1985 Book AmericiumAndCuriumChemistryAnd

Americium and Curium Chemistry and Technology
TOPICS IN {-ELEMENT CHEMISTRY
Editor
JERRY L. ATWOOD, University of Alabama, U.S.A.
Editorial Advisory Board
W. J. EVANS, University of California, Irvine, U. S. A.

M. F. LAPPE RT, University of Sussex, Brighton, U. K.
J. D. NAV RATI L, Rockwell International, Golden, Colorado, U.S.A.
A. A. PIN KERTON, University of Toledo, Ohio, U.S.A.
H. SCHUMANN, Technische Universitiit Berlin, Berlin, F. R. G.
Americium and Curium
Chemistry
and Technology
Papers from a Symposium given at the 1984
International Chemical Congress of Pacific Basin Societies,
Honolulu, HI, December 16-21, 1984
Edited by
NORMAN M. EDELSTEIN
Lawrence Berkeley Laboratory, Berkeley, California, U.S.A.
JAMES D. NAVRATIL
Rockwell International, Golden, Colorado, U.S.A.
and
WALLACE W. SCHULZ
Rockwell Hanford, Richland, Washington, U.s.A.
D. Reidel Publishing Company

A MEMBER OF THE KLUWER ACADEMIC PUBLISHERS GROUP
Dordrecht / Boston / Lancaster

library of Congress Cataloging in Publication Data
Main entry under title:

Americium and curium chemistry and technology.
(Topics in f-element chemistry)

Includex index.
1. Americium -Congresses. 2. Curium-Congresses. I. Edelstein,
Norman M., 1936- II. Navratil, James, D., 1941- III. Schulz,
Wallace W. IV. International Chemical Congress of Pacific Basin Societies
(1984: Honolulu, Hawaii) V. Series.
QD181.A5A44 1985 546'.441 85-14238
ISBN-13: 978-94-010-8904-3 e-ISBN-13: 978-94-009-5444-1

DOl: 10.1 007/978-94-009-5444-1
Published by D. Reidel Publishing Company

P.O. Box 17,3300 AA Dordrecht, Holland
Sold and distributed in the U.S.A. and Canada

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All Rights Reserved

© 1985 by D. Reidel Publishing Company, Dordrecht, Holland
Softcover reprint of the hardcover 1st edition 1985
No part of the material protected by this copyright notice may be reproduced or utilized
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without written permission from the copyright owner
TABLE OF CONTENTS
PREFACE vii
PART I
Historical Aspects and General Papers
Glenn T. Seaborg / The 40th Anniversary of the Discovery of

Americium and Curium 3
A. Ghiorso / Reminiscences of an Instrumentalist 19
R.A. Penneman / Americium, Its Early History and Gram-Scale
Separation 25
W. Muller / 20 Years of Americium and Curium Research at
the European Institute for Transuranium Elements 35
O.L. Keller Jr. / Frontiers of Chemistry for Americium and
Curium 43
PART II
Solution Chemistry and Analytical Procedures
B.F. Myasoedov and N.Yu. Kremliakova / Studies of Americium

and Curium Solution Chemistry in the USSR 53
P. Brossard and S. Lafontan / Coulometric Determination of
Americium and Curium for the Preparation of Reference
Solutions 81
M. Hara and S. Suzuki / A Study on the Stability of
Americium(V) and Americium(VI) in Nitrate Media 89
Y. Shiokawa and S. Suzuki / Radiopolarographic Study of
Americium and Curium 105
Ph. Cauchetier and C. Guichard / Americium Titration Methods 115
PART III
Electronic Structure and Thermodynamics
Earl F. Worden, John G. Conway, and Jean Blaise / Electronic

Structure of Neutral and Singly Ionized Curium 123
John W. Ward / Shifted Homologous Relationships Between the
Transplutonium and Early Rare-Earth Metals 135
L.R. Morss / Thermodynamic Systematics of Oxides of Americium,
Curium, and Neighboring Elements 147
F. Weigel and R. Kohl/Preparation and Properties of Some
New Curium Compounds 159
vi TABLE OF CONTENTS
Norman Edelstein / The Electronic and Magnetic Properties of

Am and Cm 193
U. Benedict, J.P. Itie, C. Dufour, S. Dabos, and J.C. Spirlet
/ Delocalisation of 5f Electrons in Americium Metal Under
Pressure: Recent Results and Comparison with Other
Actinides 213
Robert J. Silva / Preparation, Characterization and Solubility
Product Constant of AmOHC0 3 225
PART IV
Nuclear Studies, Environmental Studies, Separations,
and Other Technological Aspects
Darleane C. Hoffman / Heavy Ion Reactions on Curium Targets 241

N. Shinohara, S. Ichikawa, S. Usuda, T. Suzuki, H. Okashita,
T. Sekine, K. Hata, T. Horiguchi, Y. Yoshizawa,
S. Shibata, and I. Fujiwara / Synthesis of Transuranium
Nuclides from Interaction of 160 with 238U 251
I. Satoh, T. Mitsugashira, M. Hara, M. Kishimoto, and
S. Suzuki / A Study of the Production of Transuranium
Elements and Its Application to the Solution Chemistry
in Tohoku University 261
Masayoshi Yamamoto, Kazuhisa Komura, and Masanobu Sakanoue /
Geochemical Studies on Americium and Plutonium in Soil 275
James D. Navratil/Production and Recovery of Americium-24l 293
G. Koehly, J. Bourges, C. Madic, T.H. Nguyen, and M. Lecomte /
Production of Americium Isotopes in France 301
J.G. Reavis, S.A. Apgar III, and L.J. Mullins / Americium
Metal Preparation on the Multigram Scale 321
INDEX 331
PREFACE
The papers included in this volume were presented at the symposium on

"Americium and Curium Chemistry and Technology" at the International
Chemical Congress of Pacific Basin Societies in Honolulu, Hawaii,
December 16-21, 1984. This symposium commemorated forty years of research
on americium and curium. Accordingly, the papers included in this volume
begin with historical perspectives on the discovery of americium and
curium and the early characterization of their chemical properties, and
then cover a wide range of subjects, such as thermodynamic properties,
electronic structure, nuclear reactions, analytic chemistry, high
pressure phase transitions, and technological aspects. Thus, this volume
is a review of the chemistry of americium and curium, and provides a
perspective on the current research on these elements forty years after
their discovery.
The editors would like to thank the participants in this symposium
for their contributions. It is a pleasure to acknowledge the assistance
of Ms. Barbara Moriguchi in handling the administrative aspects of the
symposium and of the production of this volume.
April 2, 1985
Norman M. Edelstein
Materials and Molecular Research Division
Lawrence Berkeley Laboratory
University of California
Berkeley, California 94720, U.S.A.
James D. Navratil
Rockwell International
Rocky Flats Plant
P.O. Box 464
Golden, Colorado 80402-0464, U.S.A.
Wallace W. Schulz
Rockwell Hanford
P.O. Box 800
Richland, Washington 99352, U.S.A.
vii
Part I
Historical Aspects and General Papers

THE 40TH ANNIVERSARY OF THE DISCOVERY OF AMERICIUM AND CURIUM
Dr. Glenn T. Seaborg

Berkeley, California 94720
ABSTRACT: The recogn1t10n, in July 1944, that the unknown elements

with atomic numbers 95 and 96 should be members of an actinide
transition series was the key to their chemical identification
following nuclear synthesis, i.e., the breakthrough that led to their
discovery. That same month 239pu was bombarded with 32 MeV helium
ions in the Berkeley 60-Inch Cyclotron and sent to the wartime
Metallurgical Laboratory in Chicago where chemical separations led to
the identification of 242 96, produced in the reaction 239pu (a,n)
242 96. Neutron bombardments of 239pu in the reactors at Clinton
Laboratories, Tennessee, and the Hanford Engineer Works, Washington,
followed by chemical separations in Chicago, led to the
identification, completed in Januar~3~945, of 2~td5 and 242 96
(again), produced by the reactions Pu (n,y) Pu (n,y)
--+
s-
--->-
The names
americium (95) and curium (96) were suggested at an ACS annual Spring
Meeting in April, 1946.
The discovery of two very interesting synthetic elements--the

transuranium elements with the atomic numbers 95 and 96--took place 40
years ago. The discovery experiments for these elements, which were
given the names americium and curium, were performed at the University
of Chicago in the wartime Metallurgical Laboratory in the so-called New
Chemistry Building.
The discovery experiments took place during 1944 and early 1945.
In the course of my remarks, I shall attempt to trace for you a
somewhat detailed account, including the dates when the critical
observations were made. The preparation of this talk was a moving
experience, bringing back as it did the many emotional reactions,
including heartaches and triumphs, of that time. The understanding and
interpretation of the results took place over a longer period of time
and had more of the ingredients of a detective story than was the case
for the other elements in whose discovery I had the privilege to
participate.
N. M. Edelstein et al. (eds.), Americium and Curium Chemistry and Technology, 3-17.
© 1985 by D. Reidel Publishing Company.
4 G.T.SEABORG
A number of factors contributed to the special status that this

research holds in my memory. The experimental tools available at that
time were crude in relation to the deductions that had to be made. And
a real breakthrough in thinking had to be made in order to devise the
chemical procedures that became necessary in order to identify the new
elements. I believe that I derived more personal satisfaction from
these experiments than from those concerned with the discovery of the
other transuranium elements.
New Chemistry, the building where this work was done, stood on the
east side of Ingleside Avenue extending south from 56th Street. It was
hastily constructed during the fall of 1942, when it became apparent
that the quarters on the fourth (top) floor of George Herbert Jones
Laboratory were becoming grossly inadequate for our group of chemists,
working as part of the Metallurgical Laboratory. I was responsible for
the chemists working on the chemical processes to be used in the
extraction of plutonium from neutron-irradiated uranium and on the
basic chemistry and purification of plutonium. I, of course, was
devoting my full time and energy to this task.
By December of 1943, however, so much progress had been made on
these problems that I felt that I could devote part of my efforts to
the synthesis and identification of the transplutonium elements with
the atomic numbers 95 and 96. I asked Ralph James, a young chemist
from Berkeley who had been especially proficient in the investigations
of the radiochemistry of plutonium, to devote himself to this problem.
We began by attempting to produce isotopes of element 95 through
bombardment of 239pu with deuterons. The target material 239pu was
then just becoming available in milligram amounts as a result of its
production in the uranium-graphite reactor at the Clinton Laboratories
in Tennessee.
Albert Ghiorso was the Group Leader of our Instruments and Physical
Measurements Group and during this period he began to give more and
more of his time to this problem. As the work progressed, he devised
instrumentation and techniques of increasing complexity as required.
Other members of his group, particularly Arthur H. Jaffey, also gave us
very valuable help.
Ralph and I went to St. Louis at the end of January, 1944, and with
the help of Harry Fullbright, we bombarded 0.1 mg and 1 mg samples of
239pu with the deuterons furnished by the cyclotron at Washington
University. Measurements were made on the bombarded 239pu,
immediately at St. Louis and later in Chicago, without any attempt to
chemically separate the products. Alpha particle range measurements
were made in order to try to detect the presence of alpha particle
emitters with higher or lower energy than that of 239pu. These crude
experiments, and later crude experiments performed by Ralph and Al also
utilizing the deuterons from the St. Louis cyclotron, gave negative
results.
The 1 mg of irradiated 239pu and two other larger samples of
239pu that were bombarded with deuterons, one in the cyclotron at
Washington University and the other in the 60-inch cyclotron in the
Radiation Laboratory of the University of California, Berkeley, during
the following months, were subjected to a number of chemical
THE 40TH ANNIVERSARY OF THE DISCOVERY OF AMERICIUM AND CURIUM 5
procedures. Chemical fractions were isolated, and their radiations

examined, on the basis of several hypotheses concerning the chemical
properties of element 95. These included various assumptions
concerning the solubility properties of the compounds of element 95 and
the potential for its oxidation from a lower state, in which its
fluoride is insoluble, to an upper one in which its fluoride is
soluble, and included the assumption that it could not be so oxidized
at all. (The elements immediately preceding element 95--uranium,
neptunium, and plutonium--each has a III and a IV oxidation state that
have insoluble fluorides and a VI state that has a soluble fluoride.
Increasingly strong oxidizing agents--as we go from uranium to
neptunium to plutonium--are required to attain the VI state.) Unique
alpha particles, with energies different than those of 239pu, were
sought and in no case were they found. In retrospect, this is not
surprising because we now know that the is topes that would have been
produced, such as 240 95 and· 239 95, decay overwhelmingly by electron
capture and to such a small extent by alpha particle emission that this
could not have been detected with the available techniques. These
techniques did not permit detection of electron capture decay in the
presence of the tremendous amount of rare earth fission product (beta
and gamma) activity.
Also beginning in January, 1944, in parallel experiments, we used
the reactor at the Clinton Laboratories in Tennessee to irradiate
samples of 239pu with neutrons. Although it was thought at that time
to be unlikely, we wanted to look for the production of 240pu. If
such an n,Y reaction could occur to an appreciable extent in
competition with fission, then successive n,Y reactions might occur
leading to a beta-particle-emitting plutonium isotope and hence to an
element 95 daughter. Again, in retrospect, we now know that the near
identity of the alpha particle decay properties of 240pu and 239pu
made impossible the detection of the small concentration of 240pu
present in those neutron irradiated samples.
An important factor in the measurement of the radiation from the
isotopes of elements 95 and 96 that were being sought was the
determination of the energy of the alpha particles by absorption or
range measurements. The early absorption measurements that I shall
report here were performed by Ghiorso with thin mica absorbers and were
translated into equivalent range in terms of centimeters of air at
standard conditions.
During the spring of 1944, our search also had some of the human
elements dramatized by James D. Watson in his book, The Double Helix.
Visitors from Berkeley brought the news that John W. Gofman and his
group had good evidence for the identification of element 95 among the
products of the neutron irradiation of 239pu. I had good reason to
feel that Jack Gofman might actually have beaten us to the discovery of
element 95. I knew him as my brilliant graduate student whose thesis
problem was the discovery and proof of the fissionability of 233U, a
discovery that opened the use of the world's supply of thorium as a
nuclear fuel. On a trip to Berkeley at the end of March, I learned the
details of Jack's work. He and his co-workers had identified a 40-60
day beta-particle-emitter that had chemical properties similar to the
6 G. T. SEABORG
rare earth elements (which was reasonable for element 95) and which was
at least partially chemically separable from the rare earths. Two
weeks later, after I had returned to Chicago, I received a copy of
Gofman's first written description of his work. It immediately
occurred to me that his activity was actually the fission product,
57-day 91y, and when I communicated this thought to him, Gofman
accepted this interpretation immediately. Also, at this period of
time, Joe Kennedy, during his visits to Chicago, hinted, or at least
seemed to me to hint, that he, Art Wahl, and co-workers at Los Alamos
had uncovered evidence for transp1utonium elements. Again, knowing the
extraordinary competence of my co-workers in the discovery of
plutonium, I had more than adequate reason to believe that this might
have occurred, but nothing happened to confirm this possibility.
Following these experiments performed in the first half of 1944,
which gave negative results but provided much valuable experience, the
first breakthrough came in July. The first bombardment of 239pu with
helium ions (32 MeV) took place in the Berkeley 60-inch cyclotron on
July 8 to 10. By this time, the actinide concept had crystallized in
my mind to the extent that we decided to proceed solely on the
assumption that elements 95 and 96 could not be oxidized in aqueous
acidic solution to soluble fluoride states (i.e., they should exhibit
only the III or IV oxidation states that have insoluble fluorides).
The sample was sent to Chicago by air and the chemical procedures
started on July 12. A 2.2 mg portion of the target 239pu was
oxidized in aqueous solution to the plutonium (VI) oxidation state
(whose fluoride is soluble) and lanthanum fluoride was precipitated.
This precipitate, presumably containing the insoluble fluoride of an
element 95 or 96 isotope and a small fraction of the plutonium (nearly
all of which remained in solution in its soluble oxidized form), was
then dissolved. Most of the small amount of remaining plutonium was
oxidized and lanthanum fluoride was again precipitated to carry the
element 95 or 96. The cycle was then repeated a third time. This
final sample (labeled 49aA - #9) contained only about 0.004% of the
original 2.2 mg of 239pu, that is, about 0.09 microgram or about
12,000 alpha particle disintegrations per minute.
On July 14, 15 and 16, careful absorption measurements in mica
sheets were made on this sample. A plot of these data revealed
distinctly the presence of alpha particles of longer range than those
of 239pu. The original graph, a photographic reproduction taken from
our notebook, is shown in Figure 1.
This uses the wartime code designation "49" for the target isotope
239pu. The significance of this observation is perhaps best
summarized by quoting here the entry we made 1n our notebook (No. 221B)
on July 14, 1944:
"Plotting and comparing this data shows that a 94 239 sample
20% larger than 49aA - #9 falls to zero clm much faster than does
49aA - #9 itself. This definitely shows the presence of a
long-range alpha emitting isotope in sample 49aA - #9. This 1S
undoubtedly due to a product of the nuclear reaction of a's on
94 239 and is probably one of the following: 95 242 (by a,p
reaction) or 96 242 (by an a,n reaction) or 96 241 (by a,2n
.- .
, ... ,
..!"I i:'. ' ~:
- 0 •
"
....
-\ --
r .~
--r= -
+H
1 ....
T -,-
,
,
--'- ;-
.+ K--
,
+~+- -L -
.
J-+-
!-
, I I
T -,- i -+ -L r+
."" T
1+ ; - L -1- '1' i--r -t--
-+
-! "'T - !-- - -1- 1-;- -+-- '! i- T H- ~
1\ I r- ~
) !
'" I t-
_. h-H-
...L-_
i-
I. '- t
t~- It
.~
~-\ ; '1 -L j
.j - ,....- -- .-
-.
f-'
...
I
-\ '1' - I: -
\1
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t -\- , .J- .. -+ !
-l- -f ~ rr] !!.A, ~
~ --1-
...
~- -
~ "-;- f- -+- +- - ~
T T H-
-j ~ - r ~
I-+- IT -+- ~ l
~
+.- I\+--- ~
.
,
0-
l-
t
~
t t I
. !- 1+ H
'\ 1
I
fa, , ~ ,
~
-t -
c
-
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...
I
. '\ , - +- H- -1 j+ -+ - r
H\ t-I -
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'It
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Figure 1. Original mica absorption d239 showing presence of 242 96

alpha particles in heli~m-irradiated Pu. Ordinate--counts per
minute, Abscissa--Mg/Cm of mica. July 15-16, 1944
8 G. T. SEABORG
reaction). Other isotopes are possible, but these seem the most
likely. The isotope 95 241 from a;n,p is fairly probable.
It is difficult to estimate the range of the a-particles from
this new isotope very accurately, but it would seem to be about
4.65 ± 0.15 cm of air."
Incidentally, the range of 4.65 cm corresponds very well with the
6.1 MeV energy of the alpha particles from 242 96 as known today.
The sample 49aA - #9, a mixture of a few hundred disintegrations
per minute of the new long-range alpha activity and 12,000
disintegrations per minute of 239pu alpha activity, was then
subjected to several additional oxidation cycles to further remove the
239pu. These were successful and by August 10, 1944, the sample was
essentially free of 239pu. The sample was used to study the tracer
chemical properties of the new isotope. Following is a verbatim
extract from the Metallurgical Laboratory progress report (CS-2l35)
covering the period of August, 1944:
"About 10 mg of Pu 239 were bombarded to the extent of 40
Vahr with 32 MeV helium ions in the Berkeley sixty-inch cyclotron.
There was found in this material a new radioactivity, emitting
alpha-particles of range about 4.7 cm, which seems to be due to an
isotope of element 96 or 95. This new radioactivity is carried
quantitatively by lanthanum fluoride, even in the presence of
oxidizing agents such as dichromate or silver persulfate,
indicating that this isotope cannot be oxidized to a +6 oxidation
state in aqueous solution. The activity is carried by lanthanum
oxalate in the presence of excess alkaline oxalate and not carried
from acid solution by zirconium phenylarsonate, lead sulfate, or
bismuth phosphate."
Let me interrupt the narrative momentarily to note that as I was
studying the notebooks which recorded all of these technical events, I
came across the following entry, dated June 15, 1944, in Ralph James'
notebook: "Time out to get married~" Apparently, even discovering new
elements wasn't allowed to interfere with romance, although Ralph was
back at work on June 19.
In the following months, it became increasingly apparent that this
activity must be due to 242 96. The definitive evidence for this
isotope assignment came later through the observation of this same
alpha activity as a product of the neutron bombardment of 239pu.
As the volume of the work and the complexity of the problem
increased, we felt the need for more help. Early in September I asked
Tom Morgan, a young chemist who had come to us from the University of
Texas and who, like James, had distinguished himself in the
investigations of the radiochemistry of plutonium, to join James,
Ghiorso, and me in our search. He immediately joined Ralph in
performing the chemical separations on a large (200 mg) sample of
plutonium which in August had received a very intensive deuteron
bombardment in the St. Louis cyclotron. (Plutonium was now available
in such quantities as the result of its production in the Clinton
reactor.) The chemical procedure consisted of isolating a fraction
presumed to contain element 95 by separating it from plutonium through
repeated oxidation of plutonium to its soluble fluoride form and
carrying the non-oxidizable element 95 as its insoluble fluoride on

lanthanum fluoride.
There were some indications of an alpha particle of range longer
than that of 239pu in this element 95 fraction. On the basis of
Ghiorso's absorption measurements, this alpha particle seemed to have a
range of about 4.0 cm in air (compared to 3.7 cm for 239pu)
corresponding to an energy of 5.5 MeV. Tracer experiments were carried
out during September and October using a total of about one hundred
disintegrations per minute of this 4.0 cm alpha emitter. These showed
that it could be chemically separated from all the natural radioactive
elements (lead and above) except actinum, thorium and possibly
protactLnLum. The range of the alpha particles seemed to be
inconsistent with their being due to isotopes of any of these elements.
In retrospect, it seems we were catching a glimpse of 241 95
(whose alpha particles have a range of 4.0 cm) produced by a d,n
reaction on the tiny amount of 240pu (approximately 10- 2%) present
in the plutonium. The observed intensity of 4.0 cm alpha particles
(about 100 disintegrations per minute) was consistent with the now
known yield for this reaction. Another source can now also account for
the observed 4.0 cm alpha particles, suggesting that both sources made
appreciable contributions to the observed intensity. Originally
present in the plutonium (before the deuteron bombardment) was a very,
very small concentration of 24lpu (approximately 10- 5%). As we now
know, the 24lpu is long-lived and thus its beta particle decay would
continually produce the daughter isotope 241 95 before, during, and
after the deuteron bombardment. The amount of 24lpu and time of its
decay are consistent with the observed intensity of 4.0 cm alpha
particles.
As shown in Figure 2, which is a photographic reproduction of the
original plot in our notebook, the presence of an alpha particle
emitter other than 239pu could be clearly distinguished by alpha
particle absorption experiments with mica absorbers. In the graph, the
mica absorption range for the new isotope was again converted to its
equivalent air thickness--4.05 cm. Quoting from our notebook (No.
727B) entry for October 17, 1944, the following statement is made:
"Among the heavy isotopes (Z=80-94) Ac, Th, and Pa might
follow the observed chemistry. This activity would have to be a
new isotope of these elements, however, since none of the known
ones would have this range, or behave in this way (growth, decay).
Element 95 would also be expected to have this chem[istry]."
However, this activity had somewhat of a "will 0' the wisp"
character, and the tiny supply was finally frittered away in the course
of the chemical manipulations.
It was the neutron irradiation of 239pu to a relatively large
total exposure, first at Clinton Laboratories and then at the Hanford
Engineer Works in the state of Washington, that led to the definite
observation of an isotope of element 95 and the definite identification
of the above described product of the helium ion bombardment of 239pu
as an isotope of element 96.
Two samples of 239pu, one of 4.4 mg and the other 8.2 mg, were
placed in the reactor at Clinton Laboratories on June 5, 1944. The
o
-
en&- /1.1
" ~ /) L.J /I'- :1.1
<- nrr ~ II
.k / -. , LJ bf-l3.?-
1-
1-9 tJO q.&Z
"
" \
~..;. . . t· ·"-o.l..... . . ,1.
.. )C ,
\
tjI.{; p -It!J I ... ..... .....
~ ~.,1 . . f iI
'-.
,0,:,
'l. \
......
I :J
"I(~
l I
3 )' ~t~
•• m.M'd '" _I
c;1
Figure 2. Original mica absorption data showing presence of 241 95 alpha ;l
CIl
particles in deuteron-irradiated plutonium. Ordinate--counts per minute, tTl
abscissa--Mg/Cm 2 of mica. October 17-18, 1944. »
t:C
o
;.:l
C'l
first of these was removed on November 10 and returned to Chicago on

November 19. This sample was put through the same type of chemical
procedure described above, in which the plutonium was oxidized to the
VI oxidation state whose fluoride is soluble, and insoluble lanthanum
fluoride was precipitated with the intention of carrying any
non-oxidizable isotopes of element 95 and 96 that might be present.
After several such cycles had been completed, alpha particle absorption
measurements were made on the fraction containing any non-oxidizable
components to determine the ranges of the emitted alpha particles. A
plot of these data on December 6, 1944, showed that, in addition to the
alpha particles from the 239pu remaining in the sample, a component
with alpha particles of longer range than those of 239pu was present
at an intensity of a couple hundred disintegrations per minute.
This was very exciting. Here again, as in the case of the
long-range alpha particles that had been observed the previous July in
the non-oxidizable fraction isolated from 239pu bombarded with helium
ions, and during September and October in plutonium bombarded with
deutrons, was evidence that radiation from an isotope (or isotopes) of
element 95 or 96 had been observed. This was confirmed during the
following week when additional chemical cycles of the same type
continued to remove 239pu while the intensity of the long-range alpha
particles remained constant.
By the end of December, continuing very careful absorption
measurements on the long-range alpha particles indicated the possible
presence of two components.
The 8.2 mg 239pu sample was removed from the Clinton reactor on
December 3 and returned to Chicago. This was also subjected to the now
well developed oxidation and lanthanum fluoride precipitation procedure
to remove the 239pu and concentrate the long-range alpha particle
emitter (or emitters). Again, long-range alpha particles were found
and in greater quantity, as would be expected on the basis of the
longer neutron irradiation.
Now we were sure that we had observed transplutonium isotopes, but
there remained the task of putting together all of the pieces of the
puzzle. These began to fit together at about the turn of the year,
early in January, 1945. It was becoming increasingly clear that the
long-range alpha particles from the neutron-bombarded 239pu consisted
of two components. But it was exceedingly difficult to define the two
ranges with any accuracy.
Gradually, we were able to conclude that the ranges of these two
alpha particles in air were about 4.0 cm and 4.7 cm (compared to 3.7 cm
for 239pu). It became clear to us, and to our delight, that the 4.7
cm alpha particle was the same as that found as a product of helium ion
bombardment of 239pu. Thus it appeared that the 4.0 cm alpha
particle emitter was 241 95 and the 4.7 cm alpha particle emitter was
242 96, produced in neutron-irradiated 239pu by the following
reactions:
12 G. T. SEA BORG
239 240 pu 241

Pu (n,y) (n,y) Pu
24lpu (3- 241 95
---+
241 95 (n,y) 24295
242 95 (3- 242 96

--4-
The same isotope 242 96 had been produced 1n helium-ion-bombarded

239pu by the reaction:
Aiding us in coming to this conclusion was the information we

obtained by use of a 25 mg sample of 239pu which had received a
relatively short neutron irradiation in November in the much higher
neutron flux of one of the large plutonium production reactors at the
Hanford Engineer Works in the state of Washington. This sample, which
was received on January 25, 1945, was subjected to our by now standard
chemical separation procedure. The element 95 and 96 fraction showed
the same two component long-range alpha particles as had been observed
in the 239pu samples irradiated in the Clinton reactor. Consistent
with the higher neutron flux, the yields were much larger than had been
obtained in the Clinton irradiations. In fact, it was an enormous
quantity by our standards, of the order of fifty thousand alpha
disintegrations per minute. However, there were some aspects of the
yield of these alpha emitters that puzzled us at first. Because
242 96 is produced in a higher order neutron absorption sequence than
is the case for 241 95, it was expected that the ratio of the yield of
242 96 to that of 241 95 would be substantially higher in the high
flux Hanford irradiation than in the lower flux Clinton irradiation.
(The total integrated exposure was much greater at Hanford than at
Clinton.) Actually this ratio was nearly the same in Hanford and
Clinton irradiations. However, we soon understood the reason for
this. The short duration of the Hanford irradiation and the relatively
long interval from the end of this irradiation until we received the
irradiated plutonium favored the relative buildup of 241 95 whereas
the long duration of the Clinton irradiation allowed the 241 95 to
have a relatively longer exposure to neutrons which favored the
production of 242 96.
These conclusions were presented at a meeting of the Basic
Chemistry, Recovery, and Instrument groups of my Chemical Section at
the Metallurgical Laboratory on January 31, 1945. Figure 3 is a
photographic reproduction of a graph which was shown at that meeting
and which was printed in the minutes of the meeting (MUC-GTS-1346, Feb.
2, 1945). The graph summarizes the alpha particle absorption
measurements made on samples chemically separated from the neutron
bombardments of plutonium. This represents a clear recognition of the
formation of the two isotopes 241 95 and 242 96, with ranges in air
for the alpha particle, of 4.0 and 4.7 - 4.8 cm., respectively.
Activity
--- - - -- --
~ 2. 3 4 5'"
Absorber thickness converted
to cm of air.
I. Range Curve for 241 95 and 242 96
239
II. Comparison Range Curve for Pu
Figure 3. Summary alpha particle absorption curves presented at

