On Element 93

DR. IDA NODDACK

Zeitschrift fur Angewandte Chemie,

Volume 47, p. 653 (September, 1934)

This article was translated from German by H. G. Graetzer.

About four months ago an article was published in this journal dealing with
the missing elements in the periodic table.1 At the end of that article the
possibility of discovering transuranic elements (that is, elements beyond
uranium in the periodic table) was discussed. A few weeks later it was
reported, first in the newspapers and then also in technical journals, that two
scientists, Professor Fermi in Rome and Mr. Koblic in Joachimsthal,
independently had discovered the element with atomic number 93.

We wish to consider first the work of Fermi.2 Fermi investigated the

possibility of induced radioactivity by means of neutrons. The so-called
induced radioactivity had been discovered by Curie and Joliot in the
bombardment of atomic nuclei by alpha particles.

Fermi put beryllium powder and radium emanation (i.e., radon gas, element
86) together into a glass container. The radon emits alpha particles, and when
these strike beryllium nuclei, neutrons are released. The neutrons penetrate the
walls of the glass container and can then act on materials placed nearby. Fermi
brought a large number of materials, either in element or compound form,
near to the neutron source for irradiation. The irradiated materials were then
placed in front of a Geiger counter. Many elements were found to emit beta
particles for some time after irradiation, and so verified the induced
radioactivity.3 We will not discuss here Fermi's proposed explanation4 of the
rather complicated observations, since we are interested only in the one
example dealing with the supposed production of element 93. To study
induced radioactivity of uranium, Fermi took a solution of uranium nitrate,
from which all radioactive daughter products had been removed, and brought
it near his neutron source. With a Geiger counter he was able to show that the
solution became radioactive and emitted beta particles after irradiation. The
analysis of the decay curve showed that not only one but at least five different
radioactive half lives were produced. Fermi emphasized that it was still
uncertain whether the different radioactive decays occur in series (one after
the other) or in parallel.
Fermi was able to make a chemical separation of one of the new
radioelements, which had a half life of 13 minutes. He did this by adding
manganese salt and concentrated nitric acid to the uranium nitrate solution,
then heating to the boiling point and adding sodium chlorate. The resulting
manganese dioxide precipitate was found to contain almost all of the beta
activity with the 13 minute half life. Fermi next tried to show that the
radioelement which is responsible for this beta activity was not an isotope of
any known element near uranium. To show this he added known beta emitting
isotopes of the following elements to the acid solution of uranium nitrate:
protactinum (91), thorium (90), actinium (89), radium (88), bismuth (83), and
lead (82). When sodium chlorate is added to precipitate the manganese
dioxide, none of these beta-emitting isotopes are found in the precipitate,
according to Fermi. Since the unidentified new radioelement does precipitate
with manganese, and since it could not be an isotope of radon (86) or
francium (87) either according to its properties, Fermi concludes that it might
be the unknown element 93 (or perhaps 94 or 95).

This method of proof is not valid. Fermi compared his new beta emitter not
only with the immediate neighbor of uranium, namely protactinium, but also
considered several other elements down to lead. This indicates that he thought
a series of consecutive decays was possible (with emission of electrons,
protons, and helium nuclei), which eventually formed the radioelement with
the 13 minute half life. It is not clear why he did not investigate the element
polonium (84) which is also between uranium (92) and lead (82), and why he
chose to stop at lead. The old view that the radioactive elements form a
continuous series which ends at lead or thallium (81) is just what the
previously mentioned experiments of Curie and Joliot had disproved. Fermi
therefore ought to have compared his new radioelement with all known
elements. It is known from analytic chemistry that numerous elements will
precipitate with manganese dioxide if they are present as compounds, atoms,
or colloids in a nitric acid solution.

In order to test how various elements behave with Fermi's precipitation

method, we made up 100 cm3 of a 55% nitric acid solution containing a few
milligrams of nearly all stable elements in dissolved or colloidal form. 200 mg
manganese nitrate was added to this solution, it was heated to boiling, and
then 2 g of potassium chloride (dry) was added slowly. The resulting
manganese dioxide precipitate was then tested chemically and
spectroscopically for the presence of other elements. The precipitate contained
the following elements: Ti, Nb, Ta, W, Ir, Pt, An, and Si with almost the total
quantity of each element which had been in solution; Sb, Ph, Bi, Ni, and Co
with partial amounts.

