rubidium. Because
solvent extraction and anion exchange processes are

not effective for univalent cations, much attention

has been focused on the development of cation exchange materials for their separation. Such an ex-

changer would be useful for concentrating trace
* ANL-CSUI Honor Student. Spring, 1969.

amounts of these elements in the biota for analysi-

measurement of 7Cs from fallout, and the separa
tion of radioactive cesium and rubidium from mix
tures of nuclides produced by neutron activation o
biological or other samples.

For these purposes it is desirable to use a catia:

exchanger which will not only concentrate trac
amounts of eesium and rubidium, but will also al
low them to be eluted as weil with a high percentag
of recovery. The organic ion exchangers, Dowe

50W-X12, sodium form,‘® and Amberlite TR-100,"

have been used, but they require large columns an
are time consuming in operation. Many highly in
soluble inorganic compounds have also been investi
gated. The compoundsof zirconium,‘® the heteropoly
acids,!*") ammonium phosphomolybdate,2%!) an
various cobalticyanides“+.) and ferrocyanides (hex
acyanoterrates) 74 16-19) have been shown to hav:
exchange properties for cesium and rubidium. Th

ferroeyanides have a high specificity in particular fo

cesium, but have to be destroyed using the concen
trated sulfurie acid to get the cestum back into solu
tion. Therefore, the present study is being conducte:
in order to obtain a greater understanding of the io
exchange behavior of the zinc, copper, and zirconiun

ferrocyanides, and to evaluate their usefulness a>
exchangers for ion exchange chromatography of the=:

two elements,

METHODS AND MATERIALS
Analytical grade reagents were used in the following preparations.

Preparation of Heavy Metal Ferrocyanides
Zinc ferrocyanide was prepared as described by
Kourim, Rais and Million,“but on a larger seale

Fight hundred milliliters of 0.1 M potassium ferro-

Select target paragraph3