Metallurgical Laboratory meeting, Chicago, January 31, 1945.
A good summary of our understanding at that time can also be seen

in the following verbatum quotation from the Metallurgical Laboratory
progress report (CS-2741) covering the period of February, 1945:
"Some very interesting new alpha-radioactivity has been found,
both in plutonium irradiated with neutrons in the Clinton pile and
plutonium irradiated with neutrons in the Hanford pile. This
alpha-activity exhibits just the sort of chemical behavior which
has been predicted for the transplutonium elements. For example,
it is carried by rare earth fluorides and it has not yet been
possible to oxidize it to a state or states where its fluoride is
soluble. It seems to be chemically separable from all the rest of
the 94 elements, and the best present interpretation is that it is
due to elements 95 and/or 96. The alpha-activity is composed of
two components, one of range 4.0 cm and the other of range 4.7 cm.
A very attractive Eossibility is that the 4.0 cm alpha-tctivity
corresponds to 95 2 1 formed from the beta-decay of 94 24 which
comes from the reaction 94 240 (n 4~ 94 241 , and the 4.7 cm
alpha-activity corresponds to 9&~ (cf. reports CS-2124 an~41
CS-2135) from beta-decaying 95 2 following the reaction 95
14 G. T. SEABORG
(n,y) 95 242 • The ratio of the yields in the Hanford as compared

to the Clinton bombardment seems to be proportional to the second
power of the total neutron irradiation, as would be expected on the
basis of these particular isotopic assignments, although the
accuracy of the estimation of the neutron fluxes is not sufficient
to make this at all certain."
Soon after our results had been communicated to scientists at Los
Alamos, they made a mass spectrographic identification in purified
plutonium of a relatively volatile isotope with the mass number 241,
which they identified with our 241 95. Since this could be extracted
by volatilization from pure plutonium (from which element 95 which was
originally present had been removed in the purification process), we
knew that the parent isotope, 241pu, must have a relatively long
half-life (of the order of months or longer). Our own work had not
given us any information concerning the half-life of 241pu. In order
to test for the presence of 241pu, we subjected 250 mg of purified
plutonium, which had been produced in a Hanford reactor, to our
chemical procedure for the isolation of element 95. By March 20, we
had a purified fraction containing the extracted 241 95. The
intensity of the 4.0 cm alpha particles corresponded to about 30,000
disintegrations per minute. This established beyond doubt the identity
of our 4.0 cm alpha particle emitter. Also, we now had a large sample
with which to study the chemical properties of element 95 and, beyond
that, we knew that we had an inexhaustible supply in our large stock of
plutonium. Subsequent "milkings" led to continued extractions of the
4.0 cm alpha emitter from plutonium samples and we were able to
establish the half-life of 241pu (now known to be 14 years).
Also, in March, we had another bombardment of 239pu with helium
ions in the Berkeley 60-inch cyclotron. Again, we chemically separated
an element 96 fraction using our well-established procedures. Imagine,
then, our surprise and consternation when the alpha particles emitted
in this fraction had a range of 5.0 cm rather than the 4.7 cm of the
expected 242 96. However, we were able soon to solve this additional
puzzle. It happened that the Berkeley cyclotron had been modified
since our July, 1944, bombardment so that it now delivered 40 MeV
helium ions rather than the previous 32 MeV energy. This meant that
isotopes such as 241 96 and 24096 would now be produced in
predominating yields, due to a,2n and a,3n reactions, in addition to
the previously produced 242 96. It was possible later to assign the
5.0 cm alpha emitter to the new isotope 24096 and to detect the lower
intensity alpha particles due to the 242 96.
A few months later, in July, 1945, the isotope 238pu was
identified as the alpha particle decay product of 242 96, thus lending
further confirmation to this isotopic assignment. Decay measurements
showed that 242 96 had a half-life of about five months (and 24096 a
half-life of about one month) while 241 95 exhibited no measurable
decay (now known to have a half-life of 432 years). As soon as a
sufficient quantity of separated 241 95 was available as a decay
product of 241pu, it was irradiated with reactor neutrons to confirm
the production of 242 96 by the reactions 241 95 (n,Y)
_s- ) 242 96 • Soon thereafter W. M. Manning and L. B.
Asprey measured the half-life of 242 95 as about 16 hours.

Of special interest is the fact that we were able to produce and
definitely identify the isotope 241 95 also by charged particle
bombardments. Using helium ions from the Berkeley cyclotron to
bombard uranium, we were able to identify 24lpu and its beta-decay
daughter 241 95 produced by the reactions 238U (a,n)
The significance of this lies in the fact
that we were able to obtain declassification (permission to publish)

of this method of production much before the original method for the
production of 241 95 (via the neutron irradiation of 239pu) could
be declassified. Therefore, my first announcement at a scientific
meeting of the discovery of elements 95 and 96, in a paper presented
at an American Chemical Society symposium at Northwestern University
on Friday, November 16, 1945 (published in Chemical and Engineering
News, Vol. 23, page 2190, Dec. 10, 1945), described the production of
element 95 by helium ions rather than by neutron bombardment.
As it actually turned out, the discovery of elements 95 and 96 was
announced to the world for the first time prior to the symposium.
This occurred on the Quiz Kids national radio program on Sunday,
November 11, Armistice Day of 1945. I happened to be serving as a
guest on this radio program and one of the kids (Richard Williams)
asked me if any new chemical elements had been discovered at the
Metallurgical Laboratory during the war. As the information had
already been declassified for the symposium to be held the following
Friday, I replied in the affirmative to his question. Following is a
verbatim transcription of this question and answer:
"Richard: Oh, another thing--have there been any other new
elements discovered like plutonium and neptunium?
Seaborg: Oh yes, Dick. Recently there have been two new
elements discovered--elements with atomic numbers 95 and 96 out at
the Metallurgical Laboratory here in Chicago. So now you'll have
to tell your teachers to change the 92 elements in your schoolbook
to 96 elements."
Soon after this, on December 15, 1945, I made a guest appearance
on the Watson Davis program, "Adventures in Science," which was a
national network (~BS) radio program at that time. Following is a
verbatim transcript of a portion of that radio program:
"Announcer: By the way, I'd like to know whether you have
named these two new elements that you have discovered?
Seaborg: Well, naming one of the fundamental substances of
the universe is, of course, something that should be done only
after careful thought. We have been faced with considerable
difficulty in these cases because we have run out of planets.
Naming neptunium after the planet Neptune, and plutonium after the
planet Pluto, was rather logical. But so far the astronomers
16 G. T. SEABORG
haven't disclosed any planets beyond Pluto. So we'll have to go

to some other method of naming.
Announcer: What's that, Dr. Seaborg?
Seaborg: This hasn't been decided yet. One possibility
might be to rely on some property of these elements. We do have
an idea for the naming of element 95 along these lines and may
have a suggestion to offer pretty soon. And, by the way, you may
be interested to know that we have received lots of suggestions.
Some good and some not so good.
Announcer: Well, Dr. Seaborg, perhaps some of the listeners
to "Adventures in Science" will want to make suggestions as to the
naming of the new elements. Will you be willing to have them
write in their suggestions?
Seaborg: Well, I don't promise to follow the suggestions.
But it might be interesting to know what the public thinks about
naming new chemical elements.
Announcer: Very well, Dr. Seaborg. If you want to suggest
names for new elements 95 and 96, just drop a postcard to Watson
Davis, Science Service, Washington 6, D.C. And to all those who
write in, Mr. Davis will send them a free copy of the current
issue of Chemistry Magazine which contains Dr. Seaborg's full
technical paper and a new arrangement of the chemical Periodic
Table. It's free for the asking. So be sure to ask for the
elements 95 and 96 article and address Watson Davis, Science
Service, Washington 6, D.C."
Actually, we gave a great deal of thought to the naming of
elements 95 and 96. My theory that they should be chemically similar
to the rare earth elements was being borne out to such an extent that
we were finding it almost impossible to chemically separate them from
these elements. Although we eventually succeeded, during the period
of our futile efforts to do so Tom continually referred to elements 95
and 96 as "pandemonium" and "delirium."
Names were finally suggested for elements 95 and 96 in the course
of a talk that I gave at the annual spring meeting of the American
Chemical Society in Atlantic City on April 10, 1946 (published in
Chemical and Engineering News, Vol. 24, page 1192, May la, 1946).
Element 95 was given the name "americium" (symbol Am), after the
Americas, in analogy to the naming of its rare earth homologue,
europium, after Europe; and for element 96 we suggested the name
"curium" (symbol Cm), after Pierre and Marie Curie, in analogy to the
naming of its homologue, gadolinium, after Johan Gadolin.
This, then, is the story of the discovery of the elements with the
atomic numbers 95 and 96. I hope that I have succeeded in recapturing
for your some of the excitement, frustrations, and satisfactions that
we experienced in the course of this scientific adventure.
This work is supported by the Director, Office of Energy Research

Division, of Nuclear Physics of the Office of High Energy and Nuclear
Physics of the U.S. Department of Energy under Contract
No. DE-AC03-76SF00098.
REFERENCES:
1. Seaborg, G. T., James, R. A. and Morgan, L. 0., 'The New Element

Americium (Atomic Number 95), 'pp. 1525-1553 in The Transuranium
Elements: Research Papers, Seaborg, G. T., Katz, J. J. and
Manning, W. M., Eds., National Nuclear Energy Series, Div. IV,
Vol. 14B, N.Y., N. Y. (1949)
2. Seabo~G. T., James, R. A. and Ghiorso, A., 'The New Element
Curium (Atomic Number 96)', pp. 1554-1571 in The Transuranium
Elements: Research Papers, Seaborg, G. T., Katz, J. J. and
Manning, Eds., National Nuclear Energy Series, Div. IV,
Vol. 14B, N. Y. (1949)
3. Seaborg, G. T., The Transuranium Elements, Yale University Press
(1958)
4. Seaborg, G. T., Ed., The Transuranium Elements: Products of
Modern Alchemy, Dowden, Hutchinson and Ross, Inc., Stroudsburg,
Penn. (1978)
5. Seaborg, G. T. , 'The Plutonium Story', pp. 1-22, in Actinides in
Perspective, Edelstein, Norman M., Ed., Pergammon Press Ltd.,
Oxford, England (1982)
6. Ghiorso, A., 'A History of the Discovery of the Transp1utonium
Elements', pp. 23-56, in Actinides in Perspective, Edelstein,
Norman M., Ed., Pergammon Press Ltd., Oxford, England (1982)
REMINISCENCES OF AN INSTRUMENTALIST*
A. Ghiorso
Nuclear Science
Berkeley, California 94720
ABSTRACT. Forty years ago the methods used to detect the radiations
from new elements were not very sophisticated although they did suffice.
It is interesting to contrast the techniques used at that time with
those available today.
In thinking back over the past forty years to the time when the work
on the synthesis of americium and curium was starting I was struck by
the dramatic changes that have occurred in the instrumentation used for
analyzing the products of these discoveries. The discoveries themselves
were made possible at that time by the chemical concept that was employ-
ed so they were a triumph of chemistry as demonstrated so clearly in
Glenn's talk. But instrumentation was necessary to show the nature of
the radiations that were detected. In the first efforts the physical
methods available to us were meager and it was necessary to enhance them
in various ways to make them suitable for the searches that were under-
taken.
At that time solid state detectors were not even envisioned by any-
one since the transistor had not been invented yet. Available were
Geiger-Mueller counters for beta rays and gaseous ionization chambers
for alpha particles but these instruments merely enabled one to count
the number of particles. Nothing could be determined as to the energies
of such particles except at very low geometries, usually through the use
of magnetic devices. At about this time nitrogen was being introduced
as the gaseous medium for ion chambers and then, a little later, various
gas mixtures that made possible fast electron collection. The Frisch
grid method for the measurement of alpha particle energies was in the
process of development in England but was not yet available in the U.S.
Range measurements had been used by Europeans as a substitute for energy
measurements but suffered from the disadvantage of low efficiency be-
cause it was necessary to use a low geometry to obtain a precise end
point for the range. See Fig. 1.
It occurred to me that we could achieve our objective of making range
measurements and still have a relatively high efficiency by using 2~
geometry. In this case a range curve would be obtained with the same
19
© 1985 by D. Reidel Puhlishing Company.
20 A. GHIORSO
,
FIG. 1
LOW GEOMETRY
RANGE CURVES
\
,
l
MICA ASSl)R,eER.
I"" ICJ(NE£S Y'ffj/coJ
FIG. 2
21/ GEOMETRY
RANGE CURVES
fI\ leA ABSORBER

-rH I 0<."1£$ 'frIJ /c~
11
2!A 2!l1
PtA Am
REMINISCENCES OF AN INSTRUMENTALIST 21
end point but it would be necessary to use very flat absorbers in con-
tact with the sample to be analyzed. The range curve would then have
the shape shown in Fig. 2. The only convenient absorbers readily avail--
able to us were split sheets of mica that were carefully weighed. These
were laid over the samples and the alpha particles that penetrated all
the way through into the sensitive volume of the ion chamber were the
ones that were counted. One of the problems that we encountered was
that the surface of the mica could charge up and nullify the collecting
potential for the ions created by the alphas. This was overcome by
wiping the top surface with an acidic layer to make them conducting.
Our chambers were operated in air and they needed a large potential
(~1500 volts) to collect the ions. The collection time was quite long
so that the pulse rise time was very slow and thus the required band-
width of the amplifiers extended down to relatively low frequencies.
The net result was that the chambers made very sensitive condensor micro--
phones and tended to pick up the ambient noise in the room in spite of
acoustic shielding. On sensitive counts we would watch the oscilloscope
screens to make sure that our counts were genuine.
But the method did work and we were able to show that 242Cm and
then 241Am had distinctive ranges that separated them from 239pu and
thus gave them characteristic physical identities as well as new chemi-
cal identities. Needless to say this increased our confidence that two
new elements had indeed been discovered.
Before we got to that point, however, Ralph James and I did several
experiments at the Washington University cyclotron in st. Louis which,
in retrospect, were very foolhardy. The idea was to bombard a 239Pu
layer with a high intensity deuteron beam and then examine the target
shortly thereafter for long range alpha particle activity - alphas that
would penetrate a mica layer thick enough to stop the intense 239Pu
alpha radiation from getting into a fast nitrogen-filled ion chamber.
The hazards were two-fold. The uncovered target was a slurry of perhaps
10 milligrams of plutonium oxide evaporated to dryness onto a thick
water-cooled copper plate. I don't know which was worse - being exposed
to Pu from a target handled with short tongs and no hood or being exposed
to the very intense beta-gamma activity from the deuteron bombardment of
the copper target holder! And all of this done with no survey meters!
Of course we didn't find anything but many months later we realized
that the 241Am was already there, slowly growing in from the small
amounts of 241pu that was present in the plutonium as a result of its
production from uranium in a sea of reactor neutrons.
Speaking of these crude methods reminds me of a funny incident that
took place around this time. After we had found element 96 and then 95
we obtained more and more samples of plutonium from the Clinton pile
that had been exposed to increasing fluxes of neutrons to look for new
isotopes. Since we knew that 241pu was a long-lived beta emitter we
wanted to find 242pu. We decided that the most sensitive way to detect
it would be to look for an enhanced spontaneous fission rate since we
knew that 240pu had a surprisingly short fission half-life. One of
the chemists made up a beautiful sample by electrolysis which was about
a milligram per cm 2 thick. It was on a platinum plate about three
inches in diameter and this thin plate was cemented onto a thicker brass
22 A.GHIORSO
plate for rigidity. I put the precious sample into the fission counter
and watched for the big kicks in the oscilloscope that would signal
spontaneous fission events.
After only fifteen minutes there was an event and I went running
down the hall to alert people to the possibility that we were onto
something most unusual. Then there was another big kick and then
another! No doubt about it, the spontaneous fission half-life must be
even shorter than we had expected. Since very little was known about
spontaneous fission at that time we found this new information very
exciting. The big kicks continued to come in for several hours. Then
I began to realize that something was wrong for the counts seemed to
come in at surprisingly regular intervals. So I timed them and found
that the in~orval was indeed always about fifteen minutes! The
oscilloscope ~howed nice big kicks, just the way spontaneous fission
events always looked, so the counter seemed to be in working order.
What could be wrong? Then I had an idea. The intense alpha activity
might be charging up the platinum plate insulated from the thicker plate
by the layer of cement until it reached a potential where it would
discharge. This discharge would be picked up and register as a fission
and then the plate would begin the cycle allover again. I shorted the
two plates together and the big kicks went away.
I remember these early years as being very intense. There was an
awful lot to learn and I had a very poor background from which to start.
But the work was so fascinating that I had plenty of incentive to plod
away at it. I remember going to the library and reading about the early
experiments in radioactivity by Madame CUrie and by Ernest Rutherford
and his group. Their work was even more difficult since at first they
did not know of the existence of isotopes. with their even more primi-
tive equipment they used marvelous ingenuity and brilliance to unravel
gradually the various alpha decay series in all their splendor. In the
course of our investigations it became necessary for me to check some of
their measurements using various alpha recoil techniques. I thought
that with our somewhat better counter systems surely I would find that
some of their results would be in error. On the contrary I found that
they were always right. That was also true for the results of the
earlier Seaborg group measurements which I repeated. Gradually I
formulated the Ghiorso Uncertainty Principle - first experiments are
likely to be correct if there are enough compensating errors!
In spite of this feeling I found that Ralph James was a very cau-
tious fellow. I remember how he would agonize over the possibility that
there was a monstrous error and somehow the assignments of the new
activities were wrong. He would dream up some very unlikely scenarios
which would change the picture completely - and this many months after
he and Glenn had deduced the correct interpretations.
But we learned and gradually introduced new methods to the
discoveries of new elements. Some we invented ourselves and others we
borrowed from other experimental studies. The use of Frisch-grid ion
chambers made a big difference along with the introduction of
multi-channel pulse height analyzers. These tools enabled us to work
with fewer and fewer atoms as long as there was time enough to do
specific chemical separations.
REMINISCENCES OF AN INSTRUMENTALIST 23
G. MUt\iehbeY"9 ~i 0(. t'lS2.

F/8.3
24 A. GHIORSO
The big breakthrough came when we introduced the recoil technique

for separating element 101 and other reaction products from highly
radio-active targets. This was followed in due course in the early 60's
by the use of the helium gas jet to transport these recoils to remote
counting stations employing the just-invented solid-state detectors and
this in turn led to the extremely powerful genetic method. With this
latter technique we were able to identify particular nuclides by demon-
strating alpha-alpha correlations for elements 104, lOS, and 106 between
unknown parents and known daughters and grand-daughters. Only a dozen
or so alpha particle decays correlated in energy and time were necessary
to identify these new elements. This technique was extremely important
because the available half lives had become too short for conventional
chemical identification.
The ultimate was finally reached by Peter Armbruster's group at GSI
in 1982 when they identified one single atom of element 109 during a two
week period of bombardment of 209Bi by 58Fe ions (Fig. 3). Their
velocity separator, SHIP, was used to separate a recoiling atom of
266 109 from the intense beam and implant it at a measured position in
a silicon detecting crystal with a measured recoil energy. At this
particular position they identified a high energy alpha particle emitted
5 milliseconds later from that atom. At the same position 22 milli-
seconds later they observed only part of the alpha energy from its
daughter, 262 107, because the alpha particle from that decay had
escaped out through the face of the detecting crystal. Finally 13
seconds after that a spontaneous fission was emitted from the same place.
This last member of the chain was from 258 104, a known 13-ms SF emitter
following electron-capture decay of 258 105. Great confidence can be
ascribed to this experiment since it was accomplished in a setting with
a unique genetic chain and essentially no background.
I have been fortunate to participate in a dozen steps of this long
string of new element syntheses and to observe first hand the profound
changes that have taken place in the instrumentation essential for their
identification. Each time that a new element has been discovered has
meant that a new set of problems has been solved and thus has set the
stage for the next step. The discoveries of curium and americium were
the beginning steps for the transplutonium elements and so in some ways
were the most exciting of all.
*This work was supported by the Director, Office of Energy Research,

Office of High Energy and Nuclear Physics, Nuclear Science Division,
u.S. Department of Energy under Contract No. DE-AC03-76SF00098.
AMERICIUM, ITS EARLY HISTORY AND GRAM-SCALE SEPARATION
R.A. Penneman (Consultant)

Los Alamos National Laboratory
Group I NC-4 , MS C-346
Los Alamos, New Mexico USA 87545
ABSTRACT. For this 40th Anniversary Discovery Celebration,

The early contributions of the americium group at Los
Alamos, established in 1948, are reviewed. They include
the first major isolation of americium from impure pluton-
ium, and significant expansion of americium chemistry.
The discovery of americium was made in 1944, as just re-

counted in the first paper of this session by one of the
discoverers, Glenn T. Seaborg. The discovery was made at
the Metallurgical Laboratory of the University of Chicago.
The Metallurgical Laboratory (later it became the
Argonne National Laboratory) had been established as a
result of wartime urgency in response to December 1941
urgings of Nobel Laureate Arthur Compton. Compton was an
influential figure in American physics in those days, and
was successful in achieving consolidation and expansion at
Chicago of the atomic work begun at Columbia and Berkeley.
Thus, Fermi, Seaborg and others came to Chicago. The
pace of discovery in those days was extraordinary! At the
end of the first year, in December 1942, Fermi demonstrated
the graphite-moderated reactor, fueled by natural uranium.
Future reactors would generate neutrons and heavy elements
on a production scale, surpassing by orders of magnitude
the tiny amounts possible with the cyclotron. Within the
next two years, Seaborg and his team had painstakingly
collected enough plutonium to establish its separation
schemes, and found two new elements, americium and curium.
I was but indirectly associated with Seaborg in those
exciting days. As a young chemist just hired (July) at the
Metalurgical Laboratory, I had been sent in August 1942 to
Beverly, Massachusetts as part of a team to aid in
producing the needed uranium metal. Later, on return to
Chicago, I and another from Milton Burton's team made the
25
26 R.A.PENNEMAN
first measurements of the energy stored in graphite as a

result of neutron displacement of carbon atoms when
graphite was used as a neutron moderator in a reactor.
Part of the new knowledge being generated was in the
province of physics. However, many of our present ideas of
chemistry and of the extension of the Periodic Table of
Elements were also being formulated at that time. Indeed,
it was not until late June, 1944 that Burris Cunningham was
able to furnish W. H. Zachariasen with a sample of neptun-
ium oxide thought to be the dioxide. By x-ray diffraction
analysis, Zachariasen confirmed neptunium dioxide, and
wrote a memo formally suggesting that a ng~ §g~ig§ Qf
glgm~n~§~ ~ni£n n~ £~ll~Q !nQ~iQ~§, were in hand, n~Ying ~
Q~~§i§~~Q~ Y~l~n£~ Qf fQY~~ He based his arguments on the
stability of the dioxides, on the progressve diminution in
ionic radius from thorium(IV>, uranium(IV>, neptunium(IV>
to plutonium(IV) and the similarity of the radii of tetra-
valent cerium and uranium.
Seaborg had long thought about the properties of the
anticipated new series of elements and their properties.
In July 1944, Seaborg dictated a memo in which he suggested
that ~n~ ~l~m~n~§ fQ1IQ~ing ~£~iniYm ~g Ql~£~Q in ~ ng~
§~~i~§ £~ll~Q B£~iniQ~§. As we know, the linchpin of his
successful proposal was the placement of the then unknown
element of number 96 (curium) at the series midpoint, the
predicted increasing stability of the trivalent state, and
divalency at atomic number 102. Seaborg has mentioned earl-
ier today the importance of this latter chemistry in the
discovery of americium. As we shall see, however, americ-
ium is saved from the monotony of trivalent chemistry by
its greater number of valence states and hence displays an
americium chemistry of extraordinary variety.
In the period following the discovery of americium,
neutron irradiation of a small amount of plutonium and
separation of the americium resulting from the beta decay
of mass 241 plutonium permitted Burris Cunningham to
explore the chemistry of americium on the microgram scale.
This remarkable work was described in 1949 (1). In those
studies. tetravalent americium was demonstrated in the di-
oxide, pentavalent americium as the potassium carbonate
salt of unknown composition. Of course, trivalent americium
was demonstrated to be a very stable aqueous ion. This was
the status of americium chemistry when the Los Alamos work
began. All of it was found to be correct.
However. from the early tracer studies, and reinforced
by the location of americium in the new actinide series as
a homolog of europium. it was believed (erroneously) that
americium also possessed an attainable aqueous divalent
state. Establishing that this was QQ~ the case, was the
single major change that the Los Alamos investigators were
AMERICIUM, ITS EARLY HISTORY AND GRAM-SCALE SEPARATION 27
to make in the early work. Other major contributions were

to follow soon after.
First of all, the building had to be outfitted for the

upcoming separations work and the research anticipated to
follow. The warehouse-type building did have two great
advantages: first, it was already fitted with a exhaust
system suitable for handling alpha activity, and second, it
was contiguous to buildings where plutonium work was still
being carried on. Eventually, we were to be given the
concentrated residues from plutonium processing, and thus
had a continuing source of americium-rich residues from
which to isolate americium. I use the term americium-rich
in a relative sense. Certainly americium was present in
those residues which were often the color of used motor
oil, saturated in salt and had a specific gravity above
1.5--it was just that americium was a such m!nQ~ impurity!
When I came to Los Alamos in the fall of 1947 after
finishing my graduate studies at the U. of Illinois, the
great exodus after war's end had taken place. Thus, I
could take over an empty building wing no longer needed for
plutonium work and was able to set out to recover americium
from a potential major source. The source was a stock of
plutonium metal turnings that had been accumulated from
machining fuel rods for the Clementine reactor.
After a year of so in installing equipment and glove
boxes to handle the expected americium, we began to
dissolve plut.onium turnings on about a 250 gram scale and
to precipitate the plutonium peroxide, leaving americium in
the filtrate. As noted in a recent paper from Los Alamos,
modern-day americium separators have a much easier time of
it. Certainly in that early day plutonium and its residues
the americium content was lower, and the impurity content
higher than that observed today. It is often found now
that just one precipitation of americium hydroxide from the
plutonium peroxide supernatants results in americium of
greater than 957. purity(2).
It did stretch our intellectual muscles to finally
isolate americium from solutions that once had several
hundred times as much lanthanum as americium. The abundant
calcium was not difficult to remove since its hydroxide is
so much more soluble than that of americium. That merely
required us to wash the impure hydroxides with ammonium
nitrate. The ammonium ion tied up the hydroxide, thus
solubilizing the calcium while maintaining the pH high
enough to keep the americium hydroxide in the precipitate.
Removing the lanthanum was another matter. That removal on
a large scale was accomplished by ion exchange. Also, John
Hermann, in a thesis directed by Penneman, showed that
homogeneous generation of oxalate enriched americium over
lanthanum in the precipitate.
28 R. A. PENN EM AN
Los Alamos work began to focus on the new americium

chemistry itself by 1950. It followed the pioneer work on
americium which Cunningham, Werner and Perlman had
provided in the half-dozen years following its discovery.
We had an enormous advantage over the earlier workers in
that, once we had it isolated, we could work with americium
on the many milligram scale, utilizing spectrophotometry to
ascertain americium valence states in millimolar solutions.
Thus, we could rather quickly disp·el the notion that
americium had an attainable divalent state by observing
that the trivalent absorption persisted in spite of
reducing agents that yielded both europium(II) and
samarium(II). It was later demonstrated by Asprey that
treatment of the solid trichlorides of americium and of
samarium with hot hydrogen reduced samarium to its dichlor-
ride, but did not reduce americium trichloride.
Finally having accumulated a sufficient stock of
purified americium enabled the work to proceed without
having to stop after every experiment to repurify--a task
which plagued the earlier work. Indeed, spectrophotometry
of americium in solutions as well as in the solids was
invaluable. Advances in the art of high resolution spec-
trophotometers provided another advantage, since the ab-
sorption lines of some americium valence states are so
extremely narrow. It was especially helpful when recording
spectrophotometers were later available to aid in kinetic
studies involving Am(V) disproportionation.
Research on the isolated americium was well enough ad-
vanced through 1950 that, at the fall American Chemical
Society meeting in Chicago, the Los Alamos group could
report the following significant advances:
1. The discovery of hexavalent americium,
2. Its similarity to hexavalent uranium in their