As previously noted, Fermi also did not investigate if polonium (84) goes into
the manganese precipitate. An experiment was carried out with polonium
which showed that this element does go almost completely into the
MnO2 precipitate.5 Therefore, the proof that the new (13 minute) radioelement
has atomic number 93 is in no sense successful, since Fermi's method of
eliminating other possibilities has not been carried through to completion.

One could assume equally well that when neutrons are used to produce
nuclear disintegrations, some distinctly new nuclear reactions take place
which have not been observed previously with proton or alpha-particle
bombardment of atomic nuclei. In the past one has found that transmutations
of nuclei only take place with the emission of electrons, protons, or helium
nuclei, so that the heavy elements change their mass only a small amount to
produce near neighboring elements. When heavy nuclei are bombarded by
neutrons, it is conceivable that the nucleus breaks up into several large
fragments, which would of course be isotopes of known elements but would
not be neighbors of the irradiated element.

The finding that the new radioelement comes down together with rhenium
sulfide when this is precipitated from an acid solution also does not speak for
element 93. In the first place, rhenium sulfide readily absorbs other materials.
Secondly, the prediction of the probable properties of 93 make it appear not at
all certain that this element forms a sulfide which is stable in acid.

Furthermore, if Fermi's interpretation of his experiments were correct, then an

additional necessary conclusion, which was not given by him, is that the beta
decay of element 93 would produce element 94. It should be relatively easy to
separate this chemically from element 93.

One must await further experiments, before one could claim that element 93
has really been found. Fermi himself is careful in this respect, as has been
mentioned previously, but in one article about his experiments6 and also in the
reports found in the newspapers it is made to appear that the results are
already certain.

The second statement about the discovery of element 93 comes from Odolen
Koblic.7 He reported that he had obtained a substantial quantity of element 93
at Joachimsthal (Czechoslovakia) out of the wash water from roasted
pitchblende ore. (The pitchblende was believed to contain perhaps 1% of this
element.) He described chemical properties of the element and its compounds,
determined its atomic weight, assumed that it was the radioactive parent
substance of protactinum (91), and gave it the name "bohemium" after his
native land. This report also was uncritically accepted and widely distributed
in the newspapers of the whole world.

Through the intervention of Dr. M. Speter, Mr. Koblic sent to me two samples
of his material, with the request to investigate it for the presence of element
93. Both the chemical analysis and X-ray spectra showed that the material did
not contain any 93; it did show instead a mixture of silver, thallium vanadate
and tungstate salts, with excess tungstic acid. After being told of these
findings, Koblic became convinced of the presence of tungsten, and withdrew
his claims to the discovery of element 93.8 It is unnecessary therefore to
discuss here the reactions which Koblic attributed to the supposed new
element, since they can all be explained as reactions from a mixture of
vanadium and tungsten.9

A short time ago (August 11, 1934) news was received from the United States
that Smith and Steinbach in New Jersey succeeded in finding an element with
a higher atomic number than uranium. However there are only some not very
clear newspaper reports available, so that one cannot tell what was done so
far.

REFERENCES
1
I. Noddack, Z. Angewandte Chemie 47, 301 (1934).
2
E. Fermi, Nature 133, 898 (1934).
3
Of course not all the atoms of the irradiated material become radioactive, but only an amount which is
undetectable by weighing, perhaps several hundred atoms in this case.
4
E. Fermi, Nature 133, 757 (1934).
5
1 am indebted to Dr. J. Frnz for preparing the polonium and making the radioactive measurements.
6
Nature 133, 863 (1934).
7
0. Koblic, Chemiker-Ztg. 58, 581 (1934).
8
0. Koblic, Chemiker-Ztg. 58, 683 (1934); sterr. Chemiker-Ztg. 37, 140 (1934).
9
In withdrawing his claim, Mr. Koblic mentioned only the tungsten, not the vanadium, although he was
informed by letter concerning the approximate amounts of both elements in his samples, and the supposed
"bohemium-reactions" were explained due to a mixture containing both vanadium and tungsten.