sodium acetate compounds,
3. The oxidation of Am(III) to Am(VI) by peroxydi-

sulfate,
4. The measurement of the reversible couple,

Am(V)/Am(VI),
5. The achievement of Am(VI) by high acid dispropor-

tionation of Am(V),
6. Preliminary values of the second order rate con-

stant for the disproportionation of Am(V).
7. The failure to observe an absorption feature which

was ascribable to aqueous Am(IV).
AMERICIUM, ITS EARLY HISTORY AND GRAM-SCALE SEPARATION- 29
The reac~ion involving ~he dispropor~iona~ion of Am(V)

was shown ~o be second order in Am(V). This reac~ion ~hus
implied ~he forma~ion of bo~h Am(IV) and Am(VI):
2 Am(V) = Am(VI) + Am(IV)
Al~hough Am(VI) was observed, only ~he absorp~ion spec~ra

of ~he ~wo known species, Am(III) and Am(V) were ever
o~her
presen~. This evidence sugges~ed ~ha~ Am(IV) was rapidly
removed by o~her reac~ions such as dispropor~iona~ion, by
i~s reduc~ion by solven~ wa~er, or by oxida~ion of Am(V)
~o Am(VI), a reac~ion found la~er ~o predomina~e.
Our search for soluble ~e~ravalen~ americium was

finally ~o be successful, bu~ no~ un~il 1960 and only then
as a highly complexed anion. Consideration abou~ ~he value
of ~he Am(IV)/ (III) couple being somewhat over two volts
persuaded me ~o a~~emp~ the alkaline oxida~ion of americium
~rihydrdoxide in the a~tempt to make the ~hen unknown
~e~rahydroxide, reasoning that if i~s solubility product
were sufficiently less, say by 10exp16, this one volt would
move the oxidation po~ential of ~he ~etravalent s~ate into
the region of chemical stability. Trea~ment of the tri-
hydroxide wi~h hot sodium hypochlorite did yield a black,
insoluble ma~erial.' When dissolved in acid it did not
yield Am(IV) bu~ only ~he other known, soluble americium
species. Conserva~ion of oxida~ion number proved tha~ the
black compound was indeed the hydroxide or hydrous oxide of
~e~ravalent americium. Bu~ what to do about this very
insoluble ma~erial?
Recall ~he earlier men~ion of ammonium ion to bind ~he
hydroxide when we had to remove calcium hydroxide from the
impure americium trihydroxide slurry? I decided ~o ~rea~
the black, insoluble compound (hydroxide) of te~ravalent
americium wi~h a concentrated solu~ion of ammonium fluor-
ide. The ammonium ion was supposed to take up the freed
hydroxide and ~he fluoride ion, having ~he same charge and
size, was then to replace the hydroxide on the americium
to form a fluoride species of ~e~ravalent americium.
Imagine the agreeable surprise when a rose-colored
solu~ion resul~ed! The solu~ion gave an absorp~ion spec-
trum differen~ from those of Am<III>, Am(V) or Am(\,/I>, and
could be treated ~o yield these other valence s~ates in
solution. Ih~ ~!Y~iY~ ~Q!Y~!~ ~~~~~ Qf ~m~~i£iym h~Q
fi~~!!Y ~~~~ fQY~Q! My original idea had been ~o conver~
~he black "hydroxide" of Am(IV) into a solid fluoride, and
we were later able to crystallize ou~ the compound of amer-
icium tetrafluoride with four molecules of ammonium fluor-
ide, yielding an eight coordinated anionic species. Of
course, Larry Asprey and I were happy ~o accept the ~Q~Y~
of a ~Q!Y~!~ ~g~£i~~ Qf ~~~~~Y~!~~~ ~m~~i£iYm.
30 R.A.PENNEMAN
In a parallel study, Asprey had obtained a crystalline

product by allowing a solution of Am(V) in concentrated
potassium fluoride to stand some days. The solid, crystal-
line substance which gradually formed gave an unusual ab-
sorption spectrum. Later, it turned out that the compound
was dipotassium americium hexafluoride. So Asprey had ob-
tained the first double fluoride salt of Am(IV) from solu-
tion.
The formula (or formulas as it turned out) of the
potassium carbonate salt(s) of pentavalent americium had
been unknown since Perlman and Werner first oxidized
Am(III) in concentrated potaSSium carbonate solution to the
insoluble, tan precipitate containing pentavalent americ-
ium. Joe Nigon and I found the formula of one of the
compounds, and established that there was at least two
other formula or compound types. It remained for Tom
Keenan to make the series of 1:1 salts with the several al-
kali carbonates, each containing the dioxo americyl(V)
group. He found the best route to this series, even with
plutonium, was to use the bicarbonate rather than the
carbonate. One especially interesting finding involved the
discovery that with §QQiYm bicarbonate or carbonate,
oxidation with ozone yielded the mehQgen~=~QIQ~~Q~ §QIYQ1~
~Qm~l~~ Qf h~~~Y~l~nt ~m~~i~iHm. On the other hand, use of
~Qt~§§iHm bicarbonate or carbonate invariably stopped at
the insoluble ~~nt~Y~l~nt state.
There is an interesting story involving Zachariasen
and our compound, potassium dioxo americium(V) carbonate.
I showed the x-ray powder pattern to him, and he recalled a
similar pattern from an unanalyzed plutonium compound shown
to him years earlier. In his case, he said the plutonium
compound had resulted from potassium hydroxide addition to
a solution of ng~~Y~l~nt ~lHtQniHm and allowing the basic
solution to stand. By cell volume analYSis he had conclud-
ed that the cell should contain Qn~ QiQ~~ ~lHtQn~ll~!l ion 1
Qn~ ~Qt2§§iym and th~~~ other Q~~g~n§, then thought to be
n~Q~Q~~l§, to balance the charge on the cations.
However, from our americium studies, we knew that the
americium was ~gnt~Y~l~n~ and that the compoumd contained
~~~QQn~tg. Therefore, the compound's three oxygens came
from carbonate, not hydroxide, to give potassium pluton-
yl(V) carbonate, rather than the Pu(VI) hydroxide formula
he originally asigned. Both formulas satisfied his cell
requirements, but only one satisfied the chemistry. In
retrospect, what had evidently happened was that carbon
dioxide had gotten into the plutonium solution on standing,
and that reduction by alpha radiation had produced Pu(V)
from Pu(VI). After this, Zachariasen trusted us ~ngmi§t§ a
little more, although he always felt more comfortable with
solids whose true structure was established by x-ray!
Regarding the disproportionation of Am(V), it remained
for the availability of long-lived 243 americium isotope
and Jim Coleman to elucidate the rate. The long-lived iso-

tope reduced the radiation problem to a manageable level
(recall that self-radiation from the 432 year isotope
reduces aqueous valences higher than Am(III) at a rate of
several percent an hour).
Larry Asprey and Tom Keenan made americium halides, and
Asprey produced the metal. His observation of the fcc
phase was long questioned, even though it was later found
that the fcc phases of Am and Pu were miscible. Finally,
work at the Kernforschungzentrum in Karlsruhe, on americium
metal, confirmed his finding.
Shortly after our discovery of the hexavalent state,
Steve Stephanou showed that it was possible to oxidize
Am(III) to the fluoride-soluble Am(VI) state and to precip-
itate curium trifluoride from the Am(VI) in solution. Oth-
ers used this hint in a later patent appplication for the
separation of americium from the rare earths.
In the early 1950's, Lew Jones and I demonstrated,
using infrared absorption spectra obtained from thin
aqueous films of Molar solutions of the hexavalent ions,
that the uranyl-type, linear dioxo structure persisted from
uranium through neptunium, plutonium and americium.
Furthermore, the monovalent, dioxo ions of neptunium(V) and
of americium(V) gave similar absorption, indicating similar
structures.
This technique of observing the infrared spectrum
of aqueous solutions in thin films led to advances in other
areas, that of observing stepwise formation of complex
ions, for example cyanide complexes, by "finger-printing"
the vibration spectra of the individual ions.
To the other names mentioned in the text as being in-
voved in the early-day work with americium should be added
the name of Dale Armstrong, who was the designer of the
large-scale equipment and instrumentation so useful in many
of the cited studies. References to the main contributors
to the first decade or so of americium work at Los Alamos
are listed in references 3-28.
Finally, in closing my contribution to this 40 year

post-discovery celebration, I wish to acknowledge the major
contributions made by the European teams at their various
laboratories, especially the work on the pure metals,
chalcogenides and especialy the needed thermodynamic data.
I note as well as the considerable data produced by

the Russian workers over many years. Although we were
early in the use of alkaline oxidation, and did achieve
both Am(IV) and Am(VI}, we did not pursue it to the very
successful accomplishment of such high overall actinide
valences as they did.
32 R. A. PENNEMAN
References
1. "The First Isolation of Americium in the Form of Pure

Compounds; Microgram-Scale Observations on the Chemistry
of Americium," B.B. Cunningham, in Ih!!! I!:enl!!~!:en!.~!!! !;!!!!=
!!!!!!n~l!!, National Nuclear Energy Series, Div. IV, Vol. 14B
(McGraw-Hill Book Co. Inc., New York, 1949), Paper 19.2.
2. "Status of Americium-241 Recovery and Purification at
Los Alamos Scientific Laboratory," H.D. Ramsey, D.G.
Clifton, S.W. Hayter, R.A. Penneman and E.L. Christensen
in I!:enl!!R!~~Qn!.~m !;!!!!!!!!!!n~l!!~ e!:QQ~£~!'Qn enQ 8!!!£Q~!!!!:Y,
(ACS Symposium Series #161), J.D. Navratil and W.W.
Schulz, Eds. (American Chemical Society, Washington,
D.C., 1981), Ch. 5. pp. 73-91.
3. Stephanou, S.E., Asprey, L.B., and Penneman, R.A., Re-

port AECU-925, 1950.
4. Penneman, R.A. and Asprey, L.B., Report AECU 936, 1950.
5. Asprey, L.B., Penneman, R.A. and Stephanou, S.E., Re-

port AECU-927, 1950.
6. Asprey, L.B., Stephanou, S.E. and Penneman, R.A., J~

8!!!!!!!:~ ~h!!!!!!~ ~Q£., 1950., Z~, 1425.
7. Asprey, L.B., Stephanou S.E. and Penneman, R.A •• !'~!'Q.,

1951, Z~, 5715.
8. Stephanou, S.E. and Penneman, R.A., !'~!'Q., 1952, Z1,

3701.
9. Jones, L.H. and Penneman, R.A., J~ ~h~!!!~ ehYl!!., 1953,

~!, 542.
10. Stephanou, S.E., Nigon, J.P. and Penneman, R.A •• !'~!'Q.,

1953, ~!, 42.
11. Keenan, T.K., Penneman, R.A. and Mclnteer, B.B., !.Q!.Q.,

1953, ~!, 1802.
12. Nigon, J.P., Penneman, R.A., Staritzky, E., Keenan, T.

K. and Asprey, L.B., J~ ehY§~ ~h!!!!!!., 1954, ~~, 403.
13. Keenan, T.K., Penneman, R.A. and Suttle, J.F., !.Q!.Q.,

1955, ~y, 381.
14. Hermann, J.A., Report AECD-3637, Los Alamos Scien-

tific Laboratory, July 1954. (Thesis, U. of New Mexico)
15. Armstrong, D.E., Asprey, L.B., Coleman, J.S., Keenan,

T.K., LaMar, L.E. and Penneman, R.A, Los Alamos
Scientific Laboratory Report LA-1975, 1956.
16. Penneman, R.A. and Asprey, L.B., e~Q£~ !nt:! ~Qnf~ Qn

e~~£~fY! y~~~ Qf etQmi£ ~n~~gy, 1956, Z, 355.
17. Coleman, J.S., Penneman, R.A., Keenan, T.K., LaMar, L.
E., Armstrong, D.E. and Asprey, L.B., ~~ !nQ~g~ ~Y£!~
~b~m., 1957, ~, 327.
18. Armstrong, D.E., Asprey, L.B., Coleman, J.S., Keenan,

T.K., LaMar, L.E. and Penneman, R.A., e!~b~ ~QY~n~!,
1957, ~, 286.
19. Penneman, R.A. and Keenan T.K., "!b~ B~giQ£b~mi~t~y Qf

em~~i£iYm ~ng ~Y~iYm," National Academy of Science-NS-
3006, 1960.
20. McWhan, D.B., Wallmann, J.C., Cunningham, B.B., Asprey,

L.B., Ellinger, F.H. and Zachariasen, W.H., ~~ !nQ~g~
~y£!~ ~b~m., 1960, !§, 185.
21. Penneman, R.A., Coleman, J.S. and Keenan, T.K., iQig~~

1961, !Z, 138.
22. Asprey, L.B. and Penneman, R.A., ~~ em~~~ ~b~m~ §Q£~,

1961, ~~, 2200.
23. Asprey, L.B., Penneman, R.A. and Kruse, F.H., ~b~m~ ~ng
gng~ ~~~~, 1962, ~Q, No.8, 39.
24. Asprey, L.B. and Penneman, R.A., InQ~g~ ~h~m., 1962, 1,

134.
25. Coleman, J.S., Keenan, T.K., Jones, L.H., Carnal 1 , W.T.

and Penneman, R.A., iQig., 1963, ~, 58.
26. Penneman, R.A., Kruse, F.H., Benz, R. and Douglass, R.

M., iQig., 1963, ~, 799.
27. Asprey, L.B. and Penneman, R.A., ~b~m~ ~Dg gDg~ ~~~~~
1967, ~§, No. 32, 74.
28. Penneman, R.A., Keenan, T.K. and Asprey, L.B., "Lan-

thanide/Actinide Chemistry," Amer. Chem. Soc., eQY~D£~~
in ~b~m~ §~~i~~, 1967, Z!, 248.
20 YEARS OF AMERICIUM AND CURIUM RESEARCH AT THE EUROPEAN INSTITUTE
FOR TRANSURANIUM ELEMENTS
W. Muller
Commission of the European Communities, Joint Research Centre
Karlsruhe Establishment
European Institute for Transuranium Elements
Postfach 2266
D-7500 Karlsruhe
Federal Republic of Germany
ABSTRACT. Part of the European Institute for Transuranium Elements'

research programme which is aimed at elucidating the role of 5f elec-
trons in the chemical bond has been devoted to the study of americium
and curium. The investigation of fundamental properties, carried out
also in collaboration with foreign research institutes and institu-
tions, has involved: separation and purification of Am and Cm in multi-
gram quantities by combining various separation methods: ion exchange,
solvent extraction, extraction chromatography, precipitation; prepara-
tion of Am and Cm metals by metallothermic reduction of oxides or
thermal dissociation of intermetallics, followed by repeated sublima-
tion for purification purposes; determination of bonding related phy-
sical properties: vapour pressures (sublimation enthalpy), electrical
resistivity, magnetic susceptibility, volume or crystal structure
changes under pressure. Examples of applied research and current work
are presented.
The European Institute of Transuranium Elements at Karlsruhe is one

of four research establishments of the Joint Research Centre of the
Commission of the European Communities. The three other research
establishments are located in Italy (Ispra), Belgium (Geel) and in
the Netherlands (Petten).
The Institute for Transuranium Elements was built during the
early sixties in order to centralize the efforts of EURATOM in the
development of plutonium containing fuel for fast breeder reactors
and for fundamental research on actinide elements.
Fundamental research of actinides started immediately after the
construction of the hot cells with the reprocessing of transuranium
samples irradiated at Idaho Falls. This first reprocessing run furnish-
ed the starting material ( 243 Am, 244Cm) for early americium and curium
research. Since 1965 an important part of the research programmes of
the European Institute for Transuranium Elements has been devoted to
the study of these two elements situated in the middle of the actinide
series and characterized by the localization of 5f electrons.
35
36 W.MULLER
Three periods, in part overlapping, can be distinguished corre-

sponding to the following research areas:
isolation and purification of americium and curium,
preparation of americium and curium metals of high purity and
investigation of bonding related properties (structural, thermo-
dynamic, magnetic, electrical, electronic) of the elements.
Synthesis of well characterized binary compounds accompanied this
work, but growth of their single crystals has just begun.
The first period started in 1965, the second one in 1970, the
third period in the mid seventies. These three themes will be illus-
trated by a few examples, and the review will finish with a summary
of present work and plans for the future.
ISOLATION AND PURIFICATION OF AMERICIUM AND CURIUM
Two sets of samples were reprocessed from aluminium-clad Am02-AI powder

cermets irradiated in Idaho Falls and BR II/Mol, Belgium. The reproces-
sing schemes were based on experience gained in the United States -
using ion exchange from highly concentrated lithium - salt solutions.
Milligram quantities of highly purified 243 Am and 244 Cm were made avai-
lable to the very few groups in Europe equipped at this time for work
with a-emitting radioelements. Gram quantities of 242 Cm , resulting from
a (relatively) short time irradiation of 241Am in BR II were isolated
and in part encapsulated to fuel the first European isotope battery 1 .
Around 1970 we acquired a 109-mixture of 243 Am and 244 Cm • The ele-
ments were separated by precipitating the major part of the americium
as the Am02+ - carbonate complex and purifying the curium fractions by
a series of extraction chromatography (substituted ammonium salts,
HDEHP) and ion exchange processes 2 (Fig. I).
,-----, ,------,
r-----, 13.5" LiN0 3 I 11 M LACTIC I
18.0MLiN0 3 I
10.5" KBr03 I I ACID I
I 0.0IMHN03 I 0.05 M DTPA
,--- ---,
LACTIC ACID
L.9~..!~r~3j ILpH ~ 28
_____ ...JI L _____ ...JI
11 M HN0 3
10.5 M HN0 3 I
PU,Ce RE D ~::'~.?~AL~~~~
A H 0
L D W
____ I E E
rs·OMLiN03l Q H X
1 0.01 .. HN03 ~- u p r----'
.. HN03 l-
50
i
10.5
L.9:'~~~3J :A r;;:;-lACTlcl
ACID I
L _ _ _ _ ..J
.-------,
~5;L;N031 IT L~.:'::~_J 16____
L M HN0 3 ....J
I O.OIM HN03 I I
I1;;-LACr;C l
L.9~~~~3j I I ACID I
,----, I 10.05 .. DTPA I
11.0M HNO, I
10.5 .. KBr03:-- L~~~8_...J
L ____ ..J II r
II I
I Cm
L_
I
r - -,
I em I
IL:
I ..... / L_ -'
~ .............. A I
Fe. N,. Pb m Li.K Li, K, LACTIC ACID, DTPA
Figure 1. Purification of multigram quantities of 244 Cm by extraction

chromatography after separation from 243 Am by precipitation. (Ref. 2)
20 YEARS RESEARCH AT THE EUROPEAN INSTITUTE FOR TRANSURANlUM ELEMENTS 37
The resulting high purity fractions of americium and curium, after

transformation into oxides, are still today the starting materials
for special preparations of metals or intermetallics 3 and for the
synthesis of compounds 4 •
PREPARATION OF HIGH PURITY AMERICIUM AND CURIUM METALS
The reduction of anhydrous actinide halides by lithium or barium vapour

very often results in metals containing non-volatile impurities and
oxygen. Therefore we decided from the very beginning of our metal
preparation attempts to apply methods involving volatilization of the
actinide elements. Our preferred method was the reduction of prepuri-
fied oxides by electropositive, non-volatile metals followed by the
distillation of the actinide metals from the reaction mixture. The
principle of these methods had been developed in the case of Am metal
preparation at Los Alamos 5,6, and in the case of the em homologue
gadolinium at the Rare Earth Laboratory at Meudon/France 7 • For the
preparation and manipulation of the high purity metals, a special,
double glove box concept was developed 8 (Fig. 2).
Figure 2. Scheme of the CD

double-wall glove box for the
preparation of actinide metals:
(1) nitrogen box with vacuum ----------- --~-------- -'
equipment and induction fur-

nace, (2) argon box; for
changing of gloves, the argon
box can be moved on rails,
(3) water-cooled quartz tube.
(Ref.8)
The possibility of actinide metal preparation by thermal dissocia-

tion of actinide-noble metal intermetallics was demonstrated 9 , but
most of the metal samples were obtained by lanthanum reduction of
americium oxide 8 or thorium reduction of curium oxide 10
38 W. MULLER
INVESTIGATION OF THE PROPERTIES OF AMERICIUM AND CURIUM
Several properties of americium and curium were determined or redeter-

mined with highly purified metals.
Americium and curium metal of known isotopic compositions and of
high chemical purity were used as "spike" material for isotope dilution
analysis. The half-life (and, hence, the decay constant) of 241Am were
redetermined by measuring the specific heat output of a metal sample I I ,
which had been prepared by repeated sublimation and had been fully ana-
lysed. The newly determined value of the half-life is 432 ± 0.2 years.
The electrical resistivities of both the metals 12,13 were deter-
mined between 300 and 6K. A potentiometric method was employed to meas-
ure the electrical resistivity of an americium layer of 1.89 Mm thick-
ness. Up to 20K, the resistivity varies with temperature as T2 • 8 , at
higher temperatures deviations from the linear law were found similar
to those in uranium and neptunium (Fig. 3). The resistivity of curium
metal shows a sudden decrease of the slope around 60K (which is related
to the magnetic transition around 52K) , and at higher temperatures a
behaviour similar to that of a lanthanide metal is seen.
160
140 a-Pu
Np
Tu 120
c: 100
6
>-
I- 80
>
l- Am
(/)
60
(/)
UJ
a::
40 u
20 Po
Th
Figure 3. Electrical
resistivity of actinide 100 200 300
metals. (Ref.12) TEMPERATURE [KJ
The standard free energy of chloride formation was determined by

potential measurements in molten salts 14, IS. The enthalpies of forma-
tion of Am3+ and of Cm3+ ions were determined by measuring the enthalpy
of dissolution of the metals in diluted hydrochloric acid 16,17. The
heats of solution of the dhcp allotropes at room temperature in 1 molar
HCl were obtained as -616.1 ± 0.8 kJ/mol- 1 for americium, and
-614.5 ± 4.5 kJ/mol for curium, respectively. From these values, the
standard enthalpies of formation of the trivalent ions are deduced as
-616.7 ± 1.2 kJ/mol (Am) and -615 ± 5 kJ/mol (Cm). New values for the
heats of formation of various americium ions and compounds could be
20 YEARS RESEARCH AT THE EUROPEAN INSTITUTE FOR TRANSURANIUM ELEMENTS 39
derived. The enthalpy of sublimation was determined by a very careful

redetermination of the vapour pressures of the metals as a function of
temperature 18,19 (Fig.4). The differences between the values of the
two elements can be explained by taking into account the specific
magnetic character of condensed americium and the transition in the
gaseous state to atoms with two valence electrons, whereas Cm behaves
as a trivalent, lanthanide-like metal.
10- 5
Figure 4. Vapour
pressure of solid
americium. Full cir-
cles and open circles
correspond to differ-
ent measurements 10-8~ro~~T'-''-''-''-TO-r~~-..-~-r'-OT-r~r4
7.20 7.70 9.20 9.70 9.20 9.70 10.20
series. (Ref.18)
100001T[K]
The specific heat of americium metal has been determined 20 and

the list of the thermodynamic properties of the light actinide ele-
ments is completed21 • During a comparison of the magnetic properties
of americium and curium metals, antiferromagnetic ordering of curium
metal was observed 22. The magnetic susceptibility of americium metal
is almost temperature independent between room and liquid helium tem-
peratures. Curium metal shows Curie-Weiss-paramagnetism with antiferro-
magnetic ordering around 52K. Its effective magnetic moment supports
the hypothesis of localized Sf electrons and a metal valence of 3.
The influence of temperature 23 and of pressure 24,25,26 on the
crystal structure of americium and curium metals have been investigated.
The present state of the high pressure studies will be described in a
later paper by U. BENEDICT 27 during this conference. Recently, the
localization of Sf electrons in americium, expected and predicted by
theory for a long time, could be demonstrated by X-ray and high resolu-
tion UV photoemission spectroscopy on americium metal 28. The compari-
son with plutonium metal proved that the transition from delocalized to
localized Sf behaviour takes place between Pu and Am (Fig. 5).
40 W.MULLER
f
.j"'*'.
;
.i , ~
.
y •
, \
!
51 6_51 5 !
Am~
>-
I-
1Ii
z
W
I-
Z
z
o
0::
I-
U
W
...J
W
ot-
o
:I:
a.
Figure 5. Conduction-band
spectra of Am, Pu, and Sm metal
for 40.8-eV excitation. I
~
10
(Ref.28) ENERGY BELOW Ef reV]
EXAMPLES OF PRESENT DAY AMERICIUM AND CURIUM RESEARCH
- The americium and curium build-up in fuel of different reactors (LWR

and FBR) has been determined in order to furnish data for the assess-
ment of minor actinides arising in burnt nuclear fuel or fuel waste 29 .
If these activities are discharged to waste they constitute a long-
term radiological risk. Their recycle (especially that of 241Am as
the parent of the hazardous actinide nuclide 237 Np ) will not only
reduce that risk, but contribute to nuclear energy generation in a
fast reactor. Therefore the properties of mixed uranium-minor acti-
nide (MA = Am, Cm, Np) oxides are being studied from the point of
view of their irradiation behaviour. In particular thermal conduc-
tivity, phase diagram, Gibb's free energy, fission product composi-
tion, and the reaction between minor actinide mixed oxides and Na 29
have been measured.
- In cooperation with a commercial fuel fabrication company kg-amounts
of 241Am are being purified by repeated oxalate precipitation,
followed by calcination.
- Americium is sorbed from waste effluents by inorganic ion exchangers
containing zirconium 30
20 YEARS RESEARCH AT THE EUROPEAN INSTITUTE FOR TRANSURANJUM ELEMENTS 41
- 241Am Mossbauer sources of high resolution are prepared by deposition

of Am vapour 31
FUTURE WORK
Future work will include the continuation and extension of high pres-
sure techniques for both synthesis and investigation of amer~c~um and
curium containing systems. The growth of single crystqls that are suf-
ficiently large for physical measurements of binary americium and
curium compound systems will be attempted. The preparation and study
of actinide-intermetallics or (ternary) compounds are planned.
ACKNOWLEDGEMENTS
The author thanks his numerous colleagues for their contribution to

the development of our knowledge on americium and curium. Most of the
results presented in this review have been obtained by (in general
international) cooperation between different research institutes and
institutions.
REFERENCES
1. Muller, W., Atompraxis 1969, 15, 1.

2. Buijs, K., Maino, F., Muller,W., Reul, J., Toussaint, J.CL,
J. Inorg. Chem. Supplement 1976, 209.
3. Buijs, K., Toussaint, J.CI., Bottini, G., Intern. J. Appl. Rad.
Isot. 1975, 26, 564.
4. Damien, D., Charvillat, J.P., Muller, W., Inorg. Nucl. Chern. Lett.
1975, ..!J.., 451.
5. Johnson, K.W.R., Leary, J.A., 1964, LA-2992.
6. Wade, W.Z., Wolf, T., J. Inorg. Nucl. Chern. 1967, 29, 2577.
7. Schiffmacher, G., Trombe, F., C.R. Acad. Sci. Parisl969, 268, 159.
8. Muller W., Fuger, J., Spirlet, J.C., J. Inorg. Nucl. Chem.--
Supplement 1976, 139.
9. Muller, W., Reul, J., Spirlet, J.C., Atomwirtschaft 1972, XVII,415.
10. Muller, W., Reul, J., Spirlet, J.C., Revue de Chimie Minera~1977,
14, 212.
11. Ramthun, H., Muller, W., Intern. J. Appl. Rad. Isot. 1975, 26,589.
12. Schenkel, R., Schmidt, H.E., Spirlet, J.C., Transplutonium
Elements 1976, Muller W. and Lindner R., editors, North-Holland
Publishing Company, p. 149.
13. Schenkel, R., Ph.D. Thesis, Saarbrucken, 1977.
14. Martinot, L., Spirlet, J.C., Duyckaerts, G., Muller, W., Bull.
Soc. Chim. Belg. 1974, 83, 449.
15. Martinot, L., Reul, J.,lDuyckaerts, G., Muller, W., Bull. Soc.
Chim. Belg. 1975, 84, 657.
16. Fuger, J., Spirlet-,-J.C., Muller, W., Inorg. Nucl. Chern. Lett.
1972, 8, 709.
17. Fuger,~J., Reul, J., Muller, W., Inorg. Nucl. Chern. Lett. 1975,
..!J.., 265.
42 W. MULLER
18. Ward, J.W., Muller, W., Kramer, G.F., Transplutonium Elements

1976, Muller W., Lindner R., editors, North-Holland Publishing
Company, p. 161.
19. Ward, J.W., Ohse, R.W., Reul, J., J. Chern. Phys. 1975, 62, 2366.
20. Muller, W., Schenkel, R., Schmidt, H.E., Spirlet, J.C.,--
McElroy, D.L., Hall, R.O.A., Mortimer, M.J., J. Low Temp. Phys.
1978, 30, 561.
21. Hall, ~O.A., Lee, J.A., Mortimer, M.J., McElroy, D.L., Muller, W.,
J .. Low Temp. Phys. 1980, 41, 397.
22. Kanellakopulos, B., Blaise-, A., Fournier, J.M., Muller, W.,
Solid State Cornm. 1975, 17, 713.
23. Sari, C., Muller, W., Benedict, U., J. Nucl. Mat. 1972/73, 45, 73.
24. Benedict, U., J. Less-Cornmon Metals 1984, 100, 153. --
25. Haire, R.G., Benedict, U., Peterson, J.R., Dufour, C. Itie, J.P.,
J. Less-Cornmon Metals, in press.
26. Benedict, U., Haire, R.G., Peterson, J.R., Itie, J.P., J. Phys. F:
Metal Phys. 1985, 15, L29.
27. Benedict, U., Syrnp-.-40th anniversary of the discovery of Am and
Cm, Honolulu, HI, Dec. 19, 1984.
28. Naegele, J.R., Manes, L., Spirlet, J.C., Muller, W., Phys. Rev.
Lett. 1984, 52, 1834.
29. Koch L., Bartscher, W., Coquerelle, M., De Meester, R.,
Richter, K., Sari, C., Schmidt, H.E., to be published, Jahres-
tagung Kerntechnik 85, Mey 7-9 1985, Munchen.
30. Crispino, E., Gerontopoulos, P., Arcangeli, G., Cao, S., Forno, M.,
Muller, W., Radiochim. Acta 1984, 36, 69.
31. Spirlet, J.C., pers. cornmunication-,-1984.
FRONTIERS OF CHEMISTRY FOR AMERICIUM AND CDRIUM*
O. L. Keller, Jr.
Oak Ridge National Laboratory
P. O. Box X
Oak Ridge, TN 37831
ABSTRACT. The discoveries of americium and curium were made only after
Seaborg had formulated his actinide concept in order to design the chem-
istry needed to separate them from irradiated 239pu targets. Their dis-
coveries thus furnished the first clear-cut evidence that the series
exists and justified Seaborg's bold assumption that even though Th and
Pa appeared to presage a following 6d series, the pattern established
by the periodic table after Cs and Ba would be repeated exactly after
Fr and Ra. That is to say, a new Sf element rare earth series (the
actinides) would follow Ac in the same way the 4f rare earth series
(the lanthanides) follows La. The consequences of the resulting half-
filled Sf 7 shell at Cm were originally presented by Seaborg as a test
of his hypothesis. Recent research is outlined that substantiates
Seaborg's predictions in new and definitive ways.
Americium and curium are of historic importance in chemistry be-

cause the method used in their discovery by Seaborg, Ghiorso and co-
workers furnished the first clear-cut evidence that the actinide series
exists. And, as is evident in this Symposium, americium and curium are
still furnishing insights into the systematics and the underlying elec-
tronic phenomena implied by the formulation of the periodic table on
the basis of the actinide concept.
As everyone knows, scientists often assume the validity of some
pattern when they set up their own experiments. In his first attempts
to discover Am and Cm, Seaborg (!) made the reasonable assumption that
the pattern of chemical properties set up by D, Np, and Pu would per-
sist to elements 95 and 96. The nuclear reactions employed in these
new element discovery experiments were the bombardment of plutonium-239
with alpha-particles to produce 242Cm and with neutrons to produce 24lpu
which would then decay to 24lAm. The chemical separations of Am or Cm
from the irradiated 239pu targets were then based on the idea that they
*Research sponsored by the Division of Chemical Sciences, Office of

Basic Energy Sciences, D. S. Department of Energy, under contract
DE-ACOS-840R2l400 with Martin Marietta Energy Systems, Inc.
43
44 O. L. KELLER Jr.
would be fairly readily oxidizable to the VI state to ions analogous to

PuO~+ The experiments based on this assumption did not bear fruit,
and it became apparent that some new tack had to be taken.
There were also, of course, various assumptions about the untried
nuclear reactions that were used in these unsuccessful attempts to pro-
duce Am and Cm from the 239pu target. But Seaborg assumed correctly
that the assumptions about the chemistry were what needed changing.
In his first attempts to predict the chemistry of Am and Cm,
Seaborg chose as a guide a very simple pattern - namely, a direct ex-
trapolation from the properties of D, Np, and Pu. When this approach
did not work, he then made the very bold assumption that even in this
heavy element region it was possible to take the regularity set by the
periodic table in the lighter elements quite literally (Figure 1). Lf
the pattern established by the periodic table after Cs and Ba were re-
peated in exactly the same way after Fr and Ra, then a new Sf element
rare earth series (the actinides) would follow Ac in the same way the
4f rare earth series (the lanthanides) follows La. If such a Sf rare
earth series were actually following Ac - but the apparent analogy with
the lanthanides was not really going to be apparent until Am and Cm -
then these new undiscovered elements should have chemical properties
similar to Eu and Gd rather than D, Np, and Pu. Even though we have
had the opportunity to look in the back of the book and see the answer,
the assumptions that led Seaborg to his new formulation of the periodic
table look bold even today, and it is rare indeed that anyone has such
penetrating insights on the basis of only the scanty evidence that was
available at the time. .
In making the assumption that the straightforward regularity of
the periodic table would become apparent once again at Am and Cm,
Seaborg had very little guidance from either experiment or theory (l).
Th and Pa, the first two elements after Ac, behave chemically very much
like Hf and Ta, the first t>-w l'1embers of the Sd transition series.
Thus it was natural to assume that Th and Pa were the first two mem-
bers of the 6d transition series. On the other hand, work in the war-
time Manhattan Project was helpful in showing that something new was
going on in the D, Np, and Pu region because Np and Pu bear no resemb-
lance to Re and Os, and the chemistry of D differs in important ways
from the chemistry of W. Also, although theory did not offer any con-
crete evidence either, several computations made in the 30's and early
40' s did suggest that Sf electrons could be stabilized versus .cd in
the D/Pu region (l,l).
In spite of the extreme skepticism expressed by his colleagues
about the possible validity of the proposed actinide concept, Seaborg
went ahead and designed a new chemical scheme on the basis of it for
separating Am and Cm from the irradiated 239pu targets. His tenacity
paid off because he, Ghiorso, and their colleagues quickly met with
success. The initial evidence for the validity of the actinide con-
cept was thus established by nature of the chemistry employed in the
new element discovery experiments for Am and Cm.
In his 1945 article (~) describing the discovery of Am and Cm and
his formulation of the actinide series, Seaborg laid special stress on
the testing of his hypothesis through the extra stability that would be
FRONTIERS OF CHEMISTRY FOR AMERICIUM AND CURIUM 45
imparted to the III oxidation states of elements 96 and 103 by the

half filled 5f 7 and filled 5f 14 shells that should occur in them if
actinium really is the first member of a postulated new 5f rare earth
series. He mentioned several times in the article, in fact, that Cm
should exhibit the III state almost exclusively because of its 5f 7
half filled shell.
Experimental determination of the extra chemical stability of the
III oxidation state of curium relative to americium and berkelium furn-
ished important early support for the actinide concept. Of parallel
interest, but much later, it was shown also by R. J. Silva and co-
workers (5) that Lr has a most stable oxidation state of III as pre-
dicted by-Seaborg for the last member of the actinide series. This
experiment on Lr (the only chemical one that has ever been performed on
this element) was particularly important since shortly before it was
done the surprising discovery had been made by Ma1y, Sikke1and, Silva,
and Ghiorso that No, the second to the last member of the series, is
most stable in the divalent sta~e (&).
Although no additional chemical experiments have been possible yet
with Lr, several types of experiments have demonstrated the extra sta-
bility of the trivalent stat.e in Cm that Seaborg predicted. A good
example is the heat of sublimation of Cm over that of Am and Bk. This
effect is shown from data of Kleinschmidt, Ward, and Haire (7) in
Figure 2. Their value of the heat of sublimation for Lr was-predicted
on the basis of its trivalency, which has already been established for
the trivalent ion in aqueous solution as noted above. The low heats
of sublimation of Fm, Md, and No were predicted on the basis of their
expected divalency. Actually, the diva1ency of Fm and Md has been
demonstrated experimentally already by the gas chromatography results
of Hubener and Zvara (8) and there can be little doubt that No is di-
valent. So the heat of sublimation of Lr will be a most important
quantity to measure. It may actually be much lower than predicted by
Kleinschmidt and coworkers because, although Lr is trivalent in
aqueous solution, the electronic configuration of the metal may be
different from what would be predicted on the basis of analogy with Lu.
Strong relativistic effects in the Lr region will definitely stabilize
the 7s 2 closed shell more than the 6s 2 closed shell in Lu, and they
also could cause the replacement of the expected 6d electron, which is
very interactive, with a 7Pl/2 electron, which is relatively inert.
These two effects could work in conjunction to lower the heat of sub-
limation of Lr substantially (2).
Fortunately, it has become possible recently to experimentally
demonstrate in a direct manner the extra stability of the highly local-
ized 5f 7 shell in curium. In essence, the approach is to test the
stability of the f shells in transp1utonium metals by placing them
under a high enough pressure that they de1oca1ize into the spd bands.
That is to say that the pressure is high enough to cause the f elec-
trons to .change from a localized non-bonding character into a deloca1-
ized bonding character. A recent review has been given by Benedict (10).
All four of the metals - Am, Cm, Bk, and Cf - now have been studied
(11,12,13). An illustration using results from a paper by Roof, Haire
and coworkers (11) is given in Figure 3. In this experiment, Am metal
46 O. L. KELLER Jr.
PERIODIC TABLE SHOWING HEAVY ELEMENTS AS MEMBERS OF AN ACTINIDE SERIES

Arrangement by Glenn T. Seaborg
1945
1 1 2
H H He
1.008 1.0OB 4.003
3 4 5 6 7 8 9 10
Li Be B C N 0 F Ne
6.940 9.02 '".82 12.010 14.008 16.000 19.00 20.183
11 12 13 13 14 15 16 17 18
Na Mg AI AI Si P S CI A
22.997 24.32 26.97 26.97 28.06 30.98 32.06
35.457 39.944
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.096 40.08 45.10 47.90 50.95 52.01 54.93 55.85 58.94 58.69 63.57 65.38 69.72 72.60 74.91 78.96 79.916 83.7
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Cb Mo Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.48 87.63 88.92 91.22 92.91 95.95 101.7 102.91 106.7 107.880 112.41 114.76 118.70 121.76 127.61 126.92 131.3
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
"'e.
58)1
Cs Ba HI Ta W Re Os Ir Pt Au Hg TI Pb Bi Po Rn
r
L,
132.91 137.36 J892
178.6 180.88 183.92 186.31 190.2 193.1 195.23 197.2 200.61 204.39 207.21 209.00 222
87 88 ... I 91Pa I 92U I Np
93 I 94
Ra
89
A,
A,
senes
90
Th Pu
95 I 96 I
LANTHANIDE
SERIES
Figure 1. Reprinted with permission from Ref. 4) Copyright 1945,

American Chemistry Society.
600
".
............
'" \.
500
I·'"
". .\
400
...,E 300
~
o:I:'"
<l
200
•
100
•
0
MEASURED
EXTRAPOLATED
'
'"._-C>---r>-
o
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
ELEMENT
Figure 2. Heats of Sublimation of Actinide Metals (Data from Ref. I).
orthorhombic = a-uranium structure

( 5 f delocalization )
,
Am "
dhcpl Icc Imono
"' I.. 'v orthQ.r~ombIC
.
, ,
, ,
,
,
-, -" ,
Cm
dhcp
I Icc
II
, ,
>1 "'
orthorhombic
, , ,
, ,
, , ,
k 1
II
Icc 1<:, , "'
-- -
dhcp orthorhombic
, ,
,
, II III......... IV
CI
dhcp
I fcc
I fcc' -\ orthorhombic
10 20 30 40 50 60
Pressure (GPal
Figure 3. Phase Changes and Delocalization of f orbitals in Am

metal under pressure (Ref. ll).
~)
~.
1.0 ~
cA:,
dhcp
.,o
E
:I
"0
> .92
.,
E ... fcc
:I
"0 \,
>
.84
....... ----- a -u
.78~----~-- ____~____- J_ _ _ _ _ _~------U

o 4 8 12 is 20
Applied Pressure. GPa
Figure 4. Half-filled shell stabilization of Cm metal shown by

anamalously high pressure for f orbital delocalization (Ref. ~).
48 o. L. KELLER Jr.
ultimately assumes the alpha uranium structure which is associated

with fspd hybridization.
Thus the high pressure technique gives an ideal way to determine f
orbital stability because the more stable the orbitals, the higher the
pressure required to bring about their delocalization. The results for
the four metals Am, Cm, Bk, and Cf are given in Figure 4 (14). Since
the pressure required to delocalize the f orbitals in Cm is-much higher
than in Am or Bk, its extra stability is clearly shown. Thus the sta-
bility of the f shell in Cm is demonstrated directly and its position
as the middle member of the actinide series is verified in a most de-
finitive way.
Another verification of the actinide concept comes from the discov-
ery by J. L. Smith and R. G. Haire (15) of superconductivity in Am
metal. The superconductivity is allowed in Am metal because it has a
nonmagnetic ground state like La, which is also a superconductor. But
the important point for adding to our understanding of the systematics
of the actinide series is that Am metal is trivalent and nonmagnetic
because it has a unique f6 configuration in the ground state. Even
europium, americium's homologue in the lanthanide series, does not ex-
hibit the f6 configuration in the metal (as shown by its divalency) and
is not superconducting. Smith and Haire point out also that the f elec-
tron character in Am and La must be important in allowing superconduc-
tivity since other trivalent elements that do not have available f
orbitals are not superconducting. Studies of Am superconductivity
under high pressures should be most enlightening in elucidating the
role of f Qrbitals in this phenomenon, and hopefully we will be treated
to the results of such experiments in the near future.
The discovery of Am and Cm was especially useful for developing an
understanding of the underlying 5f electronic properties of the series
because they introduced a simplicity that was not offered by U, Np, and
Pu. But suppose, for example, that Am had turned out to be divalent
like No! Then it would have been even more difficult to discover Am
although, fortunately, Cm would still have saved the day. Actually,
even with the simplicity introduced by the discovery of Am and Cm,
there was still enough confusion that many scientists provisionally
classified the elements Th through Cm as both sub-group elements and as
a second rare earth series at the same time. One of the scientists who
did that was Seaborg himself (Figure 1). But within a few years it be-
came obvious that Seaborg was correct in placing them as a second rare
earth series and the sub-group classification disappeared.
Certainly a key result of the efforts of transuranium chemists
over the last 40 years has been the validation and elucidation of the
actinide concept. As we move ahead into further investigations of the
architecture of the periodic table through chemical studies of Lr, the
first members of the transactinide series and beyond, we are fortunate
to have as a guide the valuable lessons from the work of Seaborg and
his coworkers in those exciting early days of the discovery of Am and
Cm.
ACKNOWLEDGMENT. I thank Drs. R. G. Haire, J. K. Gibson, and U.

Benedict for helpful discussions during the preparation of this
article.
REFERENCES
1. Seaborg, G. T. Man-Made Transuranium Elements, Prentice-Hall,

Inc., Englewood Cliffs, NY (1963).
2. van Spronsen, J. S. The Periodic System of Chemical Elements,
Elsevier, Amsterdam (1969).
3. Seaborg, G. T., Katz, J. J., and Manning, W. M. The Transuranium
Elements, Part II, McGraw-Hill Book Company, Inc., New York (1949),
pp. 1492-1524.
4. Seaborg, G. T. Chern. Eng. News, ~l, 2190 (1945).
5. Silva, R., Sikkeland, T., Nurmia,-M., and Ghiorso, A. Inorg.
Nucl. Chern. Letters, 2, 733 (1970).
6. Maly, J., Sikkeland, T., Silva, R., and Ghiorso, A. Science, 1~~,
1114 (1968).
7. Kleinschmidt, P. D., Ward, J. W., and Haire, R. G. Proc. Symp. on
High Temp. Materials, Chern II, Vol. 83-7, Z. A. Munir and D.
Cubicciotti, eds., The Electrochemical Society, Inc., Pennington,
NJ (1983), pp. 23-31.
8. Hubener, S. and Zvara, 1:-"-
Radiochemica Acta, lL 89 (1982).
9. Keller, Jr., O. L. Paper presented at the International Confer-
ence on Nuclear and Radiochemistry, Lindau, FRG, October 1984. To
be published in Radiochemica Acta.
10. Benedict, U. J. Less-Common Metals, 1QQ, 153 (1984).
11. Benedict, U., Peterson, J. R., Haire,-R~ G., and Dufour, C. J.
Phys. F: Met. Phys., 1~, L43 (1984).
12. Benedict, U., Haire, R~-G., Peterson, J. R., and Itie, J. P. J.
Phys. F: Met. Phys. (to be published).
13. Roof, R. B., Haire, R. G., Schiferl, D., Schwalbe, L. A., Kmetko,
E. A., and Smith, J. L. Science, ~QZ, 1353 (1980).
14. Haire, R. G., Benedict, U., Peterson: J. R., Dufour, C., and Itie,
J. P. J. Less-Common Metals (in press, 1985).
15. Smith, J. L. and Haire, R. G. Science, ~~~, 535 (1978).
Part II
Solution Chemistry and Analytical Procedures

STUDIES OF AMERICIUM AND CURIUM SOLUTION CHEMISTRY IN
THE USSR
B.F.Myasoedov and N.Yu.Kremliakova

V.I.Vernadsky Institute of Geochemistry and
Analytical Chemistry USSR Academy of Sciences
19 Kosygin street, 11797 Moscow, USSR
ABSTRACT. The historical review of the fundamental

achievements on Americium and Curium properties study
in the USSR is presented in the paper. The main atten-
tion is payed to the properties of these elements in
the highest oxidation states. Methods of obtaining,
kinetics of redox processes, mechanism of transformation
and stability of Am(IV), Am(V), Am(VI), Om(IV) and
Cm(VI) are discussed. The values of redox potentials
for a number of reactions are presented. Amerioium
behaviour in the highest oxidation states during extrac-
tion, sorption and precipitation, as well as the new
methods of this element determination are disoussed in
conclusion.
The ohemical properties of americium and curium in solu-

tions were well studied for forty years sinoe the time
of their discovery by G.T.Seaborg, L.O.Morgan, R.A.James
and A.Chiorso (1,2). Numerous data concerning the methods
of americium and curium preparation and stability in dif-
ferent oxidation states, the kinetics of redox reaotions,
the hydrolysis and complexation and the composition of
forming compounds have been accumulated. On the base of
fundamental knowledge of the chemical properties of ame-
rioium and curium a lot of Simple and effective methods
of isolation, oonoentrating and separation with the use
of solvent extraction, sorption, precipitation and co-
precipitation have been suggested. Highly sensitive and
selective methods for the determination of amerioium and
curium in different materials, both technological and
natural have been developed. The investigations of the
chemical properties of these elements are carried out in
many oountries, but espeoially widely and actively in
the USA, USSR, France, GFR and England. In the present
review we would like to give briefly the main results of
53
N. M. Edelstein et al. (eds.). Americium and Curium Chemistry and Technology, 53- 79.
54 B. F. MYASOEDOV AND N. Yu. KREMLIAKOVA
americium and curium ohemical properties investigations,

oarried out in the USSR. But the authors have not attemp-
ted to give an exhaustive analysis of all of the Soviet
literature concerning this question. The works of the
fifties-seventies are quite fully summarized in reviews
and monographs (3-6).
The period of investigation of the ohemical proper-
ties of amerioium and ourium in our oountry can be divi-
ded oonditionally into two stages. The first (till the
seventies) mainly dealt With the study of ohemical pro-
perties of amerioium and ourium in the trivalent oxida-
tion state and their behaviour during the prooesses of
solvent extraotion, sorption and oopreoipitation. The
seoond stage, starting at the beginning of the seventies,
gave its prinoipal attention to the investigation of ame-
ricium and ourium chemical properties in "unusual", ohi-
efly, the highest oxidation states and the utilization
of the latter in new separation and isolation methods.
1. CHEMICAL PROPERTIES OF TRIVALENT AMERICIUM AND CURIUM

1.1. Complex Formation
The study of americium and ourium oomplexation with in-
organic and organic ligands has been performed in the
Soviet Union sinoe 1951. Speotrophotometry,methods of
solubility, e1eotromigration, solvent extraotion, ion
exchange and others have been used for this purpose. The
oomposition of simple and complex americium and ourium
oompounds, isolated from solutions has been also studied
by different methods. The oomplex formation with inorganio
ligands, suoh as perchlorate (1), ohloride (1,8), nitrate
(9,10), thiooyanate (11), sulfate (9), carbonate (1),
phosphate (12,13), as well as trtmetaphosphate (14) has
been studied. Amerioium (III) and ourium {III) hydroxides
are preoipitated by ammonium hydroxide and alkali (15)
as pink gelatinous oompounds. Am(OH)3 solubility in 0.3 M
NH40H solution is equal to 2.4 mg Am7l at 20°C (16) and
that of Cm - 10 mg dmll (15). Yakovlev and oollaborators
(11) prepared amerioium sulfate Am2(S04)3.5 H20, and the
double sulfates of americium With potassium, rubidium,
oesium and thallium. They studied phase diagrammes, ab-
sorption spectra and solubilities of these oompounds.
The double sulfate of ourium With potassium has been
desoribed in a paper (15). Its solubility varies from 10
to 20 mg Cm/l depending on acidity. Curium oarbonate has
been shown to dissolve completely in 40% K2C03 solution
(15) •
The oomplexation and the oomposition of amerioium
and curium ions with organio ligands, important in dif-
AMERICIUM AND CURIUM SOLUTION CHEMISTRY IN THE USSR 55
ferent chemical analytical procedures, including the iso-

lation and determination of these elements have heen
studied in detaile In ac~tate sol~tions Am~III) and Cm(III)
form c~mplexes of the ML + and ML2 types. The stability
of CmL2 complexes is higher than that of americium (18).
Great attention has been given to Am(III) and Cm(III)
complexation with oxalate-ions. These complexes have been
studied by ion-exchange (9,19,20), solvent extraction
(21,22) and electromigration (23). The composition of
these complex compounds, their stability and solubility
in different media have been determined (16). Lebedev
and coworkers (24) determined the composition of americium
oxalate Am2(C204)3.9H20. In tartaric acid solutions with
pH 2-9 americium and curium form like rare earths t com-
plexes of the ML+ ~~d MLe types t21 22,25) and with cit-
rate ions - MLO, M~-and M(HL)~ (23~. Stability constants
of americium and curium with some ~-oxycarboxylic acids,
widely used in ion exchange separation methods, such as2+
with lactate (26,27) and oC-oxybutyrate-iona (of the Mn ,
ML[ and MLj types) (28-30) have been determined. Triva-
lent americium and curium form the most stable complexes
w1~h polyaminopolyacetic acids. The formation of MLo and
ML - complexes with nitriletriacetic acid in the pH re-
gion of 2 to 6 has been established. Their stability con-
stants differ little from the analogous rare earths (21,
22,31). Americium and curium form with ethylenediamine-
tetracetic acid (EDTA) complexes mainly of the ML- type
(20-22,32). These complexes exist in solution in a pH
range of 1-3,3. At high acidities (pH<2) they form proto-
nated complexes MHLO. Americium and curium form complexes
with 1,2-diaminocyclohexanetetraacetate - (21,22,33) and
diethylenetriam1nepentaacetate (DTPA)-ions (34) that are
more stable than these with EDTA. The stability constant
of americium and curium complexes with DTPA of the MHL-
type, d,termined by the electromigration method, is equal
to 2·10 4 (34). Complexation of americium and curium with
phosphororganic ligands has been studied by a number of
workers (35-39).
1.2. Isolation and Separation Methods
Precipitation,solvent extraction, sorption and electro-
chemical methods all have been developed to separate and
isolate trivalent americium and curium.
1.2.1. PreCipitation. In early work in order to isolate
microquantities of americium and curium coprecipitation
with the following precipites has been widely studied:
lanthanum fluoride (40), potaSSium sulfate (41,43), double
sulfate of potassium and lanthanum (44-46), oxalates of
calcium, uranium (16) and lanthanum (47) as well as some
organic coprecipitants (48-50).

1.2.2. Solvent Extraotion. Bxtractants of different
classes such as organophosphorous compounds, high-mole-
oular-weight amines, beta-diketones and others, as well
as their mixtures (synergistio extraotion) have been used
for extraotion and separation of americium and curium.
The application of neutral organophosphorous compounds
have been studied most. Trialkylphosphates (RO»)PO, tri-
alkylphosphonates (RO)2RPO, trialkylphosphinates (RO)R~O
and trialkylphosphine oxi~es R)PO belong to this olass_
According to the data of the papers (51,52) the extracta-
bility of Am and em deoreases in the order R)PO) (RO)R~O
> (RO)2RPO ) (RO}3PO. The effeot of structure and the
nature of substituents at the phosphorous atoms (51,5),54)
the concentrations of acids and salting out agents in the
aqueous phase (55,58). and the extractant concentration
(40) on americium and ourium extraotion effioienoy have
been thoroughly studied. Different authors (55.57,58,59)
proved that the composition of extracted amerioium and
curium speoies with any of four kinds of reagents is
Me(N03»)-)A. Tributylphosphate (TBP) and phosphine oxides
are often used in practice. More recently bidentate orga-
nophospborous compounds have been intensively studied for
americium and ourium extraction from high acidity solu-
tions in the presence of large amounts of salting out
agents (60,61). As for other organophosphorous compounds,
dialkylphosphoric acids, particularly di-2-ethylhexyl-
phosphoric acid (HDEHP), have been widely employed as
extractants for amerioium and curium. Kosyakov and co-
workers (62) have shown the efficiency of amerioium extra-
otion from 0.5 M RNO) by HDEHP solutions to be inversely
proportional to solvent polarity. The efficienoy also
increases with the elongation of the normal alkyl radical.
For back extraction of americium from the organic phase,
they suggested the use of 2-4 M RNO, or K2co) solutions
(62). Americium and curium separati6n from some rare-earth
fission elements takes place during extraction from con-
centrated LiCl solutions (62,6). Among the extractants
of the other class, used for TPE isolation, including tri-
valent Am and em, tertiary amines have been the most in-
vestigated. It has been shown in the referenoe (64) that
Am and C14 extraotion by 'lOA solutions in oyolohexane- is
greatly influenoed by the nitrio acid conoentration and
the nature of the salting out agent and diluent. Chudinov
and ooworkers (65) calculate the separation factor of Am
and Cm in the system of methy1diocty1amine-nitrate in
xylol-LiNO) to be close to ) and to depend weakly on amine
and LiNO) concentrations. Hydrochlorio acid solutions have
proven to be useful for Am and Om separation from rare
earths. Thus the effeot of chloride-ion, H+-ions and metal
ion oonoentrations on the separation faotor of Cm and Eu

have been studied in detail (6). The largest separation
faotor has been obtained in the system of 20% tridecyl-
amine in xylol - 11.2 M LiCl solution. The diluent nature
oonsiderably affects americium and ourium isolation, but
has praotically no effeot on the rare earths.
Beta-Diketones have also been used for amerioium and
ourium isolation and their following determination. 1-phe-
nyl-)-methyl-4-benzoyl-pyrazolone-5 (PMBP) is the most
thoroughly studied example in the works of the soviet
authors (66). It extraots a number of elements, inoluding
ourium (67) from more aoid media than thenoyltrifluoro-
aoetone (TTA). The presenoe of salts greatly influenoes
amerioium extraotion by this reagent (68). The usage
of PMBP allowS the attainment of a high degree of amerioi-
um separation from plutonium, based on the extraotion of
the latter by 0.1 M PMBP solution in benzene from) M
lINO) solution (69). The efficienoes of ameriQ.ium t:)I.nd ourium
extraotion by beta-dike tones inorease strongly in the
presenoeof organio phase donor aotive additives such as
TPB and TOPO (synergistio extraction). The most attention
has been paid to amerioium and ourium extraction in the
systems: TTA, PMBP.TBP, TOPO (67,70). In PMBP-TBP system
the oomposition of extracted ourium oompound has been
found to be Cm(PMBP»).2TBP (70). The americium extrao-
tion oonstant in suoh a system is two fold greater than
in TTA-TBP system (71). The diluent nature influenoes the
synergistio effeot: amerioium and ourium extraotion cons-
tants and adducts stability oonstants decrease with the
increasing of diluent polarity (71).
1.2.). Sorption. For americium and curium isolation and
separation praotically all known methods have been stu-
died: ion exohange on organic resins, extraotion chroma-
tography, partition and thin-layer chromatography, and
sorption on inorganio and ohelate resins. Cation exohan-
gers of different types have been used for the separation
of maoroamounts of americium and curium by ammonium J:.-
oxybutyrate solutions (15)i for group ooncentration of
TPE in HCl04 solutions (72), for TPE and REB separation
in HCl solutions (6) or in the presence of alcohols (7);
for americium and ourium separation from La and Pu in 1 M
RNO) solution (10,72). The applioation of anion exohangers
and aqueous-organic solutions as eluents gives new possi-
bilities for the separation of elements with close chemi-
cal properties (75-81). Amerioium and curium separation
proves to be the best on anion exchangers with small DVB
{-4%) content and in 0.5 M RNO) solution in the presenoe
of 80% of CH30H. Their concentration is best made on the
resins with high DVB content (8%) and from ~0.5 M RNO)
solutions containing ~ 90% alcohol (78). By sorption on
58 B. F. MY ASOEDOV AND N. Yu. KREMLIAKOV A
anion exchangers from 0.5-1 M HNO) in 90% alcohol Am and

Cm can be separated from other elements, which are poo~
ly sorbed under these oondi tions: elements with Z < 56,
as well as Hf,Ta,Re,U,Np(V). The separation from fission
rare earths occurs during resin washing with 0.5 M
NH4NCS solution in 80% alcohol (76,79,80), and the sepa-
ration of the americium and curium remaining on the resin
is carried out with 0.5 M HNO in the presence of 85% of
alcohol (81). The system anio~ exchanger-aloohol solution
in nitric acid can be successfully used for the isolation
of americium curium and the other TPE in a highly pure
state (82,83~. Introducing oC-hydroxyisobutyric acid in
water-alcohol solutions of nitric acid considerably in-
creases the separation factor of Am-em pair to~ 6 (85,
86).
There are some references, summarized in the review
(87), ooncerning the application of inorganic sorbents
for americium and curium separation and isolation from
solutions of inorganic acids and their salts. In order
to improve the selectivity of sorbents, different chelate
groups are introduced into them. Myasoedov and Molochni-
kova (88) have studied the possibility of the application
of chelate resins on the base of aminopolystyrene and
araenazo I for americium and curium isolation from Hel,
HNO) and H2S04 solutions. This sorbent has proven to be
very useful f6r the separation of these elements in in-
organic acids solutions and for their separation from
europium. The possibility of the separation of americium
and curium tracer quantities from uranium and plutonium
by thin-layer chromatography on silicagel with TBP has
been studied in the paper (89).
1.2.4. Electrochemical Methods. These methods are not
widely used for americium and curium separation. They are
usually employed for electrochemical isolation of these
metals, for making samples for radiometric measurements
and for the investigation of their states in aqueous
solutions (13,23,30, 32-34,39). In paper (90) the authors
have suggested a method for separation of tracer amounts
of americium and curium, based on their selective sorp-
tion by a platinum anode.
1.3. Methods of Determination
Spectrophotometric, radiometric and emission spectrometry
methods have been developed for the detection and quanti-
tative determination of americium and curium in the early
papers. The first colored reaction of Am and em with the
use of arsenazo III has been described in paper (91). The
spectrpphotometric method based on this reaction allows
the determination of these elements down to concentra-
tions of 0.02 mkg/ml (92). Absorption speotra of amerioium

in different oxidation states in aoid solutions and the
use of oharaoteristio absorption bands for the quantita-
tive determination of these elements have been thoroughly
studied in papers (7,16,93,94). This method has been wide-
ly used for the investigation of Am(V) disproportionation
in perohlorio (16,98), nitrio (16,95) and sulfurio aoids
(7,16,95,96), as well as Am(V) self reduotion in solutions
of perohlorio (7,16,94,95)t sulfurio (16,95), nitrio (16,
95,97) and hydroohlorio (7) aoids.
In order to determine Am in samples of air, waste
waters and other samples in the presence of Pu and U, an
oC-radiometrio method with a preliminary ion exohange iso-
lation of ~~rioium has been developed (98). Th23~etermi-
na tion bf Am by the 0' -rays of the daughter Up, is
oarried out by ~he extraotion of the latter with a mixtu-
re of PMBP and TBP (99).
The emission speotrum of amerioium has been well stu-
died. Some oharaoteristio bands have been suggested for
the quantitative determination of this element (100).
2. CHEMICAL PROPERTIES OF AMERICIUM AND CURIUM IN THE

HIGHEST OXIDATION STATES
Transplutonium elements are known to be characterized by

a larger number of oxidation states than the analogous
4f-elements-lanthanides (Table 1). In aqueous solutions
most of TPE are in the trivalent oxidation state in the
absence of oxidizing or reducing agents. However Am,Cm,
Bk and Cf can exist in the highest oXida~ions states, whi-
le Md can be rather easily reduced to Md~. The most stab-
le oxidation state for No in aqueous solutions is +2. Re-
cently the existence of Am(VII) (101) Cm(VI) (102),
Cf(V) (10) and Cf(IV) (104) and Md(I) (105), under dif-
ferent conditions has been proved. As mentioned earlier,
the main emphasis in studies of amerioium and curium pro-
perties in the second period in the USSR has been given
to the investigation of their unusual oxidation states
and to their use in methods of isolation, separation and
determination.
2.1. Oxidation State+4
Both americium and curium can be prepared in the +4 oxi-
dation state. Attempts to obtain americium and curium in
the tetravalent state in aqueous solutions have long been
unsuccessful due to the very high values of the potentials
of the Me(IV)!Me(III) pair, whioh for these elements are
equal to 2.44 and ~3V respectively. In acids or in car-
bonates of alkaline metals, Am(V) or Arn(VI) have been
'"o
TABLE I. Oxidation states and standard redox potentiala of TPE
Oxidation Am em Bk Cf Es l"m Md No Lr
states
+7 t
+
+6 +1.1 ±
+
+5 +1.1 +
+ + -;t +
+ -
+4- +2.45 +3:1 +1.67 +3.1 +4.5
+ + + + + + + +
+3 -2.6 -3.8 -2.8 -1.7 -1.2 -0.65 -0.15 +1.45 +
?'
+2 + + + + + + ~
- - - - t t a::
><
;l>
+1 +
- '"0tT!
t:I
0
<:
;l>
+ - the most stable oxidation state in aqueous solutions. Z
t:I
+ - relatively stable oxidation state. :z:
t - unstable oxidation state. p><
;0::
Redox potentials are in volts (versus normal hydrogen electrode) and belong ::<I
tT!
to neighbouring (in vertical) couple of ions. a::
t-'
s;'
;0::
0
<:
;l>
obtained by the action of oxidizing agents on Am(III)

solutions. And upon dissolving amerioium dioxide in aoids
the mixture of Am(III) and Am(VI) is obtained. Only in
strong complexing media in which an essential decrease
of redox potentials is observed has it been possible to
develop reliable methods for americium and curium stabi-
lization in the tetravalent oxidation state.
Asprey and Penneman were the first (106) to obtain
Am(IV) in aqueous solutions by dissolving Am(OH)4 in satu-
rated ammonium fluoride solution. Over the last few years
a number of convenient practical methods for oxidizing
Am(III) to Am(IV) in 8-15 M H3POt have been developed.
Electrochemical and chemical ( 07,108) (by the mixture
of ~3P04 and (NH4)2S208 (108-112) methods have been use~
Am(IY) stability in phosphoric acid solutions has been
studied in detail (109,110,112,113). In 8-15 M H3P04
Am(IY) reduces to Am(III) and in 2-7 M H3P04 Am(VI) forms
together with Am(III). Besides the characteristic bands
at 742 and 920 nm in the absorption spectrum of Am(IV)
in H3P04 solution there is af intense band in the UV area
( £ 3331:1942, e370=1085:t:20 m- cm- 1). This band is used for
spectrophotometric determination of americium in solutions
oontaining curium (108).
It has recently been proven (114), that Am(IY) can
be obtained in acetonitrilic solutions, containing 0.3-
2,0 M H3P04. With +1.4Y anode potential with respect to
mercury-sUlfate electrode, americium can be completely
oxidized to Am(IV) in 30 minutes. Oxidation occurs both
in pure acetonitrilic solutions and in aqueous-acetonit-
rilic with water content up to 50%. On standing Am(IV)
gradually reduces to Am(III) according to the first order
reaction with a half-life of 5.6 hours. Am(IY) dispro-
portionation is not observed under these conditions. Valu-
es of the formal redox potential of the Am(IY)/Am(III)
couple in 0.3-2.0 M H3P04 solutions in acetonitrile
(1.3-1.1V with respect to the mercury-sulfate electrode)
and in solutions containing 0.5 M H3P04 up to 20% of wa-
ter have been measured. The l? ossibili ty of quantitative
oxidation of americium to Am{IY) in H3P04 solutions in
acetonitrile has been used for the coUlometric determina-
tion of americium in microgram amounts by Am(IY)/Am(III)
couple with an accuracy of 1-2%.
Americium (III) oxidation to Am(IY) can also be car-
ried out in solutions of unsaturated heteropolytungstates,
K7PW11039 or K10P2W17016. Significant changing of the
redox potential of the Me(IY)/Me(III) couple occurs due
to the strong complex formation of tetravalent actinides
ions with unsaturated phosphotungsten acids. The maximum
changes for Am,Bk,Ce and plutonium take place at pH 4-5
and are equal to 0.9-1.0V relative to Eo for the corres-
ponding oouple in 1 M HCI04 (115.116). Oxidation of
Am(III) to Am(IV) in solutions of unsaturated heteropoly-

tungstates is carried out by persulfate ions with heat
(115, 117-121), or electrochemically (115.120). Kylyako
et al.(112) have studied in detail the kinetics of elec-
trochemical oxidation of americium. Quantitative oxida-
tion of americium takes place at the anode potential of
+1.77V. Under these conditions Am(IV) is stable in the
presence of oxidizing agents for several days (117 J 119);
and without oxidants it is reduced at a slow rate \about
1% per hour) (115,120) by radiolysis products and by wa-
ter. It also has been proved that americium (III) can be
oxidized to Am(IV) without heating by a mixture of AgNO)
with (NH4)2S20a in 0.1-6 M RNO) solutions containing a
four-fold excess of K10P2W17061 with respect to Am (12).
In such solutions at HNO) concentration ~) M, .Am(IV) is
stable for 5-7 days. Obtaining stable Am(IV) in phospho-
tungstate solutions undoubtedly provides an opportunity
to use such a system for analytical purposes.
In dilute solutions of Am(Cl04») containing N20,
S20~- or XeD), exposed to y -rays or pulses of electrons t
a non-stable Am(IV) appears, which transforms very quick-
ly (~10-Jsec) to Am(V) and Am(VI) (124-126). As has been
mentioned above, tetravalent americium is stable in solu-
tions of potaSSium phosphotungstate for several days (12).
This stability has allowed recently the establishment for
the first time of the conditions for tetravalent americium
extraction (127) • .Am(IV) is quantitatively extracted from
0.5-1 N H2S0~ solutions by )% dioctylamine (DOA) solution
in dichlorethane (DCE) in the presence of heteropolyanio-
na, which on passing to the organic phase, stabilize tet-
ravalent americium (Fig.l).
100
~
~
80
60
241Am (lyJ
40
20
2 3 4 5
[H2Sa.],N
Fig. 1 Americium extraction by dioctylamine from
H2 S04 solutions in the(Dresence~f 10-) M
K10P2W17061. 1-10 M .Am IV); 2- Am{IV);
3-10 M Am(III).
~
t"=1
)<'
Pi
~
»
~
n
c:::
)<'
~
'"o
t=;
>-l
TABLE II. Selective coulometric determination of americium oZ

n
==
tTl
S!:
~)<'
Composition of the Oxidation time, Detection Relative ><:
Couple solutions Hrs limits, standard Z
deviation >-l
==
tTl
c:::
'")<''"
Am(VI)/Arn(V) 2M H2P0 4+O.1M HCI04 1.5 5 0.015
Am(IV)/(IIl) 0.5M H)P04 in CH3CN 0.5 5 0.02
Am(lV)/Am(III) 0.1M HCl0 4+6·10- PW 0.25 6-70 0.03
Am(IV)/Am{lIl) 1-2M Na2CO) (pH.10) 0.5 5 0.025
0'>
w
64 B. F. MY ASOEDOV AND N. Yu. KREMLIAKOVA
The presence of Am(IY) in the organio phase has been pro-

ved spectrophotometrioally (Fig.2) •
• 00 ~ 480 5ro ~ 600 6ioO (110 !lIl1 tl20

.A.NM
Figure 2 Ab.sorption spectra of 10-3 M Am(III) and
Am(IY}. 1-Am(II~); 2-Am{IY} in 1 N H2S04 in the
presence of 10- M K10P2W~7061; J-Am{IY) in inor-
ganic extract (DOA in DOE).
The period of half-reduction of Am(IY) in the organic
phase is equal to 2.5 hours. The existence of reversible
electrochemical couples for Am(YI)/Am(Y} and Am(IY)/
Am(III) has permitted the development of coulometric met-
hods for americium determination with a high sensitivity
and accuracy (Table 2). The possibility of electroohemi-
cal oxidation of Am(III) up to Am(IY) and Am(YI) , and a
high stability of the higher oxidation states of ameri-
cium under certain cond.i tions underlie thes e methods.
Recently the stable Am(IY) has been shown to exist not
only in 10-15 M phosphoric acid solutions but to be for-
med during electrochemical oxidation of Am(III) in 0.3-
2.0 M H3P04 solutions in acetonitrile. The available
eqUipment allows the determination of 5-10j"g of ameri-
cium with an error of 1-2%.
It is possible to determine 5 to 100~g of americium
by the Am(IV)/Am(III) couple in 0.1 M HOlO, in the pre-
sence of 6.10- 3 M potaSSium phosphotungstate (128). In
this solution Am(III) is completely oxidized to Am(IV)
in 15 minutes under a potential of 1.7Y. Am(IV) is very
stable in the presence of phosphotungstate-ions and so
the 10-fold excess does not prevent americium determina-
tion. Many elements oxidizable under these conditions
(Pu,Oe and others) also do not prevent this determination,
since they are not reduced at the potential of 1.17Y. The
measurement error does not exceed 3% even in the presence
of 100-fold quantities of other metals.
Coulometric determination of americium by the
Am(IV)/Am(III) couple can be carried out in an acetonit-

rile solution of phosphoric acid where Am(III) has been
established to be oxidized rapidly and reversibly elec-
trochemically to Am(IY) (114). Microgramm amounts of ame-
ricium can be determined with a measurement error of 1-2%
in 0.5 M H3P04 solutions in acetonitrile.
Curium in the trivalent oxidation state is very
stable in aqueous solutions and in most cases it is not
oxidized under the conditions that Am(III) oxidation oc-
curs. This can be explained by the high values assumed
by the o~idation potentials of the Cm(IV)/Cm(III) couple,
which are about 0.6-o.7V higher than that of Am(IV)/
Am(III) one. Tetravalent Cm was originally obtained by
dissolving CmF4 in a concentrated solution of cesium and
ammonium fluoride (129). However, curium (III) can be
oxidized to Cm(IV) by potassium persulfate in KIOP2W17061
solution on heating (115,117), though the stabi 1ty of
Cm(IV) under such conditions is not high. It completely
reduces in 1.5-3 hours. The solution absorption spectrum
of Om(IV) and the data on its reduction are presented on
Fig.3. The Cm(IY) absorption spectrum in solution is cha-
racterized by a broad-band with maxima at 520,748 and 932
nm (115).
90 2
90
ItDO 510 710 880 10100

",ef""9tn • lito
Fi~ure 3. Absorption spectra of Om(III) (1) and

Cm(IY) (2-5) in solution of potassium phosphotung-
state. 0 .4.06x10-4 M, 25°C. Time after oxida-
tion, 2-0.5 min; 3-60 min; 4-110 min; 5-140 min.
2.2. Pentavalent Americium
Several methods of Arn(V) preparation in solution are
known. Recently convenient methods have been suggested
of electroohemioally obtaining Am(V) by Am(YI) reduotion
in 1~10 M NaOH at an anode potential of 0.2V (130), in
1 M K2C03 at potential of 0.54V (131) and in dilute
HC104+H3P04 solution (132) at potential 1.27V. Am(VI) is

quantitatively reduced to americium (Y) in 30 minutes.
Am(V) is stable in dilute H3P04 and reduced slowly to
Am(III) by radio1ysis products at a rate of about 0.2%
hour. In weak acid solutions Am(Y) is generally more
stable than Arn(VI) (133-135). With increasing acidity
Arn(V) stability falls due to the increase of the dispro-
portiona~on rate (the same effect is observed with incre-
ase of P =ion concentration (136». In solutions of many
acids Am( ) is immediately oxidized by Am(IY) to Am(VI)
(137). In K10P2W17061 solutions this reaction is not com-
plete and it is possible to observe the existence of ame-
ricium in four oxidation states - III,IY,V and VI (138,
139). The reaction between Am(V) and Am(III) in phospho-
tungstate solutions has been studied. It leads to the for-
mation of Am(IV) (140). In 5 M NaOH Am(III) can be com-
pletely oxidized electrochemically to Am(Y) (at an anode
potential of +1Y) and then to Arn(VI) (130).
Americium oxidation by persulfate-ions on heating
in carbonate solutions results in Am(V) and Arn(YI). The
kinetics of this process has been studied in detail (141).
Am( III) in 1 M K2C0 1 at a potential of 1V transforms it
into Am(VI), which teduces electrochemically at 0.9V to
Am(V) (130). Partial oxidation of Am(III) to Am(V) and
been also observed (142).
r
.Am.(VI) in 3-5 M K2COl under strong -irradiation has
Effective extraction methods for americium separa-
tion from other TPE, based on the usage of pentavalent
americium, have been developed. These methods are especi-
ally useful for the isolation of tracer quantities of
americium for its further determination in solutions of
complex composition (143). Am(V) can be extracted from
aqueous solutions by PMBP (144), IIDEHP (145) and ammonium
pyrro1idinedithiocarbaminate (PDTC) (146). The extraction
of trivalent actinide-ions can be suppressed with the
help of potassium phosphotungstate (PT) as is seen from
Fig.4. The data of Table 3 show that Am(V) is well extrac-
ted by all named extractants from the solutions with
pH 5. The authors of papers (147,145) were the first who
extracted macroamounts of Arn(Y) using PMBP (147) and
HDEHP (145). They also obtained absorption spectra of
Arn(V) in the organic phase and data on its stability un-
der these conditions. The separation factor of americium
and curium using .Am(V) extraction by PMBP or HDEHP is
equal to 0+ 6).10.3 (145,147). Trivalent TPE, on the con-
trary, can be extracted with high distribution ooeffici-
ents by extractant mixtures (PMBP with TOPO, TTA with
TOPO or picrolonic acid with sulfoxide) from weak acid
solution, while Arn(V) remains in the aqueous phase under
these conditions. A high degree of Arn(Y) separation from
TPE also takes place (132,143,148). Effective separation
~m
~
TABLE III. Am(V) isolation from TPE a
distribution c
_;;~~~:.::::-________~:::::-~~~____________~rr.~~~t:r.;n______________________ n~
ratio n
Aqueous phase Organic phase compo- Am(V) Me(III) Am(V)!Me(III) ~
2
composition sition 00
o
~
c~
oz
0.01M NH4NO), pH.5 0.06M NH4PDTC in isopen- 30 0.02 1.5.10 3 n
~
(acetate buffer) tanol-ethanol-mixture m
~
~
~
0.01M NH4N0 3 , pa.5 0.05M PMBP in isopen- 12.1 0.002 6.4.10 3 ~
(acetate buffer+ tanol z

~
~
0.00114 PW) m
c00
00
0.1M NH4N0 3 , pH-5 0.5M HDEHP in octane 30 0.01 ).0.10 3 ~
(acetate buffer+0.001M
PW)
0.1M HCl04+0.01M H3 P04 0.05M PMBP+0.025M TOPO 0.02 900 4.5.104*
in cyclohexane
2*
0.1M RN0 3 0.16M PA in methyl 0.26 194 7.)·10
isobutyl ketone
*Me(III)/Am(V)
0\
--..l
68 B. F. MYASOEDOV AND N. Yu. KREMLlAKOVA
of americium (Y) and Cm(III) can be performed by extrac-

tion chromatography with HDEHP as the stationary phase
(149). Americium purification from curium is equal to
5.103 and that of ourium from amerioium is some what
worse and equal to~60. The utilization of zirconium
phosphate has proven to be very promising for Arn(Y) sepa-
ration from curium (150-152).
IlO r-~=::::::::::::::::---'"---'
..L;:2=~3:::::~4:::!;:::,,~5
o ~1
pH
~igure 4. Effect of pH on Am(III) (1,3) and Am(Y)
(2) extraction by 0.5 M HDEHP solution in octane
from acetate solutions ( 0 and 0) and from 1(j..1M
solution of PW ( • and .).
2.3. Hexavalent Oxidation State
Americium and curium are both known in oxidation state
(VI). T~ty exist in solution in the form of the oxygena-
ted MeO~ -ion. The potential of the Am(VI)/Am(III) oouple
in acidic solution is equal to 1.69Y, and that of Am(YI)/
Arn(V) couple is equal to 1.60Y. Many methods of Am(III)
oxidation to Am(VI) have been desoribed (3).
The following methods of obtaining Arn(YI) have been
reoently developed: in phosphoric aoid solutions - elec-
trochemically (107,10a) and by a mixture of Ag3P04+
(:t?S20a (108,110,153); in HCl04 solutions with a small
a ture of H3PO~ - electrochemically (132); in nitric
acid solution with a mixture of AgN03+(NH4)2S,:>OA in the
presence of K10P2W1706j (123) or by Na2S20a with heating
(139);fn 5-M NaOH solutions :.. electroohemically (130);
and in acetate solution - electrochemically (154).
The conditions of Am(YI) preparation in H3P04 and
HNO) solutions in the presence of K10P2W17061 fiave been
stuaied in detail. Quantitative americium ox dation to
Am(YI) takes place in 0.1-3 M H3P04 solutions by Ag3P04+
(NH4)2S20a mixture at room temperature (153). Electroche-
mical Am(lII) oxidation at an anode potential of about
2.0Y in 0.1 M HCI04 solution in the presenoe of 10-5-2 M

H3P04 is a oonvenient method for Am(YI) preparation in
solution. The yield of Arn(VI) in nitrio aoid solutions
in the presenoe of phosphotungstate-ions during the oxi-
dation by persulfate-ions depends on the pH of the solu-
tion and on P2W17061-ion ooncentration. Quantitative ame-
ricium oxidation to Am(YI) takes place in solutions with
pH 1 and with an excess of P2W17061-ions (139).
Investigations of Am(VI) stability in aqueous solu-
tion of different content have shown (132-135,139,153,155,
156) americium to reduce gradually to Arn(V) due to its
own uC-radiation. Am(VI) is the most stable state in
H1 P04 solutions (156) and in the presence of K1~P2W17.061
(123,139). In the latter case it practically ~Q sn't
reduce during several days. Thus the rate of 4 Am(VI)
reduction in 6.10- J M Kl0P2W17061 solutions is equal to
20% for 400 hours, witn Am(T), Am(IV) and Am(III) being
the products of its reduction (139).
Americium oxidation to Am{YI) is used as a method of
separation from other elements and its determination.
Hexavalent americium is extraoted by iDEHP solutions
(149,157,158) and by a mixture of HDEHP with TOPO (158).
Americium (VI) extraotion by 0.5 M lIDEHP solution in ben-
zene occurs at americium concentrations .) 2 mg/ml (149).
Hexavalent americium is rather stable in the organic phase
and this permits the measurement of the amerioium (VI)
absorption spectrum and the study of the meohanism of its
reduction (157). The mixture of EMBP with TOPO (143) in
oyclohexane has proven to be very effective for americium
and curium separation. Americium is first oxidized to the
hexavalent state. During the extraotion process it is re-
duced to the nonextractable pentavalent state. Curium and
other trivalent elements pass into the organic phase with
high distribution coeffioients (Fig.5). The method provi-
des quantitative americium isolation and a high degree of
americium purification from curium (>10 3 ) and fission
products (143). It has been used for the isolation of
macroamounts of americium from irradiated plutonium, as
well as for final purification of americium samples from
curium and radioactive isotopes of rare-earth elements.
Curium content in the final americium sample thus purified
is equal to 10-6 % (by weight).
Efficient separation of Arn(YI) from em(III) can also
be achieved by extraction chromatography using HDEHP as
the stationary phase (149) on zirconium phosphate (150)
and on ca_lcined calcium fluoride_ powder. The s~paration
factor of Am(VI) from Cm(III) d~ring quantitative ameri-
cium isolation is equal to 2.10 and that of Cm from Am -
10 2 (148).
A coulometric method of americium determination by
the Am(VI)/Am(Y) couple using a 2 M H3P04+0.14 M HCI04
tgE
.~
.,-
+2 AIII~I/
,
I
,,
I
.t I
I
I
I
-t
AM(V)
-3 -2 -I 0
tgllOl'O]
Pigure 5. Am(V} and Cm(III} extraction by mixture
of 0.05 M PMBP with TOPO in cyclohexane. 1-Cm(III}
from 0.1 M RN03; 2-Cm(III} from 0.1 M RN03 in the
presence of 50 mg/ml (NH4)2S20S; )-Am after oxida-
tion from 0.1 M RNO), containing 50 mg/ml
( NH4}2 S20S·
mixture as the electrolyte has been developed (159). The
method allows the determination of microgram amounts of
americium in the presence of great quantities of curium
and plutonium. The method of spectrophotometric titration
has been recently suggested for Am(VI) determination in
the presence of both Am(V) and Am(III) (160).
2.3.1. Curium (VI). Until recently attempts to prepare
hexavalent curium have failed. Krot was the first to pre-
dict theoretically the possibility of curium existence in
the penta- and hexavalent state (161).
According to theoretical estimates (162), the stan-
dard oxidation potential of Cm(VI)/Cm(V) couple is not
very high (+1.54) and Cm(VI) can exist in aqueous solu-
tions and will be more stable than Am(IV) and Cm(V) (16).
However its direct preparation by Cm(III} oxidation is
difficult due to the b;fh potential of Cm(IV)/Cm(III)
couple. Cm(VI) (as Cm022l2ha~ been shown to appear fol-
lOwing the .fl -decay of Am2 in solid K3Am02(CO)2 and
to exist in solution after americium caroonate is dissol-
ved in 0.1 M NaHCO).
2.4. Heptavalent Americium
The first attempts to obtain Arn(VII) were carried out
immediately after the preparations of Np(YII) and Pu{YII)
(101). Alkaline solutions were used in order to obtain
Arn{VII) (164). O--ion radicals and ozone in ) M NaOH
were utilized for Arn(YI) oxidation. Absorption spectra
of AIn(YII), obtained under such conditi-
ons, have a characteristic absorption maximum at 740 DDt

with l"'330 (Jig.6). Am(VII) isn't stable in alkaline so-
,,
\
\
,, . -,'",,
\
,,
·It·,
\
, .
\
"
\
t \2... '" ,
" ....
ItOO &00 1000 .t, nm
Figure 6. Absorption speotra of heptavalent aoti-
nides in alkaline solution. 1-Np; 2-Pu; 3-Am.
lutions and the time for half-reduotion to Am(VI) at OOC
is equal to 8 min. Hydrogen peroxide, hydrazine, hydro-
xylamine sulfi te-, and ferrothyanide-ions, N'p(VI) and
Pu(VI) transform Am(VII) to hexavalent or lower oxidation
states (165). The potential of the Am(VII)/Am{VI) couple
has been estimated from the linear dependenoe of electron
speotra of Np(VII), Pu(VII) and Am{TII) on their potenti-
als. It proves to be ejUal to 1.05V in 1 M NaOH. The po-
tential of the Am(VII) Arn(VI) oouple decreases with alka-
line oonoentration and reaohes the potential of Am(VI)/
Arn(V) couple. So Am(VII) oan be obtained in 12-18 M NaOH
solutions owing to Arn(VI) disproportionation (166).
3. CONCLUSION
In olosing this brief review of the main aohievements in
the study of the chemioal properties of amerioium and ourium
ium and their behaviour during extr aot:lD n and sorption
separation processes, we would like to underline some
trends of further investigations in these direotions.
First of all it is necessary to investigate the ohemical
properties of these elements in their rare oxidation
states, inoluding the oomposition and the structure of
their complexes in solutions. It is also necessary to
search for and to use new complexing media, such as car-
bonate solutions, to stabilize the highest oxidation
states. As for the extraotion,it is attractive to use
multiphase systems including aqueous ones and to study
the kinetics of interphase equilibria. !Urther investiga-
tion should be carried out of chemical properties of tran-

splutonium elements in unusual oxidation states. The app-
lication of new extractants and sorbents are likely to
provide soon effective isolation and separation methods
for radioactive elements and reliable techniques for
their control in radiochemical industries.
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COULOMETRIC DETERMINATION OF AMERIClm: AND CURIUM FOR THE PREPARATION
OF REFERENCE SOLUTIONS
P. Brossard and S. Lafontan

CEA - Service CQ
B.P. 12
91680 Bruyeres-le-Chatel
France
ABSTRACT. ful improvement of the method for the determination of

amerlClum by constant - current coulometry is proposed in order to
prepare standardized samples used in alpha-spectrometry and mass
spectrometry. The use of a microcomputer for automatic data acquisition
and their numerical treatment is described. This method gives a precision
of about 0,2 %for 100 micrograms of americium (relative standard devia-
tion of the mean, 95 %confidence). The same technique is also suitable
to prepare 244Cm reference solutions.
I. INTRODUCTION
During the past few years a lot of work has been done focusing on the
preparation of actinide reference samples to be used in alpha-spectro-
metry. Any method to measure the concentration of a standardized solution
must be, besides accurate and reproducible, absolute. For example the
well-known EDTA-complexometry, which is quite accurate, cannot be used
for reference materials since the result depends on the EDTA concen-
tration of the reageants. (1)
To achieve such a goal in the case of americium, the potential
imposed coulometry, currently used for plutonium and uranium, was first
proposed (2), (3). Unfortunately, the reproductibility was not very good
since the americium-IV is dismuted in Am III and Am V. Only recently, a
method which meets the required conditions was described (4) (5). The
idea was to combine the EDTA complexation of americium with the cons-
tant - current coulometry. Since it gives very good results, the method
is now widely used. However for each determination one needs a fairly
large amount of americium and this appears to be a serious problem since
pure americium solutions of high isotopic quality are not largely avai-
lable.
The present work was carried out in order to improve this method,
i.e., lowering the quantities needed for one determination.
In principle, the method is quite simple. The coulometric determi-
nation is based on the electrochemical equilibrium between mercury-EDTA
complex and americium :
81
N. M. Edelstein et al. (eds.), Americium and Curium Chemistry and Technology, 81 -87.
82 P. BROSSARD AND S. LAFONTAN
Hg EDTA 2- + + (1)
The free mercury ions are removed by cathodic reduction on a mer-

cury-pool electrode. The, number of coulowbs needed for a total elimina-
tion of the ions Hg2+ is then directly proportional to the amount of
americium previously added. The detection of the end-point is done by
amperometry with two polarized indicator electrodes (dead-stop-end-point).
In order to minimize the random error on the end-point determina-
tion, these are automatically calculated by a microcomputer which has
previously recorded the titration curves.
2. EXPERIMENTAL
2.1. Apparatus
The device used for the coulometry of amerlClum has been described in a
previous paper (4). It mainly consists of a coulometric cell (figure 1)
connected to an electrochemical buret (wich delivers and integrates the
reduction current) and an amp~rometry detection unit. The later imposes
a low potential (20 mV) between the two droplet-mercury electrodes and
the current passing through is measured. This current is directly related
to the concentration of the free mercury ions in the solution.
2.2. Reagents
2.2.1. Acetic buffer: For one liter of solution, 2.20 grams of mercury
are dissolved in nitric acid. Then one adds 3.7 grams of Na2EDTA and 57
ml of pure acetic acid. The pH is then adjusted to about 5 with ammonia.
2.2.2. Solution of americium: The solution of the desired isotope is

prepared from the oxide and purified by reverse phase chromatography on
HDEHP-gas chrom-Q column. Then the solution is treated with oxalic acid.
The oxalate is calcined into an oxide which is finally dissolved in
nitric acid to the desired concentration.
2.3. Procedure
One pours in the cell about 8 cc of mercury and 6 cc of "acetic buffer".

The auxiliary compartment is filled with 1M ammonium nitrate. The nitro-
gen pressure is set to the pressure in this compartment. Then a first
reduction of the free Hg2+ ions present in the solution is performed.
The current measured between the two detection electrodes is recorded
as a function of the delivered number of coulombs. When the end point
has been detected the reaction is stopped and an accurately weighted
amOll'lt of the americium solution is introduced into the cell. The
reduction is then repeated and the second end-point determination is
recorded. This procedure leads to titration curves like those presented
on figure 2. One can compute the unknown concentration of americium, C,
with the relation :
COULOMETRIC DETERMINATION FOR THE PREPARATION OF REFERENCE SOLUTIONS 83
Stirrer
Auxiliary
Amperometric
Electrode
Electrodes
Coulometer
Amperometric
Detection ~ :.-. ~
Solution
~~
Unit
Mercury Curren,t
~ Generator
Working
Electrode
Interfaces
8-bits, 48 kO memory
,
Microcomputer
Figure 1. Apparatus used for the coulometric determination of

americium and curium.
Aliquot
First I ntroductio n Secona
Il A
Reduction
~ Reduction
.. I
I
\
\ I
I
I
\ I
I
1\
I \ I
I
1------0-----.;
Coulombs
Figure 2. Titration curves obtained during the constant-current

coulometry of americium and curium.
Difference with the

Cone. found Std. Deviation
Method theoretical value
(mg/g) (%)
(o/w
Hand-
3.186 0.50 0.2
determination
Polynomial
fitting 3.204 1.07 0.76
(fifth degree)
Polynomial
fitting 3.191 0.34 0.36
(eighth degree)
Fast Fourier
3.183 0.23 0.1
Transform
Table I. Comparison between the numerical methods in the case of the

titration of cadmiu~ (Co=3.1797 ± 0.006 mg/g, 8 determinations, aliquot
weight: ~100 ~g).
Weight of the
6O-120g
aliquot
Number of
determinations
8
Measured concentration
of americium (mg/g)
2.009 + 0.004
Alpha-spectrometry
value (mg/g)
2.01 + 0.02
Table II. Typical results obtained in the coulometric titration of

americium and comparison with alpha-spectrometry.
C Q M (2)
2mF
where M is the atomic weight, m the weight of the aliquot and F the
Faraday constant (96 484.57 C/Mole), Q is the difference between the
number of coulombs given by the second end-point (Q2) and the first
one (Ql)'
2.4. Determination of the end-point
The problems arise with the determination of the end-points. The elec-
trical noise cannot be reduced to zero without affecting the reproduc-
tibility. Then, because of the presence of oscillations along the curve,
the minimum cannot be read directly. The method to obtain it consists in
drawing two tangents at the inflexion points on each side of the curve
(dashed lines on the figure 2). If the curve is symmetric, the inter-
section point will give the minimum. Unfortunatelly, this does not occur
very often. Even more important is ~he fact that two operators will never
draw exactly the same tangents and thefore will not found the same
result. This discrepancy will become wore important if one lowers the
amount of americium used to make the determination. The reason is that
the current measured by the amperometric detection unit is, somehow,
proportionnal to the concentration of Hg2+. Therefore the height of the
amperometric wave is decreasing with the decreasing weight of the aliquot,
so the determination becomes more difficult.
To avoid these difficulties the idea is to record the titration
curves into the memory of a microcomputer and to obtain the minimum by
numerical means. This is possible since both the coulometer and the am-
perometric detector have BCD-coded outputs. Such a connection represents
only i'.. slight modification to the apparatus but has great advantages.
Figure 1 gives a schematic view of the modified apparatus. To perform
the automatic data acquisition and the calculations we used an Apple II
microcomputer with 48 k¢ of RAM-memory. The interfacing is done by three
parallel interfaces of 16 bits each.
Once the experimental data points are recorded one has to fit them
with a smooth curve in order to determine the minimum. Several methods
are then available ; for this kind of curves the most popular ones are
the polynomial approximation and the Fourier Transform.
For the first one we may need up to the eighth degree polynomials. For
the second one, the frequencies contained in the signal (digitized in
a power of two number of points) are computed by the Fast Fourier Trans-
form. Then the higher frequencies are set to a zero value and the inverse
transform is computed to get a smoothed titration curve.
3. RESULTS AND DISCUSSION
In order to see which of the two methods is the best according to our
problem, we first performed a set of runs with a cadmium solution instead
of americium; the procedure was exactly the same. The cadmium solution
was prepared from a reference sample of metal dissolved in nitric acid,

all dilutions being done by weighing. The exact concentration of the
solution was 3.1797 mg/g (± 0.02 %). Eight runs were carried out with
aliquots of about 100 l1g.
The results are presented in table i. Values directly obtained by
hand-determination of the minimum are also given.
One can easily see that we did, indeed, improve our results by using
the microcomputer. The polynomial fitting is good only if the polynomial
is of the eighth degree. We also concluded that, the Fourier Transform
appears to be the most suitable method for smoothing such titration
curves. The explanation comes from the fact that the electrical noise
in the signal represents the most disturbing factor.
These results gives us confidence in choosing the Fast Fourier
Transform. However the computationnal time was quite long
(about 15 minutes for a 512 points signal). To overcome this disadvantage
the program was written dOl1n in assembly language. This leads to affor-
dable times (less than 2 min.).
Finally we performed measurements of americium solutions. The
aliquot weights were ranging from 6n to 120 l1g (in americium). The
concentration of the solution was also determined by alpha-spectrometry.
The results are given in table II. If we are in good agreement with
alpha-spectrometry, we also get an excellent reproducibility. In fact,
comparing with results previously published (4), we manag~d to keep the
accuracy and the reproducibility at very low values even though we used
ten times less material. The next step is to prepare reference solution
of curium 244. Runs are underway and the first results indicate a good
reproducibility with 80 l1g curium 244 aliquot weights.
4. CONCLUSION
The use of a microcomputer appears to be of a great help for the prepa-

ration of reference solutions of americium and curium by coulometry. It
allows the amount of material used for the measurement to be lowered
without affecting the quality of the coulornetric determination. One can
reach a precision of about 0,2 %with only 100 l1g of material for each
determination. Associated with a-spectrometry, such a method will cer-
tainly permit the preparation of certified solutions.
5. REFERENCES
(1) Buijs K. and W. Bartscher, Anal. Chim. Acta, 88, 403 (1977)
(2) Koehly G., Anal. Chim. Acta, 33, 410 (1965) --
(3) Stokely J.R. and w.n. Shults,-Anal. Chim. Acta, 45, 417 (1969)
(4) Bergey C. and L. Fouchard, Talanta, 26, 445 (1979J
(5) Bergey C., Mikrochimica Act~n),=~, 207 (1981)
A STUDY ON THE STABILITY OF AMERICIUM(V) AND AMERICIUM(VI) IN NITRATE
MEDIA
M. Hara and S. Suzuki

The Research Institute for Iron, Steel and Other Metals,
Tohoku University
Katahira 2-1-1, Sendai 980
Japan
ABSTRACT. The oxidation of Am(III) to Am(VI) with sodium bismuth tri-

oxide was investigated in a nitric acid solution, and a procedure was
developed to oxidize Am(III) at low concentrations completely. The oxi-
dant was added to a nitric acid solution of Am(III), and the mixture was
mechanically stirred; the &~(VI) solution free from the excess oxidant
was obtained by filtering the mixture. An Am(V) solution was prepared by
passing the Am(VI) solution through a column of Celite 545 containing
bis(2-ethylhexyl)hydrogenphosphate, which reduced Am(VI) to Am(V). The
stability of Am(V) and Am(VI) at concentrations lower than 10- 6 M in
nitric acids and in solutions containing ozone gas, fluoride, or phos-
phate ions was investigated by means of the coprecipitation technique
with BiP04 and ThF4. It was found that 241Am(V) and 241Am(VI) were grad-
ually reduced to Am(III) in nitric acids at low acidities and high tem-
peratures, but the reduction was effectively inhibited by the presence
of ozone gas or fluoride ions. On the other hand, 243Am(V) and 243Am(VI)
were found to be rather stable in nitric acids. But, they were readily
reduced to Am(III) in the phosphate solutions in the same manner as
241Am(V) and 241Am(VI).
INTRODUCTION
Most investigations on the chemical properties of Am(V) and Am(VI) have

been carried out by the use of an alpha-emitter 241Am(t1/2 = 433 y); its
alpha-decay leads to the radiolytic reduction of Am(V) and Am(VI).(1,2)
When the long-lived isotope 243Am(t1/2 = 7400 y) is used, the radiolytic
reduction is not so remarkable as that in 241Am solutions. (1) On the
other hand, Am(V) disproportionates to Am(VI) and Am(IV) in moderately
concentrated acids. (1-2) The radiolytic reduction and disproportionation
have been investigated by means of spectrophotometry using 241Am and
243Am solutions at concentrations of 10-3 M or above.
The 241Am and 243Am solutions diluted to about 10-7 and 10- 6 11,
respectively, can be studied by radiometry. In dilute solutions, Am(V)
may be free from any disproportionation, while the radiolytic reduction
of 241Am(V) and 241Am(VI) may proceed, as suggested by the rate laws.(1-
89 -
90 M. HARA AND S. SUZUKI
2). Am(V) and Am(VI) may also be reduced by small amounts of impurities.
The information concerning the stability of Am(V) and Am(VI) at low
concentrations is rather poor. Only a little information was obtained
from previous works(~,I) in which the stability of Am(V) in several
media was studied by means of solvent extraction with 2-thenoyltrifluo-
roacetone and of column chromatography using bis(2-ethylhexyl)hydrogen-
phosphate, HDEHP, as an extractant, where the rapid reduction of Am(VI)
by HDEHP was observed.
When the solutions of Am(V) and Am(VI) were submitted to the copre-
cipitation method with some fluorides and phosphates at 0 - 5 OC, no
change of oxidation states of americium was observed.(8,9) However, this
finding can not guarantee a high stability of Am(V) and Affi(VI) in fluo-
ride and phosphate solutions at room temperature or above.
An acidic solution of Am(VI) at low concentrations has been conven-
tionally prepared by the oxidation of Am(III) with silver-catalysed
ammonium persulfate,(2) but this method has disadvantages as described
below. First, the acidity of the solution must be lower than 0.2 M
because persulfate decomposes via an acid-catalysed path(10) to produce
peroxymonosulfuric acid which would rapidly reduce any AmCVI) formed.
Second, the resulting Am(VI) solution suffers contamination from the
p.xcess oxidant and its reduction products. Such disadvantages would make
it more difficult to investigate the chemical properties of Am(VI) such
as its stability, complex formation, and redox reactions.
By the way, sodium bismuth trioxide was previously used for the
determination of manganese. This method is known to be fatally flawed by
the presence of Co(II) and Ce(III) because they are oxidized to Co(III)
and Ce(IV) with the reagent.(11) The standard potential for the Bi(III)-
Bi(V) couple must be quite enough to oxidize Am(III) to Am(VI) with
Bi(V), since the potentials for the Am(III)-Am(VI), the Co(II)-Co(III),
and the Ce(III)-Ce(IV) couples are 1.69,(4) 1.95,(12) and 1.74 volts,
(11) respectively. The low solubility of sodium bismuth trioxide in acid
solutions is an advantage since the reagent not dissolved can be easily
removed from the reacting solution, although the oxidant dissolved in
the solution can oxidize only a small amount of materials.
In this work, the oxidation of Am(III) with sodium bismuth trioxide
was investigated at low concentrations of americium, and a study in
nitric acid solutions has resulted in successful developments.(li) The
oxidation reaction was followed by the coprecipitation method with
BiP04. The stability of Am(V) and Am(VI) in nitric acid solutions and in
solutions containing ozone gas, fluoride or phosphate ions was also
investigated.(12) The change of americium oxidation state with time was
followed by the coprecipitation method with BiP04 and ThF4.
MATERIALS AND METHODS
Dissolution of oxidant
Sodium bismuth trioxide powder, min. 80 wt%, was added to the nitric
acid solution in a glass test tube, and the mixture was vigorously
stirred. -The mixture was then filtered with a glass fibre filter-paper,
STABILITY OF AMERICIUM(V) AND AMERICIUM(VI) IN NITRATE MEDIA 91
Whatman GF/A, or a column packed with quartz glass wool, A grade(1-5 pm).
The concentration of Bi(V) and total bismuth(Bi(III) + Bi(V)) in the
filtrate were determined by iodometry and chelatometry, respectively.
Potassium iodide, and solutions of sodium thiosulfate and starch were
used for iodometry; sodium dihydrogenphosphate was used to hinder a yel-
low coloration resulting from the formation of bismuth iodide. Disodium
ethylenediaminetetraacetate and xylenol orange were used as a chelating
agent and an indicator, respectively.
Oxidation of Am(lll) with sodium bismuth trioxide
The powdered oxidant was added to a nitric acid solution of 241Am(III)

or 2 4 3Am(III) in a glass test tube, and the mixture was vigorously
stirred. Then, an aliquot of the mixture was analysed by the coprecipi-
tation test with BiP04. In some cases, the undissolved oxidant was
filtered off from the mixture and an aliquot of the filtrate was also
analysed by the coprecipitation test.
Coprecipitation test
The test was carried out under such conditions that Am(III) was quanti-
tatively carried down, while most of Am(V) and Am(VI) remained in the
solution.(8) BiP04 and ThF4 were precipitated at 0 OC from the americium
solution to which nitrate solutions of Bi(III) and Th(IV) were added,
respectively, followed by the addition of excess precipitants under the
conditions described below:
Precipitate BiP04 ThF4
Volume of the mixture 5 ml 3 ml

Acidity of the mixture 0.5 M 0.1 M
Amount of metal ion Bi3+ 10 mg Th4+ 1 mg
Precipitant NaH2P04 NH4F
Time of mixing 7 min 10 min
The mixture was either filtered by a glass fibre filter-paper or

centrifuged at 6000 rpm for 5 min. The fraction of americium carried, Y,
was determined as usual by measuring the gamma-activity in the mixture
and the filtrate(or the supernatant). The gamma-ray assay was performed
by the use of a flat NaI(Tl) scintillation probe connected to a scaler
or by the use of a Ge(Li) detector connected to a multi-channel pulse-
height analyzer.
Preparation of Am(Y) and Arn(YI) solutions
Ten mg/ml of sodium bismuth trioxide was added to a 0.1 M HN03 solution
of Am(lll), and the mixture was mechanically stirred for 50 min at room
temperature and then for 10 min at 0 °C. An Am(VI) solution was obtained
by filtration of the mixture with a glass fibre filter-paper.
Am(V) solution was prepared at 0 °C by passing the Am(VI) solution
through a column of Celite 545 containing HDEHP, which rapidly reduced
Am(VI) to Am(V). Solutions of nitric acid and ammonium fluoride or ,

sodium dihydrogenphosphate were added to the Am(V) and Am(VI) solutions
making 241Am and 243Am concentrations up to about 10-7 and 10-6 M,
respectively. A reference Am(VI) solution was prepared as usual by the
oxidation of Am(III) with silver-catalysed ammonium persulfate.(2)
stability of .Am(V} and .Am(VI}
The Am(V) and Am(VI) solutions were maintained in a thermostat at a tem-

perature kept constant to ~ 0.5 oC. Appropriate aliquots of the stock
solutions were analysed by the coprecipitation test at controlled time
intervals.
RESULTS AND DISCUSSION
Dissolution of oxidant
The concentration of total bismuth ions in a nitric acid solution was

found to be almost independent when the amounts of the oxidant used was
in the range of 2 - 20 mg/ml. Solutions containing more than 20 mg/ml
oxidant could not be effectively stirred. Thus the amount of oxidant was
adjusted to 10 mg/ml in the following experiments.
It was observed that the concentration of Bi(V) was apparently
constant in a nitric acid solution when mixed with the oxidant, but
increased with increasing acidity and temperature, as shown in TABLE I.
However, the concentration of Bi(III) (equal to the difference between
the concentrations of total bismuth and Bi(V» increased rapidly with
time of mixing at 30 oC, especially at high acidities, while it remained
at low levels at 0 oC, as shown in Figure 1.
TABLE I. The concentration of Bi(V) in the nitric

acid solution mixed with NaBi03.
[ HN03] [Bi(V)],* 10-3 M
M 0 OC 30 OC
0.25 0.04 ~ 0.01 0.03 ~ 0.01

0.5 0.05 ~ 0.01 0.05 ~ 0.02
1.0 0.13 ~ 0.01 0.16 ~ 0.01
2.0 0.17 ~ 0.04 0.26 ~ 0.03
4.0 0.47 ~ 0.05 0.74 ~ 0.04
* The mean of the four values measured every 15

min of mixing.
The concentration of Bi(V) in the solution free from the undis-

solved oxidant did decrease more rapidly with time at 30 OC, especially
at high acidities, as shown in Figure 2. That is, the increase in the
concentration of Bi(III) seemed to be closely correlated with the
10
• o °c c
8 0 30°C
~
C") 6
I
0
~m 4
L.J
Time of mixing, min
Figure 1. The concentration of Bi(III) in 1 M(a), 2 M(b), and 4 M(c)

HN03 mixed with NaBi03 at 0 and 30 oc.
10~----------~----------~----------~
o O·C
~~ 6
I
o
c
b
a
20 40 60
Time of standing, min
Figure 2. The concentration of Bi(V) in 1 M(a), 2 M(b), and 4 M(c) HN03

free from undissolved NaBi03 at 0 and 30 oc.
decrease in the concentration of Bi(V).

The chemical species of Bi(V) generated by the dissolution of oxi-
dant powder may be neutral species such as NaBi03 or HBi03' The concent-
ration of Bi(V) seemed to be constant at a constant acidity and tempera-
ture because the reduction of Bi(V) to Bi(III) with water or hydrogen
ion was apparently balanced by the dissolution of the oxidant, irrespec-
tive of the acidity and the temperature of the solution. This situation
would be the same even if low concentrations of americium were present.
Oxidation of Am(III) with sodium bismuth trioxide
Figures 3 and 4 indicate the results of the coprecipitation test which

was carried out on the americium solution mixed with the oxidant. With
lower acidity and/or higher temperature, the fraction of americium
carried decreased rapidly with the reaction time to an apparently cons-
tant value. This value was in good agreement with the value which was
obtained from the reference Am(VI) solution. Therefore, it was concluded
that the oxidation of Am(III) to Am(VI) in solution was completed when
the value given above was found in the coprecipitation test.
When the mole fraction of each oxidation state of americium in the
reacting solution is expressed as fX(X = III, V, and VI), Y, which is
obtained by the coprecipitation test, may be given by an equation:(~)
Y = fIllY III + fVYV + fVIYVI (1)
where YX(X = III, V, and VI) means the fraction of Am(X) carried, which
can be determined by the coprecipitation test on corresponding single-
component solution. The values for YX·were determined as follows: YIII =
0.99 ~ 0.01, YV = 0.25 ~ 0.03, and YVI = 0.05 ~ 0.02 by the BiP04 copre-
cipitation test, and YIII = 0.99 ~ 0.01, YV = 0.12 ~ 0.02, and YVI =
0.30 ~ 0.02 by the ThF4 coprecipitation test.
In the reacting solutions containing excess oxidant Am(V) could be
ignored because the standard potentials for the Am(III)-Am(V) and Am(V)-
Am(VI) couples are 1.74 and 1.60 volts,(~) respectively, in comparison
with the potentials for the Am(III)-Am(VI) and Bi(III)-Bi(V) couples, as
discussed before. That is, Am(V) would be readily oxidized to Am(VI)
even if initially present. Then, Eq. 1 may be rewritten as:
Y = fIllY III + fVIYVI. (2)
Using the YIII and YVI given above, and the Y shown in Figures 3
and 4, the fVI could be deduced by solving Eq. 2 because fIll + fVI = 1.
It was also plotted in each figure. It is clear that the oxidation reac-
tion of Am(III) with NaBi03 proceeded more rapidly at lower acidities
and/or at higher temperatures. The reaction time needed for half or com-
plete oxidation of Am(III) is given in TABLE II for several cases. The
rate of oxidation does not depend so much on the concentration of Bi(V)
as on the acidity and the temperature. This finding explains qualita-
tively the oxidation process, for which kinetic and stoichiometric
analysis has not been given.
The recommended procedure for the preparation of an Am(VI) solution
1·0
0 y
0·8
• tV!
0.6
....:;:
L-
0
> 0·4
90
Reaction time, min
Figure 3. Oxidation of Am(III) with NaBi03 in 0.35 M(a), 0.5 M(b),

0.7 M(e), and 1.0 M(d) HN03 at OOC.
o y
0·8
• fV!
_ 0·6
....>
L-
o
> 0·4
o'o----~~--3LO~----~~6~0---------790·
Reaction time, min
Figure 4. Oxidation of Am(III) with NaBi03 in 1.0 M HN03 at OOC(a),

10 °C(b), 20 OCee), and 30 0C(d).
is as follows: the solution resulting from the reaction of Am(III) and

NaBi03, and when allowed enough time as given in TABLE II, must be
allowed to stand at as iowa temperature as possible until the undis-
solved oxidant is filtered off. The acidity of the solution is main-
tained at 0.2 - 2 M in order to avoid both the contamination by a large
amount of Bi(III) and the precipitation of its hydrolysis products.(li)
TABLE II. The time required for the half and complete
oxidation of Am(III) to Am(VI) with NaBi03
[HN03], Temperature, Time for half Time for complete

M oC oxidation, min oxidation, min
0.5 0 4 30
0.5 10 <3 25
0.5 20 <2 20
0.5 30 <1 5
1.0 0 16 50
1.0 10 9 40
1.0 20 <3 22
1.0 30 <2 12
2.0 20 15 40
2.0 30 <4 18
Stability of Am(V) and Am(VI)
In HN03 solutions. The BiP04 coprecipitation test was carried out on the
nitric acid solution of 241Am(V) and 241Am(VI). The results for the 0.5
M HN03 solutions at 0 - 40 OC and for the (0.125 - 2 M) HN03 solutions
at 30 OC are shown in Figures 5 and 6, respectively. The measured value
for Y increased with time of storage, especially at high temperatures
and at low acidities. Dependence of the increase in Y on acidity was
found only for the Am(VI) solutions at the temperatues higher than 20
OC. The increase in Y may be caused by the reduction of Am(V) and Am(VI)
to Am(III) in the stock solutions, because Am(III) is more effectively
carried by BiP04.
The rate law for the radiolytic reduction of Am(V) can be expressed
by an empirical equation:
d[Am(V) ] d[Am(IU) ]
= (3)
dt dt
where kl is an apparent rate constant and [Am]T means the total ameri-
cium concentration. The decrease in Am(VI) concentration with time can
be expressed by an equation:
d[Am(VI)]
(4)
dt
'·0
0 Am(V)
0·8
• Am(VI)
e
e
>
d
c d
0·2 c
b
a
0
0 2 3
Time of standing, hour
Figure 5. Result of the BiP04 coprecipitation test carried out on the

0.5 M HN03 solutions of 241Am(V) and 2Q1Am(VI) stocked at 0 OC(a), 10
0C(b), 20 0C(c), 30 0C(d), and 40 OC(e).
'·0
0 Am(V)
0·8 • Am(Vl)
0·6
>-
0·4
c
d
0·2 e
Figure 6. Result of the BiP04 coprecipitation test carried out on the

0.125 M(a), 0.25 M(b), 0.5 M(c), 1.0 M(d), and 2.0 M(e) HN03 solutions
of 241Am(V) and 241Am(VI) stocked at 30 0c.
where k2 is an apparent rate constant. Values for kl and k2 have been

estimated to be 0.01 and 0.03 h- 1, respectively, in dilute acid solu-
tions.(1,2) If no reactions other than radiolytic reduction proceed, the
growth of-Am(V) in the Am(VI) solution can be expressed by an equation:
d[Am(V)]
(5)
dt
If the radiolytic reduction predominantly proceeds in the stock

solutions of 241Am, Eq. 1 can be expressed by the following equations,
using the solutions of Eqs. 3 - 5:
for the case of 241Am(V) solutions,
Y = YV + (YIII - YV)klt, (6)
and for the case of 241Am(VI) solutions,
Y = YVI + {(YIII - YVI)kl + (YV - YVI)k2}t.
Unfortunately, the linear relations expected by Eqs. 6 and 7 were

valid only when the stock solutions were at high acidities and at low
temperatures, as shown in Figures 5 and 6. It is clear that reactions
other than radiolytic reduction also occurred, especially at low acid-
ities and at high temperatures. They are assumed to be first-order reac-
tions such as Am(VI) ---> Am(V) and Am(V) ---> Am(III), while the radio-
lytic reduction of Am(V) and Am(VI) is zero-order reaction with respect
to Am( V) and Am( VI) •
The rate law for the above-mentioned reactions can be expressed as:
in the case of 241Am(V) solutions,
d[Am(V)] d[Am(III)]
- - - - = - - - - = kl '[Am(V)], (8)
dt dt
and in the case of 241Am(VI) solutions,
d[Am(VI)]
- - - - = k2'[Am(VI)], and (9 )
dt
d[Am(V) ]
- - - - = k2'[Am(VI)] - kl '[Am(V)], (10)
dt
where kl' and k2' are apparent rate constants. If these first-order
reactions predominantly proceed in the stock solutions, Eq. 1 can be
written as follows z using the solutions of Eqs. 8 - 10:
for the case of 24IAm(V) solutions,
YIII - Y = (YIII - Yv)exp(-kl 't), ( 11)

and for the case of 241Am(VI) solutions,
YIII - Y = c·exp(-kl't) + (YIII - YVI - C)exp(-k2't), (12)
where C = (YIlI - YV)k2'(k2' - kl,)-l.

As YIII is nearly equal to unity, Figures 7 and 8 illustrate the
plot of log(l - Y) vs t, using the data shown in Figures 5 and 6. The
relationship expected by Eqs. 11 and 12 was confirmed for the stock
solutions of low acidities and at high temperatures. Thus, it is reason-
able to assume that the radiolytic reduction and first-order reactions
compete in the dilute 241Am solutions.
The values for kl' and k2' were estimated by means of curve-fitting
techniques; the results are shown in TABLE III. The values for kl' and
k2' fluctuated, and seem to depend upon whether the nitric acid solution
(used to prepare the stock solutions) was freshly prepared by dilution
of conc. nitric acid or was allowed to age slightly. Therefore, some
material which induced first-order reactions was probably introduced
into the stock solutions from the nitric acid.
TABLE III. Apparent rate constants for the reduction of

241Am(V) and 241Am(VI) in HN03 solutions
[ HN03 ], Temperature, Apparent rate constant, h- 1
M OC kl,a) kl ,b) k2,b)
0.125 30 0.14 :!: 0.01 0.14 :!: 0.02 2.37 :!: 0.11
0.25 30 0.12 :!: 0.01 0.14 :!: 0.02 2.07 :!: 0.23
0.5 30 0.13 :!: 0.01 0.09 :!: 0.02 0.69 :!: 0.23
0.5 20 0.06 :!: 0.01
0.5 40 0.40 :!: 0.01 0.30 :!: 0.05 2.00 :!: 0.43
a) Results for Am(V) solutions.

b) Results for Am(VI) solutions.
When the 0.05 M HN03 solutions of 243Am(V) and 243Am(VI) were

investigated, no change in Y with time of storage was observed even on
stock solutions at 30 oC. This finding may be explained only bt the
large difference in emission rate of alpha-particles between 2 lAm and
243Am. Therefore, first-order reactions are considered to be the radio-
induced reactions which may be caused by a product resulting from the
interaction between the radiolysis product and the material introduced
from the nitric acid.
This assumption was supported by a finding for the 241Am(V) and
241Am(VI) solutions containing ozone gas; Y was constant for the time of
storage during which the stimulative smell of ozone gas was present in
the stock solution vessel. It can be concluded that ozone gas effec-
tively eliminates any reducible materials as chlorine gas does.(~)
In HN03-NH4F solution. The coprecipitation test with ThF4 was carried

out on the 0.05 M HN03-(0.05 and 0.5 M) NH4F solutions of 241Am(V) and
a
b
c
d
0·6
>
0·4
o Am(V)
e
• Arn(V!)
e
o 2 3
Figure 7. The plot of log(l - Y) vs t for 0.5 M RN03 solutions of

241Am(V) and 241Am(VI) stocked at o-OC(a), 10 0C(b), 20 0C(c), 300C(d),
and 40 0C(e).
e
d
> c
o Am(V)
• Am(V!)
O.4L---------~---------L--------~
o 2 3
Figure 8. The plot of loge 1 - Y) ~ t for 0.125 M(a), 0.25 M(b), 0.5
M(c), 1.0 M(d), and 2.0 M(e) RN03 solutions of 241Am(V) and 241Am(VI)
stocked at 30 °C.
ST ABILITY OF AMERICIUM(V) AND AMERICIUM(Vl) IN NITRATE MEDIA 101
241Am(VI) at 30 oC, and the result is shown in Figure 9. The Y for the
stock solutions containing the fluoride increased more slowly than for
the case without fluoride, and no change in Y was observed for the 0.5 M
NH4F solutions. The stock solutions of acidity higher than 0.05 M called
for high fluoride concentrations to minimize the variation in Y.
This finding can be explained by the suggestion that 241Am(V) and
241Am(VI) become free from all reduction reactions if they form fluoro
complexes 4 as in the case of the acetate(I) and the chloride solutions
(11) of 2 1Am(V). The excellent stability of 243Am(V) and 2 43Am(VI) in
the ozonized fluoride solutions was also confirmed as expected.
In HN03-NaH2P04 ozonized solutions. The coprecipitation test with BiP04

was carried out on the 0.05 M HN03-(0 - 2 M) NaH2P04 and on the (0.025 -
0.2 M) HN03-0.5 M NaH2P04 solutions of 241Am(V) and 241Am(VI) at 30 OC.
The Y for these ozonized phosphate solutions increased rapidly with time
of storage, especially for the solutions of low acidities and high phos-
phate concentrations. The plot of log(l - Y) ~ t is illustrated in
Figures 10 and 11; a good linearity was obtained in most cases.
The same result was obtained both for the 0.05 M HN03-0.5 M NaH2P04
solutions of 241Am(V) and 241Am(VI) at 0 - 40 oC and for the (0.05 - 0.5
M) HN03-1 M NaH2P04 solutions of 243Am(V) and 243Am(VI) at 30 0C. Evi-
dently, the variation in Y with time for the phosphate solutions of
241Am(VI) and 2 43Am(VI) can be explained neither by Eq. 7 nor by Eq. 12.
1· 0
0 Am(V)
0·8 • Am(VI)
0·6
>
0·4
o 30 60 90 120
Figure. 9. Result of the ThF4 coprecipitation test carried out on the

0.5 M HN03-(0 M(a), 0.05 M(b), and 0.5 M(c» NH4F solutions of 241Am(V)
and 241Am(VI) stocked at 30 oc.
, . 0 e;:::::::C>==:::O:====O====:::ZC:===ll:=:~===:------:J
~~~~~~~__+-~L-__- .__ Q
0·5
>
0·,
0·05
o Am(V)
d
• Am(VI)
o 30 60 90
Figure 10. The plot for log(l - Y) vs t for 0.05 M HN03-(0 M(a), 0.1
M(b)~ 0.5 M(c), 1.0 M(d), and 2.0 M(eT) NaH2P04 solutions of 241Am(V)
and ~41Am(VI) stocked at 30 oe.
'·0....------..-------........---------.
0·5 c
> b
0·1
0,05 o a
o Am(V)
Q
• Am(VI)
o 30 60 90
Figure 11. The plot for log(l - Y) ~ t for (0.025 M(a) 0.05 M(b), and
0.2 M(c» HN03-0.5 M NaH2P04 solutions of 241Am(V) and 241Am(VI) stocked
at 30 oe.
STABILITY OF AMERIClUM(V) AND AMERIClUM(Vl) IN NITRATE MEDIA 103
It is known that Am(VI) at such high concentrations as 2 x 10-3 M

(243Am 85 %and 241Am 15 %) is readily reduced to Am(lll) in phosphoric
acids.(18) It may also be assumed that Am(V) and Am(VI) at low concent-
rations~re reduced to Am(lll) in the ozonized phosphate solutions, and
that the reduction rates are given by the following equations:
d[Am(V)] d[Am(III)]
= = k1*[Am(V)], and (13)
dt dt
d[Am(VI)] d[Am(III)]
= = k2*[Am(VI) ], (14)
dt dt
where k1* and k2* are apparent rate constants. If the change of oxida-
tion states of americium in the ozonized phosphate solutions is predomi-
nantly caused by these reactions, Y can be expressed as follows, using
the solutions of Eqs. 13 and 14:
for the case of Am(V) solutions,
YIII - Y = (YIII - Yv)exp(-k1*t), (15)
and for the case of Am(VI) solutions,
YIII - Y = (YIII - YVI)exp(-k2*t). (16)
As YIII is nearly equal to unity, Eqs. 15 and 16 can explain the

linearity obtained by the plot of log(1 - Y) ~ t, as shown in Figures
10 and 11. Therefore, it seems reasonable to assume that Am(V) and
Am(VI) are reduced to Am(III) in the ozonized phosphate solutions.
Values for k1* and k2* were obtained from the slope of the straight
lines. They were found to be larger for the stock solutions at low acid-
ities, at high phosphate concentrations, and at high temperatures, as
summarized in TABLE IV. The reduction of 2 43Am(V) and 243Am(VI) pro-
ceeded more rapidly than in the solutions of 241Am because the 243Am
concentration was about ten times higher than the 241Am concentration.
The available information concerning the behavior of americium in
phosphoric acid(18) and the phosphato complex formation of neptunium and
plutonium(19,20)-Suggests that Am(V) and Am(VI) may form the phosphato
complexes suc~as Am02H2P04 and Am02H2P04+, respectively in the phos-
phate solutions investigated. Therefore, the rapid reduction of Am(V)
and Am(VI) might result from an intramolecular electron transfer in the
phosphato complexes formed.
References
1. Hall, G.R.; Markin, T. L.; J. Inorg. Nucl. Chem., 1957,4,296.

2. Yakovlev, G. N.; Kosyakov, V. N.; Proc. 1st Int. Conf. On the
Peaceful Uses of Atomic Energy, Geneva(1955), 1956, 1, 363.
3. Coleman, J. S.; morg. Chem., 1963,2, 53.
TABLE IV. Apparent rate constants for the reduction of Am(V)

and Am(VI) in HN03-NaH2P04 ozonized solutions.
[ HN03 ], [NaH2P04 ], Temperature, Apparent rate constant, h- 1

M M oC k1* a) k2* a)
0.05 0 30 -0.02 :!: 0.03 -0.05 :!: 0.02

0.05 0.1 30 0.67 :!: 0.01
0.05 0.5 30 1.44 :!: 0.04 1. 28 :!: 0.02
0.05 1.0 30 2.32 :!: 0.05 2.13 :!: 0.04
0.05 2.0 30 6.10:!: 0.04 4.78 :!: 0.04
0.05 0.5 0 -0.06 :!: 0.03 0.00 :!: 0.02
0.05 0.5 40 7.63 :!: 0.06 6.08 :!: 0.06
0.025 0.5 30 4.23 :!: 0.04 2.71 :!: 0.02
0.1 0.5 30 0.65 :!: 0.04 0.55 :!: 0.04
0.2 0.5 30 0.40 :!: 0.03 0.30 :!: 0.05
0.05 0 30 0.02 :!: 0.01 b ) 0.02 :!: 0.02 b )
0.05 0.1 30 1.00 :!: O. 02b ) 1.39 :!: 0.02 b )
0.05 1.0 30 10.5 :!: 0.1 b ) 8.98 :!: 0.02 b )
0.5 1.0 30 2.89 :!: 0.02 b ) 5.80 :!: 0.03 b )
a) Result for 241Am solutions except as otherwise noted.

b) Result for 243Am solutions.
4. Penneman, R. A.; Asprey, S. B.; Proc. 1st Int. Conf. on the

5. Yakovlev, G. N.; Kosyakov, V. N.; Proc. 2nd Int. Conf. On the
6. Hara, M.; Bull. Chern. Soc. Japan, 1970, 43, 89.
7. Hara, M.; Suzuki, S.; Bull. Chern. Soc. Japan, 1974, 47, 635.
9. Moore, F. L.; Anal. Chern., 1963,35,715.
10. Kalthoff, 1. M.; Miller, 1. K.; J. Am. Chern. Soc., 1951,73, 3055.
11. Lundell, G. E. F.; J. Am. Chern. Soc., 1923, 45, 2600.
12. Johnson, D. A.; Sharpe, A. G.; J. Chern. Soc., 1964, 3490.
13. Conley, H. L.; Thesis, UCRL-9332, 1960.
14. Hara, M.; Suzuki, S.; J. Radioanal. Chern, 1977, 36, 95.
16. Olin, A.; Acta Chern. Scand., 1957, 43, 1445.
17. Kasha, M., J. Chern. Phys., 1949, 17, 349.
18. Myasoedov, B. F.; Mikhailov, V. M.; Lebedev, I. A.; Koiro, O. E.;
Frankel, V. Ya.; Radiochem. Radioanal. Lett., 1973, 14, 17.
19. Moskvin, A. I.; Peretrukhin, V. F.; Radiokhimiya, 1964, 6, 206.
20. Kenotkina, R. G.; Shevelenko, U. B.; Zh. Neorg. Khim., 1967, 12,
2345.
Radiopolarograpbic Study of' Americium and Curium
Y.Shiokawa and S.Suzuki

The Research Institute for Iron, Steel and other Metals,
Tohoku University
Japan
ABSTRACT. The radiopolarographic behavior of americium and curium in

non-complexing aqueous media was examined as a function of
concentration, specific activity and pH. At pH=3.0, a single wave of
americium was observed below [Am]=8.0x10- 7 M having a plateau at a
potential more negative than -2.02 V (main wave). An additional pre-wave
was observed above [Am]=9.6x10- 7 M. At lower pH«2.6), the pre-wave
appeared even at a concentration smaller than 8.0x10-7 M and the
potential at maxmium height was shifted slightly with the concentration.
The radiopolarographic behavior of curium was found to be similar to
that of amer~c~um. The main waves of americium and curium were
diffusion-controlled, but the pre-waves were not. It was found that the
pre-waves occured independently of the main waves, and that the main
waves were due to the reduction to the metallic state. The transfer
coefficients ~ and the cathod~c rate constants Kg at E=O V were obtained
as r;i. =0.41 and K~=8.8x10- 0 cmls for Am(III)/Hg(Am); 01.=0.50 and
K~=9.1X10-48 cmls for Cm(III)/Hg(Cm), respectively.
INTRODUCTION
The dc polarograms of lanthanide(III) ions exhibit two waves beyond the

hydrogen ion discharge in a non-complexing aquoues medium, with the
exception of Sm(III), Eu(III) and Yb(III). According to Large and
Timnick, the first wave can be attributed to the reduction of the
hydrogen ions produced by the protolytic dissociation of the hydrated
lanthanide(III), while the second wave is due to the adsorption of the
hydrolytic products of lanthanide(III)(1). Both waves are not
diffusion-controlled. Therefore, the reduction of lanthanide(III) into
the metallic state cannot be observed by dc polarography. There is no
data available on the kinetic parameters of the electrode reaction of
lanthanide(III) in an aqueous solution.
When a radioisotope is reduced to the metallic state at the mercury
dropping electrode with the potential E, the radioactivity A collected
in a given number of mercury drops is proportional to the number of
reduced ions. The activity A - potential E curve is the radiopolarogram.
In radiopolarography, the observed quantity is not the flux of
electrons(current), but the amount of amalgamated radioisotopes. This
quantity corresponds to the mass transfer accompanied with the
amalgamation and not to the electron transfer. Therefore, the reduction
of lanthanide(III) into the amalgam can be studied by radiopolarography
105
106 Y. SHIOKAWA AND S. SUZUKI
and from the data the kinetic parameters of this reduction can be
derived. We have studied the reduction wave for the reduction
Gd(III)/Hg(Gd) by radiopolarography(2).
The reduction of Am(lll) and Cmelll) into the amalgam in an aqueous
solution can be observed by radiopolarography, because their chemical
behavior is quite similar to lanthanide(lll). The radiopolarographic
behavior of Am(lll) and Cm(lll) has been investigated by Samhoun and
David (1) , but detailed behavior and the kinetic parameters of
amalgamation are still unknown. In order to determine these parameters,
we have investigated the radiopolarographic behavior of Am(lll) and
Cm( III) •
Materials and Methods
Radiopolarographic Cell
In a conventional radiopolarographic cell, the solution examined is in

direct contact with the insulating phase(CC1 4 ), in which the radioactive
amalgam is accumulated. In such a cell the radiopolarographic reduction,
in an organic solution or in an aqueous solution containing some soluble
substance in the carbon tetrachloride phase, is difficult because of the
direct contact with the organic phase(CC1 4 ). Also some experimental
troubles can result from the direct contact.
In this work we used a new radiopolarographic cell, shown in
Fig. 1, in which the solution examined is in direct contact with an
argon phase, not with the carbon tetrachloride. The inner surface of the
part of capillary E(inner diameter, 3 rom) below the stopcock F as is
shown in Fig. 1, was treated with dimethyldichlorosilane vapor. The
increased surface tension between the solution and the inner surface of
the capillary E held the solution above the argon phase, but the mercury
drops passed through the solution and the argon phase, and were
accumulated into the carbon tetrachloride phase.
Procedures
The 241 Am , 243Am and 243,244Cm used in this work were purified by the
standard ion exchange technique(~,2). An aliquot of the americium or the
curium solution(ca. 1M HC1) was evaporated to dryness by an infrared
lamp. The residue was dissolved in a small amount of distilled water and
the solution was evaporated to dryness. The residue was dissolved in 0.1
ml of 0.1 M HCl and 1 ml of 1 M LiCl and the solution was diluted to 10
ml. The pH was adjusted with HCl and/or LiOH and then solution was
heated. After cooling the radiopolarographic reduction was performed.
The final concentration of supporting electrolyte LiCl was 0.1 M.
The radiopolarographic procedures were as follows. The deoxidized
carbon tetrachloride and the solution to be examined were introduced
into the cell, and the tube connected to the needle valve I was filled
with argon. A constant potential was imposed at the dropping mercury
electrode(DME) for 10 min, while the mercury drops were accumulated in
the compartment on the stopcock G. Then the stopcock F was closed and
RADIOPOLAROGRAPHIC STUDY OF AMERICIUM AND CURIUM 107
the needle valves I and J, and the stopcock G were opened. By the flow
of CC14(J~G~I), the amalgam was rinsed in order to remove the
radioactive solution and dropped into the compartment on the stopcock H.
After the stopcock G was closed, the amalgam was taken out from the cell
with a small amount of carbon tetrachloride. The dried amalgam was
weighed, and then the amalgamated metal was extracted with 1 ml of 0.5 M
HN0 3 for 10 min. An aliquot of the extraction solution was determined by
means of d -ray or ~-ray spectrometry.
The pH value did not differ by more than 0.1 pH unit before and
after experiment. The radiopolarographic cell was thermostated at 25~1°C
in a constant-temperature box. The polarograph and the DME drop knocker
which controlled the constant lifetime of the mercury drop, were
deSigned in our laboratory.
A
Figure 1. Radiopolarographic cell.
A:DME, B:Hg anode, C:SCE, D:amalgam, E:capillary

F,G and H:stopcocks, I and J:needle valves.
Results and Discussion
Radiopolarographic Behavior
The radiopolarographic behavior of AmCIII) and CmCIII) in 0.1 M LiCl was

studied as a function of concentration, specific activity and pH of the
solution.
At pH=3.0, the concentration and the specific alpha activity of
americium were varied from 3.3x10- 6 M to 1.1x10- 8 M and from 0.009
~Ci/ml to 0.65 ~Ci/ml, respectively. The radiopolarograms are shown in
Fig. 2. In solutions with the same concentrations and different specific
activities, no significant changes were found between the
radiopolarograms. Near the electrode potential of -1.92 V(£) the
concentration of americium had a large effect on the radiopolarographic
behavior.
o 0
2 1: [Am]=3.3x10- 6M=0.32pCi/ml
D=3.0x10- 6cm 2 /s
o o 0 3 2: [Am]=1.6x10- 6M=0.057pCi/ml
D=3.0x10- 6cm 2 /s
4 3: [Am]=9.7x10-7M=0.37ftCi/ml
D=3.0x10-:- 6cm 2 /s
o 5 4: [Am]=9.6x10- 7M=0.035pCi/ml
D=3.0x10- 6cm 2 /s
6 5: [Am]=7.9x10-7M=0.65~Ci/ml
D=3.0x10- 6cm 2 /s
7 6: [Am]=3.1x10- 7M=0.011pCi/ml
D=3.2x10- 6cm 2 /s
7: [AmJ=1.1x10-BM=0.00B'iUCi/ml
D=3.2x10- 6cm 2 /s
-1.8 -2.0 -2.2

E vs. SeE I v
Figure 2. Radiopolarograms of Am(lll) at pH=3.0 in 0.1 M LiCl.

RADlOPOLAROGRAPHlC STUDY OF AMERICIUM AND CURIUM 109
A single wave with a half-wave potential E1/2 of approximately -1.88 V

was observed at 3.3x10- 6 M and the limiting activity, coresponding to
the limiting current, was found at a potential more negative than -1.92
V. But at a concentration of 1.6x10- 6 M, a pre-wave with a maximum
height at approximately -1.92 V and a main wave with a plateau at a
potential more negative than -2.02 V, were observed. The pre-wave was
observable at a concentration as low as 9.6x10- 7 M. Below 8.0x10- 7 M the
pre-wave disappeared and only a main wave was observed having a
half-wave potential of approximately -1.96 Vi the concentration of
americium had no effect on the radiopolarogram.
The diffusion coefficients calculated from the limiting activities,
shown in Fig. 2, were found to be almost constant and did not depend on
the concentration of americium. This shows that the limiting activity
and not the sum of the pre-wave height and the limiting activity, is
proportional to the concentration. It suggests that the main wave having
a plateau more negative than -2.02 V does not vary with the
concentration, and that the pre-wave is concentration dependant.
Therefore, the changes of the radiopolarogram, as is shown in Fig. 2,
can be attributed only to the pre-wave. The diffusion coefficients
obtained are lower than the values published in the literature(7). This
may be due to deamalgamation in the carbon tetrachloride phase(l).
2
1 : [Am]=3.2x10- 6M, pH=2.4
D=4.0x10- 6cm 2 /s
-
"2
:l
3 2: [Am]=6.7x10- 7M, pH=2.2
D=4.4x10- 6cm2 /s
>-
100
11 3: [Am]=6.7x10- 7M, pH=2.8
D=3.0x10- 6cm2 /s
~
c(
4
4: [Am]=7.9x10-~, pH=2.5
D=4.0x10- 6cm2 /s
-2.2
E vs. SeEI V
Figure 3. Radiopolarograms of Am( III) at various pH in 0.1 M LiCl.

Figure 3 shows the v~riations of the radiopolarograms with pH. At

pH=2.4 and [Am]=3.2xl0- M, a pre-wave and a main wave were observed.
The pre-wave was not observable at pH=3.0 and [Am]<8x10- 7 M but at a
lower pH(~2.5) the pre-waves appeared even at [Am]<8X10- 7 M, as it is
shown in Fig. 3. The potential of the pre-wave was shifted slightly with
concentration of americium. Though the half-wave potential of the main
waves was independent of pH, the diffusion coefficients at lower
pH«3.0) are slightly larger than the ones at pH=3.0. However, the
pre-waves apparently varied with pH.
Figure 4 shows the variation of the radiopolarograms of Cm at
pH=3.0. We could not examine a wide range of the concentration because
we used 243Cm(t1/2=28.5y) and 244CmCt1/2=18.11y). The pre-waves were not
observed at the concentration investigated. The half-wave potential of
Cm was found to be approximately -2.01 V. The diffusion coefficients
calculated are found to be almost constant, which shows that the wave
height is proportional to the concentration.
-
c
:::J
2
1 : [Cm]=1.6x10-8M=O.25foCi/ml
D=3.0x10- 6cm 2 /s
...>- 2: [Cm]=8.3x10-9M=0.13~ei/ml
-...
~
:0
«
3
D=3.6x10- 6cm 2 /s
3: [em]=1.6x10-9M=0.02~ei/ml
D=3.6x10- 6cm2 /s
-1.8 -2.2
E vs. SeEI V
Figure 4. Radiopolarograms of CmCIII) at pH=3.0 in 0.1 M LiCl.
Figure 5 shows the variations of the radiopolarograms of em with

pH. Similar to Am, the pre-waves of Cm were observed at lower pH, and
they disappeared at pH= 2.8. Also, the half-wave potential of main waves
did not vary with pH. The potential of the pre-waves of Cm is almost
equal to that of Am.
... 2
1: [Cm]=2.8x10- 8M, pH=2.3
D=4.0x10- 6cm 2 /s
-
>-
....
1!! 3 2: [Cm]=3.5x10- 8M, pH=2.8
:.0 D=2.6x10- 6cm 2 /s
....
«
3: [Cm]=8.9x10-9t1, pH=2.5
D=3.6x10- 6cm 2 /s
-2.0 -2.2
E vs. SeE I v
Figure 5. Radiopolarograms of CmCIII) at various pH in 0.1 M LiCl.
Figure 6 shows the dependence of the wave height on the mercury

column height. The abscissa is expressed as m2 / 3t 1/ 6 (m;the flow rate of
mercury, t;the lifetime of a mercury drop). The radiopolarograms
corresponding to the conditions of No.1 for Am and No.4 for Cm of
Fig. 6, exhibit single waves, and their limiting activities are found to
be diffusion-controlled. The radiopolarograms corresponding to the
conditions of Nos.2 and 3 for Am, and Nos.4 and 5 for Cm, exhibit the
pre-waves and main waves. The main waves are diffusion-controlled as
shown in Nos.2 and 5 of Fig. 6, but the pre-waves are not as shown in
Nos.3 and 6. These results show that the pre-waves occur independent of
the main waves. Because if this would not be the case, the main waves
would not be diffusion-controlled. This consideration is also supported
by the fact that the constant diffusion coefficients are obtained
independently of existing the pre-waves, as is shown in Fig. 2.
Thus, the pre-waves are not diffusion-controlled, and their height
and their potential of the maximum height are dependent on the pH and
the concentration of Am and Cm. The pre-waves may be the result of the
adsorption. This effect has been reported previously in dc polarographic
studies of lanthanide(III) ions(l). At present, we cannot explain
explicitly why the pre-waves occur.
On the other hand, the main waves are diffusion-controlled and

their heights are proprotional to the concentrations. Also the half-wave
potentials are constant within the pH range of our investigation. The
corresponding electrode reactions are considered to be totally
irreversible.
8 r---------.---------.----..,o.8
2?
Am
4 Q.4
c
'E y
-
52
-
U
c 0
0.5 1.0
?:' 8
...
:~
.::i
em
1.0
~----------~O~.S~----------~l~.O~------~O
m2/3tl/6 I mg2/3s-1/2
Figure 6. Dependence of the wave height on Hg column height

in 0.1 M LiCl.
1 : [Am]=7. 4x1 O-~, pH=3.0 and E=-2.050V

2: [Am]=7.0x10- 7M, pH=2.2 and E=-2.075V
3: [Am]=7.1x10- 7M, pH=2.2 and E=-1.905V
4: [Cm]=8.5x10- 9M, pH=3.0 and E=-2.050V
5: [Cm]=3.5x10- 8M, pH=2.2 and E=-2.106V
6: [Cm]=3.5x10- 8M, pH=2.2 and E=-1.926V
Kinetic parameters of the electrode reactions
For a totally irreversible electrode reaction, the following relations

in dc polarography are derived(~):
(RTid,nF) ln [ X(5.5-X)/5(1-X) ] = E1/2 - E (1)
with X=I/Id and the half-wave potential E 1 /2:
E1/2 = (RT/emF) ln [ 0.89 Kg (t/D)1/2 ], (2)
where I is the current at the potential E; I d , the limiting current; D,

the diffusion coefficient; t, the lifetime of a mercury drop; d, the
transfer coefficient; Kg,
the cathodic rate constant at E=O n, the V;
number of electrons; R, F and T have usual meanings. Equations (1) and
(2) are also valid for radiopolarography, if I and Id are replaced by
the activity A and the limiting activity Ad' respectively.
Now, from Eqs.(1) and (2) we can get the next relation:
(RT/d-nF){ ln X(5.5-X)/5(1-X) - 0.5 ln t } =
(RT/d-nF) ln ( 0.89 Kg/D1/2 ) - E.
According to this, a plot of log [X(5.5-X)/5(1-X)] - 0.5 log t vs. E

should result in a straight line for a constant lifetime t and should be
reduced to a single straight line for the different lifetimes. From this
plot one can obtain the transfer coefficient ~ and the cathodic rate
constant Kg .
....
CI
.B
,,
I
- "
~ /
.0
I
Am Cm l
--
x 0
.....
I 0 f
.,.t
0
°
10
f
I
0
f
>f
.0
,/
,.,
-1
.
,0
10
ui &
x
"-"
0
, 0
CI ,.'
S -2 2 •
I
-1.8 -2.0 -1.8 -20
E vs. SCE I V
Figure 7. Log plots for waves of Am(III) and Cm(III) at pH=3.0

in 0.1 M LiCl.
0: t=3.2 s, +: t=5.0 s
The radiopolarograms for the different constant lifetimes, t=3.2 s

and t=5.0 s, were obtained at pH=3.0 and concentration of [Am]=6.8x10- 8
M and [Cm]=8.1x10- 9 M, respectively. They exhibit only main waves. The
log plots according to Eq.(3) are shown in Fig. 7. These plots are
straight lines which are independent of the lifetime. The results
suggest the main waves of Am and Cm are attributed to the reduction to
the metallic states and not to a nonfaradic process such as an
adsorption.
KO/D 1/2 KO
;-1/2 cm ;-1
Am 0.41 3.6x10- 37 8.8x10- 4O
Cm 0.50 3.7x10- 45 9.1x10- 48
Table I Kinetic parameters of electrode reactions for Am(III)/Hg(Am)

and Cm(III)/Hg(Cm) in 0.1 M LiCl at pH=3.0 and 25°C.
Table I shows the kinetic parameters of Am(III)/Hg(Am) and

Cm(III)/Hg(Cm), where the diffusion coefficients are assumed to be
6.0x10- 6 cm 2 /s for both ions.
We observed the reduction of Am(III) and Cm(III), by
radiopolarography, to the metallic state in an aqueous solution and
obtained the kinetic parameters of this reaction, which were unknown
until now.
Literature Cited
1. Large, R.F,; Timnick, A. Anal.Chem. 1964, 36, 1258.
2. Shiokawa, Y.; Suzuki, S. Bull. Chem. Soc. Jpn. 1984, 51, 2910.
3. Saffihoun, K.; David, F. J. Inorg. Nucl.Chem. 1979, 41, 357.
4. Hulet, E.K.; Gutmacher, R.G.; Coops, M.S. J.lnorg.Nucl.Chem.
1961, 11, 350.
5. Choppin, G.R.; Harvey, B.G.; Thompson,S.G. J.lnorg.Nucl.Chem.
1956, 2, 66.
6. All electrode potentials in this paper are with respect to the
saturated calomel electrode(SCE).
7. Latrous, H; Oliver, J; Chemla, M. Radioanal.Radioanal. Lett.
1982, 53, 81-
8. Oldham, K.B,; Parry, E.P. Anal.Chem. 1968, 40, 65.
AMERICIUM TITRATION METHODS
Ph. CAUCHETIER - C. GUICHARD

Commissariat a l'Energie Atomique
IRDI - DERDCA - SEACC
P.O Box 6
F 92260 Fontenay-aux-Roses
France
ABSTRACT. To determine americium, we use either of the following me-

thods : spectrometry at 60 keV, spectrophotometry of Am (III) at 503 nm
or isotopic dilution mass spectrometry. These methods need reference
materials. Now only certified for activity materials exist. So we deve-
lopped titrimetric methods. The first is an original redox method. After
quantitative oxidation to Am (VI) at once by persulfate and argentic
oxide, we mix rapidly equal parts of the solution with different knowned
quantities of Fe (II) and dilute with molar perchloric acid until fixed
volume. Then we measure the Am (III) absorbance and infer its molar ex-
tinction coefficient and the americium concentration. The second method
is complexometry with EDTA : americium takes the place of mercury in the
Hgy2- complex and the quantity of free mercuric ions is determined by
pulse coulometry. We work in hexamethylene-tetramine medium at pH 5,5 or
in ammonia medium at pH 9,0. The results agree in a 2% range. We give
obtained molar extinction coefficients.
1. INTRODUCTION
The methods most commonly used to determine amer~c~um rely on a previous

calibration against a know americium solution, but the only reference
materials available are certified not in americium content but in acti-
vity only. This implies a proper knowledge of the half-life for which,
until very recently, the literature has contained two groups of values
different by 5%.
2. USED METHODS
Three principal methods are used in our laboratory to determine ameri-

c~um :
-ospectrometry on a solid source after evaporation of the solution.
The reproducibility obtained is better than 1%. Self-absorption effects
are much slighter than ~ spectrometry, which allows this method to be
used in many cases without previous separation. Thus a few ppm of 241 Am
115
N. M. Edelstein et al. (eds.), Americium and Curium Chemistry and Technology. 115-119.
116 PH. CAUCHETIER AND C. GUICHARD
can be measured in plutonium or mixed oxides, as can americium 241 con-

tained in spent fuels, after simple evaporation of the corresponding
~lutions. The method depends on the existence of reference materials,
which means that at present a mass can only be d~t3rmined through the
half-life value, and is also specific to 241Am. Am may be measured
as well with less sensitivity, but in this case the branching ratios
of the two isotopes must also be known.
- Direct absorption spectrophotometry using the characteristic Am (III)

peak at 5Q3 nm. The advantages of this method lie in its sensitivity
(high molar extinction coefficient), specificity (sharpness of peak)
and as the case may be non-destructiveness, since americium is usually
in the oxidation state (III) only. We use it regularly, especially for
the analysis of 243Am solutions used to prepare tracers for mass spec-
trometry or to milk off 239Np. It is also used for the determination
of americium in spent fuels, without separation as long as the Am/pu
ratio is at least 3.10- 3 , as well as in fission products. However the
technique demands either the use of reference materials of certified
americium content or a sufficiently accurate knowledge of the molar
extinction coefficients under the measurement conditions, and this can
only be obtained experimentally from known solutions.
- Mass spectrometry, which gives access to the isotopic composition and

through the isotopic dilution method to the concentration. It is ob-
viously necessary in both cases to separate elements possessing iso-
topes of identical mass, essentially plutonium and curium. This opera-
tion takes place in three stages.Plutonium and uranium are fixed on
anionic resin in 12 M HCl solution. The eluate containing rare earths
and trivalent actinides is itself separated into groups by passage over
anionic resin in nitric-methanol solution. Finally the fraction con-
taining americium and curium is separated over fine-particle cationic
resin at 80 0 C with «-hydroxy-isobutyric acid I 1 I. This method requi-
res tracer solutions (241Am or 243Am according to the isotopic composi-
tion of the americium to be measured) of known concentration.
3. CAL1BRATI0N METHODS
We have attempted to calibrate these methods and offset the absence of

americium reference materials by the use of titration methods involving
quantitative oxidation-reduction or complexation reactions. Coulometric
techniques have been proposed I 2,3,4 I, also an EDTA complexometric
method I 5 I.
Owing to the instability of higher americium valencies it is difficult
to apply coulometric methods and we prefered to use the fast reaction
reducing Am (VI) to Am (III) by Fe (II). The solution in question
(~10-2 M in M HCl 04, prepared from pure Am 02) is oxidised hot by a
mixture of argentic oxide and persulphate. After rapid cooling and vo-
lume adjustment equal fractions are mh:ed with exactly known quantities
of Fe (II). Each of the solutions obtained is diluted to known volume
in M HCl 04 and its absorption spectrum measured from 530 to 490 nm.
AMERICIUM TITRATION METHODS 117
Finally the peak heights are plotted against the quantities of Fe (II)
added (fig.l) : the curve is linear as long as the amount of Fe (II)
is sub-stoichiometric and the ordinate at the origin is zero.From this
curve we derive both the concentration of the americium solution and
the molar extinction coefficient of Am3+ in perchloric medium. The quan-
titativeness of the oxidation and the stability of Am (VI) were checked:
the amount of Am (V) present 10 minutes after oxidation, the moment at
which Fe (II) is added, is less than 1.5 % and Am (III) is undetectable
(0.9 % present after 4 hours).
A
0,.
FIGURE 1 : Reduction of Am(VI) by Fe(lll: Arn(lll) absorbance at 503 nm

versus added Fe~ll) amount.
The accuracy of the results obtained by this method, probably subject

to certain interferences (Pu, Np, Cr+ Mn .. ), was checked by another
method using the displacement by Am3 of mercuric ions complexed with
EDTA (Hg y2-) and the coulometric reduction of liberated Hg2+. The me-
thod is similar to that published by Bergey / 6 / but the medium chosen
was hexamethylene-tetramine at pH 5.5, non-complexing for Hg2+ and
hence more suitable than acetic solution for detection of the equivalent
point. This is accomplished by amperometry with two silver electrodes
amalgamated by dipping, between which is applied a potential difference
of 20 mV. A TACUSSEL TT700 'coulometric burette" combined with a TACUSSEL
Titrimax apparatus is used for the pulsed current generation and measu-
rement. An individual relative standard deviation of 1% is obtained for
a sample of about 300 pg, and 0.6% in the 2 mg region. It should be
noted that neptunium interferes here but not quantitatively, and that
about 1600 ppm is formed per year from 241Am.
118 PH. CAUCHETIER AND C. GUICHARD
The same methode has also been used in ammoniacal medium at pH 9 and
the results are not significantly different.
4. RESULTS
For purposes of comparison the molar extinction coefficient values for

the Arn3+ ion at 503 nm deduced from these calibration methods are given
in table I, and cross-check satisfactorily. They differ from already
published values / 7, 8 /. This ties in with the fact that the americium
contents found in reputedly pure oxide 'are lower by about 4 % than ex-
pected from the stoichiometry of Am 02'
Table I : Molar extinction coefficient values of Am 3+ in different me-

dia, deduced from various calibration methods.
x Obtained by comparaison of spectra (fig. nO 2)
xx Obtained by extrapolation of other values
Calibration method
Medium Fe (II) EDTA pH 5,5 EDTA pH 9,0
xx
HC10 4 - 0,9 M 422 430 + 3 426 + 4
HC10 4 - 0,9 M
420 ± 6
H2 SO4 0,16 M
HC10 4 0,08 M
H2 S0 4 0,92 M
411
x
419 * 415 x
HC10 4 0,08 M
HN0 3 3,68 M
327 x 333 * 330. *
HN0 3 4 M 319 'Xx 322 ±3 319 ± 3
AMERICIUM TITRATION METHODS 119
0,6
0,5
0,4
0,3
0,2
0,1
500 510 Anm
FIGURE 2 : Absorption spectra of solutions with the same Am concentration

(395 mg of Am0 2 per liter) in medium:
1- HelD. M
2 - HelD. 0,08 M - H2SO. 0,92 M
3 - HelD. 0,08 M - HN0 3 3,68 M
References :
/ / A. BILLON
J. Radioana1. Chern. ~l (1979), 297
/ 2 / G. KOEHLY
Anal. Chirn. Acta 33 (1965), 418
/ 3 / J.R. STOKELY, W.D~= SHULTZ
Anal. Chirn. Acta ~~ (1969), 417
/ 4 / R.C. PROPST
Anal. Chern. ~..!. (1969), 910
/ 5 / S. S. YAMAMURA-
Anal. Chern. ~Q (1968), 1898
I 6 / C. BERGEY, L~-FOUCHARD
Ta1anta ~§ (1979), 445
/ 7 / B.F. MYASOEDOV and a1.
Analytical Chemistry of trartsp1utonium elements (1972)
Israel Program for scientific translations
/ 8 / A.W. HARMON and a1.
LA-UR 81 2885 - Conf. 811025-5 (1981)
Part III
Electronic Structure and Thermodynamics

ELECTRONIC STRUCTURE OF NEUTRAL AND SINGLY IONIZED CURlUM*
Earl F. Worden
Lawrence Livermore National Laboratory
P.O. Box 808, L-464
Livermore, CA 94550
John G. Conway
Berkeley, CA 94720
Jean Blaise
Laboratory Aime Cotton
CNRS II
Batiment 505
91405, Orsay, France
ABSTRACT. Extensive observations and analyses of the emission spectra

of neutral and singly ionized curium, Cm I and Cm II, have resulted in
the determination of 785 Cm I and 598 Cm II energy levels. The levels
found combine to classify 9145 of the more than 14,250 lines of
244Cm observed between 240 and 2650 nm. Most of the levels have
Lande g-values from Zeeman effect data and isotope shifts from
measurements of spectra from sources with various enrichments of
244Cm, 245Cm, 246Cm and 248Cm. These data allowed us to
assign many levels to specific electronic configurations. The ground
configurations of Cm I and Cm II are [Rn] 5f 76d7s 2 and
[Rn] 5f77s 2 , respectively. The relative energies of other
electronic configurations of Cm are given and compared with analogous
configurations in other actinides and in Gd its lanthanide analogue.
1. INTRODUCT ION
There is now considerable knowledge of the electronic structure of

neutral and singly ionized curium, Cm I and Cm II. This has resulted
from our extensive observations and analyses of the curium emission
spectrum. The analyses have yielded over 390 odd and 395 even levels
of Cm I (most of these are published in Ref. 1) and over 434 odd and
164 even (nearly all unpublished) levels of Cm II. These odd and even
levels of the two spectra combine to classify over 9145 or 64 percent
of the more than 14,250 atomic emission spectrum lines of 244Cm
123
N. M. Edelstein et al. (eds.) , Americium and Curium Chemistry and Technology. 123-134.
© 1985 by D. Reidel Puhlishing Company.
124 E. F. WORDEN ET AL.
observed between 240 and 2650 nm. Most levels have Lande g-values
from Zeeman effect data and almost all of the levels have known
isotope shifts obtained from measurements of the spectra taken with
sources enriched in various percentages of the isotopes 242Cm,
244Cm, 245Cm, 246Cm and 24BCm (see Table I and Ref. 2). These
data, especially the extensive isotope shift data, have permitted
assigning a number of levels to specific electronic configurations and
the g-values allow term assignments of the levels.
Table 1. Isotopic Composition of Curium Samples Used for
Electrodeless Lamp Preparation.
Sam~le Percent of Isoto~e (>1%) Use
244 245 246 248
1 95 1.5 3 Wavelengths, Zeeman

effect, spectrum
assignment and reversal.
Isotope shift on strong
lines.
2 27 16 55 Isotope shift
3 55 23 21 Isotope shift
The analyses of these spectra have progressed to the point where

all levels expected below 15,000 cm- l have been identified in each
spectrum. As is the case in all very complex spectra, many levels
still remain to be found at high energies. However, the analyses are
quite complete and give a very good description of the electronic
structure of Cm I and Cm II.
Levels belonging to the most important electronic configurations in
the first, Cm I, and second, Cm II, spectra of curium have been
determined. These configurations and the lowest identified level in
each are given in Table II for Cm I and in Table III for Cm II. The
configurations for each spectrum are grouped as odd or even according
to spectroscopic rules. For the configurations considered here, a
configuration is odd if the total number of f plus p electrons is odd
and it is even if that total number is even. The energy of the lowest
level for each configuration is given. In our discussion we will use
the energy difference between the lowest levels as the energy
difference between the electronic configurations. These differences
will be representative of the promotion energy between
configurations. Tables IV and V contain similar sets of data for Gd I
and Gd II. In the tables the term designation, the Lande g-value and,
in the case of Cm, the isotope shift 246Cm - 244Cm are given for
each level.
ELECTRONIC STRUCTURE or NEUTRAL AND SINGLY IONIZED CURIUM 125
Table II. Lowest levels of identified configurations in Cm I.
Configuration Lowest Level Desig. Lande Isotope Shift

(cm- l ) g-value (10- 3 cm- l )
Odd
5f76d 7s 2 0.00 2.563 000

5f76d 27s 1014LL 93 2.B73 -339
5fB7s 7p 17656.63 1.621 -463
5f7 6d 3 30443.92 2.53 -619
5f76d7sBs 34255.16 2.064 -220
Even
5fB7s 2 1214.1B 1.452 -279

5f77s 27p 9263.37 2.li2 +118
5f76d7s7p 15252.70 2.835 -269
5f B6d7s 16932.72 1.466 -586
5f 76d 27p 325B1.06 a 2.043 -527
5f B7sBs 33013.09 1.54 -460
aLowest level of this configuration has not been found. It should be

11GI near 32000 cm- 1
Table III. Lowest levels of identified configurations in Cm II.
Configuration Lowest Level Desig. Lande Isotope Shift

(em-I) g-value (10- 3 em-I)
Odd
5f 7 7s 2 0.00 1.935 000
5f 76d7s 4010.66 2.492 -496
5f 76d 2 14830.15 3.009 -962
5f 8 7p 27065.li 1.51 -972
Even
5f87S 2093.88 1.500 -738

5fB6d 17150.79 1.415 -li77
5f77s7p 240l16.39 2.098 -403
5f76d7p 32034.44 2.933 -923
Table IV. Lowest levels of identified configurations in Gd I. a

Configuration Lowest Level Oesig. Lande
(cm- 1 ) g-va1ue
Odd
4f75d 6s 2 0.00 90 2 2.651
4f 75d 26s 6378.15 11F2 2.980
4f7 5d 3 22429.16 11F2
4f86s6p 25658.06 906 1.580
4f7 5d6s7s 31907.02 1103 2.496
4f76s 27s 34719.13 95 4 1.980
Even
4f8 6s 2 10947.21 7F6 1.480
4f 76s 26p 13433.85 9P3 2.225
4f75d6s6p 14036.03 11F2 2.955
4f85d6S 24255.10 9G7 1.515
4f75d 26p 25069.18 11Gl 3.764
4f86s7s 40439.51 9F7 1.550
aJ. Blaise, J.-F. Wyart and Th. A.M. Van Kleef, C.R. Acad. 5c. Paris,
1970, 70, 261-263, and J. Blaise, J. Chevillard, J. Verges,
J. F. Wyart and Th. A.M. Van Kleef, 5pectrochim. Acta, 1971, 26B,
1-34.
Table V. Lowest level of identified configurations in Gd II. a

Configuration Lowest Level Oesig. Lande
(cm- 1 ) g-value
Odd
4f75d 6s 0.00 100 512 2.557
4f76s 2 3444.24 85 7/2 1.920
4f75d 2 4027.16 10F3/2 3.163
4f 86p 32595.35 80 1112 1.565
Even
4f 86s 7992.27 8F13/2 1.537
4f85d 18366.85 8G15/2 1.465
4f76s6p 25668.69 lOP7/2 2.190
4f75d6p 25960.07 10F312 3.095
a J. Blaise, J. F. Wyart and T. A.M. Van Kleef, J. Phys. (Paris),
1971, 32, 617, and J. Blaise, J. Chevillard, J. Verges,
J. F. Wyart and Th. A.M. Van Kleef, 5pectrochim. Acta, 1971,
26B, 1-34.
ELECTRONIC STRUCTURE OF NEUTRAL AND SINGLY IONIZED CURIUM 127
Comparison of Tables II and IV and III and V show some

similarities in the energies of like configurations for the two
spectra of the elements but there are also some notable differences.
The general ordering of the configurations considered here for the
first spectra (Cm I and Gd I, Tables II and IV) is the same except for
f 7d3 . The Sd electrons are relatively more tightly bound in Gd
than the 6d orbital electrons are in Cm. This is true in both the
neutral and singly ionized configurations involving f7. More
striking is the relative positions of configurations involving f7
and fB. The even configuration SfB7s 2 in Cm I is only 1214
cm- l above the Sf76d7s 2 ground configuration in Cm I while in
Gd I 4f B6s 2 is 10947 cm- l above the equivalent ground
configuration 4f7Sd6s 2 . All equivalent fB configurations in
em I are lower in energy by 7000 to 9000 cm- l than the corresponding
configurations in Gd.
Changes in the relative ordering of the electronic configurations
because of differences in binding energies of orbital electrons in the
two elements is more evident in the singly ionized or second spectra,
Tables III and V. Here, the ground state of em II is Sf 77s 2 some
4010 cm- l below Sf76d7s the configuration equivalent to the ground
configuration in Gd II, 4f 7Sd6s. The promotion energy f7 s2 to
fBs is only 2094 cm- l in em II while it is 4550 cm- l in Gd II.
As a result, the configuration ordering in Cm II is f7 s2, fBs,
f 7ds f 7d2 while in Gd II it is f 7ds f7 s2 f 7d2
fBs.' The p orbital electrons do sho~ some'diffe~ences but not the
marked differences exhibited by f and d orbital electrons.
Fig. 1 shows the relative positions of three electronic
configurations each in neutral actinides and lanthanides. In the
figure, the lowest level of the fN- 1ds 2 configuration is set at
zero energy and the positions of the lowest levels of the fNs2 and
fN-l dsp configurations are shown. The promotion energy for s to p
is about the same in the actinides as in the lanthanides and nearly
constant across the series. This relationship and other trends in
these and similar plots with more configurations are useful in the
analyses of actinide and lanthanide spectra since estimates can be
made of the position of unknown lowest levels of various
configurations (dotted lines in the figure).
Fig. 1 shows that the f to d promotion energy changes consjderably
across the series. The general trend is for the fN s2
configuration to become more stable as the series are ascended. The
Sf N7s 2 configuration is less stable than 4f N6s 2 relative to
fN- 1ds 2 for N less than or equal 7 but the opposite is true when N
is equal to or greater than B. Thus the two curves cross between N
equal 7 and B. The Sf orbital electron is more stable relative to the
6d orbital electron in the heavier actinides than is the 4f orbital
electron relative to the Sd orbital electron in the heavier
lanthanides.
The increased stability for the Sf orbital electron versus the 6d
orbital electron is more clearly shown in Fig. 2 where the fN s2
configuration is set at zero energy. This increased stability of the
5f orbital electron is related to the tendency toward divalent

character for the higher members of the series found by nuclear
chemists before the positions of the electronic configurations had
been established by spectroscopists. Again, one can see that the
promotion energy for 7s to 7p orbital electron is nearly constant
while the 7s to 6d promotion energy increases across the series.
N 2 3 4 5 6 7 8 9 10 11 12 13
20
16
12 4fllo 5d6s6p
8
~
I
E
(,.)
4
'"o 5f N - ' 6d7s 2
o
4(' 5d6s""
>-
01
Qj -4
I::
w
-8
- 12
-16
-20
- 24
Th Pa U Np Pu Am Cm Bk Cf Es Fm Md
P P S E G TI D.. Y n
Fig. 1. Energy differences of the lowest levels of the fNs2 and

fN-l dsp configurations relative to fN- 1ds 2 in the neutral or
first spectra of some actinides (Sf configurations--dark) and
lanthanides (4f configurations--light).
N 2 345 678 9 10 11
32
28
... fN-'dsp
I
24
20
~
16
I
E
u
M 12
0
c:
>
8
...
CI
Q)
c:
w 4
-4
-8
-12 I
~
Th Pa U Np Pu Am Cm Bk Cf Es
Fig. 2. Energy of the lowest levels of several configurations

relative to the lowest level of fN s2 in neutral actinides. In the
configurations shown, the electrons are Sf, 6d, 7s and 7p. The
increase in stability of the fN s2 configuration across the series
is evident.
Only the lowest levels of various configurations have been shown

thus far. A large number of complete terms have been found for many
of the configurations of Cm I and Cm II. Table VI shows levels of the
5f87s configuration of Cm II. This table clearly illustrates the
value of isotope shift in making assignments of levels to
configurations. The term assignments are made by use of the
experimental Lande g-values. The constancy of isotope shift and the
agreement of the observed g-values with values from theory or with the
LS g-values substantiate the validity of the assignments.
Table VI. Low levels of the 5f87s configuration of Cm II.
Level a ISb
(cm- l ) J gobs gLS gcalc (mk) Desig.
2093.88 13/2 1.500 1.540 1.499 -738 8F

3941.46 11/2 1.424 1.455 1.432 -765 6F
5919.28 9/2 1.527 1.577 1.529 -736 8F
6347.92 11/2 1.500 1.554 1.495 -744 8F
7067.14 7/2 1.485 1.620 1.492 -748 8F
8144.32 9/2 1.400 1.435 1.404 -765 6F
8436.11 5/2 1.656 1.716 1.655 -733 8F
9073.60 7/2 1.444 1.398 1.439 -753 6F
9127.87 3/2 1.834 2.002 1.847 -733 8F
9801.32 112 3.740 4.007 3.739 -729 8F
10433.80 5/2 1.300 1.315 1.305 -763 6F
11250.911 3/2 1.167 1.067 1.155 -759 6F
11978.47 1/2 -0.420 -0.670 -0.425 -760 6F
aJ. Blaise, J. F. Wyart, J. G. Conway and E. F. Worden, Phys.
Scripta, 1980, 22, 224.
bIsotope shifts are relative to the 5f 77s 2 8S7/j ground
state. They are 246Cm- 244 Cm in mK (1 mK = 10- cm- l ).
The level structure of the lowest terms in Cm II are shown in
Fig. 3. The electronic configurations and LS term designations are
indicated. The structure of the levels of the 5f87s configuration
given in Table VI is more clearly illustrated in the figure. The
closeness in binding energy of the 5f, 6d, and 7s orbital electrons is
evident.
Fig. 4 shows the range of isotope shifts observed for assigned
levels in the Cm I and Cm II spectra. It should be noted that there
is overlap of observed shift for a number of configurations. In these
cases, theory, Lande g-values, transition intensities and other
factors are important for assigning the level to the appropriate
configuration. As seen in the figure, we report the shifts relative
to the ground state as x. For the shifts shown in Table II, III and
VI, x is zero. The shifts are the frequency of 246Cm minus the
frequency of 244Cm. As is well known, the isotope shift is caused

by interaction with the nucleus of the penetrating s orbital electrons
and to a lesser extent by the P1/2 electrons. Since f electrons act
to shield or reduce the penetrations of the sand p electrons, the
configurations with smallest isotope shift of those shown should be
f 7d3 and f 7d2p in Cm I and f 7d2 and f 8d in Cm II. Thus
the value of x should be about + 0.7 cm- l for Cm I and about
+1.2 cm- 1 for Cm II.
ODD EVEN
14
sF
12
I 10 8 D
E
(,)
M
0
0-
8
r:::
>
...Cl 5f 7 6d7s
Q)
r::: 6
w
5f 7 7s 28 S
0
5/2 9/2 13/2 1/2 5/2 9/2 13/2
Fig. 3. Low lying energy levels of singly ionized curium. The

electronic configurations and LS term designations are given.
Cml Cmll
+0.2 ODD EVEN ODD EVEN +0.2
15f77S27P I
B
X X
15f7Sd7S2'
-0.2 -0.2
7
E
.."
.5
-0.4
..
-0.4
I"',",, I
"i
CD
N
:: -O.S
5f'7s7p -O.S
~
5f'Sd 27p
g"
Q.
~ -0.8 5f8 Sd7p -0.8

5f8 Sp-
-1.0 -1.0
5f 7Sd 2
-1.2 -1.2
Fig. 4. Range of observed isotope shifts for several electronic

configurations of curium I and II. The value of x is about
+0.7 cm- l for Cm I and about +1.2 cm- 1 for Cm II.
Investigation of the isotope shifts with sources 2 and 3 listed in
Table I were very important in obtaining reliable isotope shift values
for the levels. The use of exposures from all three of these samples
on the same plate made resolution of many confusing shifts on
individual lines possible. By use of lines with large isotope shift
and with negligible or no 245Cm hyperfine structure, we were able to
determine the relative isotope shift values shown in Fig. 5. The
relative isotope shift for 242Cm was obtained from data of Conway
and McLaughlin. 2 For lines with small isotope shift more accurate
246Cm - 244Cm shifts could be calculated from the more accurately
measured 248Cm - 244Cm shift and the relative isotope shift
values. The odd-even staggering common in the actinides is shown by
the position of 245Cm in Fig. 5.
We show in Table VII a listing of papers dealing with observations
of the atomic emission spectra and energy level analyses of Cm I and
Cm II. The major contribution of each paper is noted in the Table.
The early investigations 1 and 2 were limited by the small quantities
of material, sources and spectrographs. The production of 2 mg of
highly purified 244Cm by E. K. Hulet, the use of electrodeless lamps
as sources, the use of the 9.15 m grating spectrograph at Argonne
National Laboratory with the associated high quality 2.4 T magnet, and
finally the use of the Fourier Transform Spectrometer at Laboratory
Aime Cotton all contributed to the successful acquisition of the very
high quality data needed for the analyses of these complex spectra.
Table VII. Papers and reports on the atomic emission spectrum of

curium, Cm I and Cm II.
Paper or Report Major Contribution
1. J. G. Conway, M. F. Moore and About 200 emission lines from
W. W. T. Crane, J. Am. Chern. a spark source 252 to 500 nm.
Soc., 1951, 73, 1308.
2. J. G. Conway and R. D. McLaughlin, Isotope shifts 244Cm- 242Cm
J. Opt. Soc. Am., 1956, 46, 91. of 183 lines on large
spectrograph 305 to 525 nm.
3. Leo Brewer, J. Opt. Soc. Am., Energies of electronic
1971, 61, 1101 and J. opt. Soc. configurations of neutral,
Am., 1971, 61, 1666. singly, doubly and triply
ionized actinides.
4. R. H. Gaddy, Applied Analytical methods for
Spectroscopy, 1972, 26, 49. impurities in Cm and Cm in Am.
5. E. F. Worden and J. G. Conway, Energy levels of Cm I, 335
J. opt. Soc. Am., 1976, 66, 109. odd and 348 even levels,
isotope shift, Zeeman effect,
relative energies and
isotopic shifts of
configurations.
6. J. G. Conway, J. Blaise and Atomic emission lines Cm I
J. Verges, Spectrochim Acta, and II 850 to 2640 nm, energy
1976, B31, 31. levels, and energy level
classification of lines.
7. E. F. Worden, E. K. Hulet, Wavelength, isotope shifts,
R. G. Gutmacher, and J. G. Conway, g-value, intensities,
Atom. Data and Nucl. Data Tables, spectrum assignment and energy
1976, 18, 459. level assignments for 2034 of
the strongest 244cm lines
of em I and II in the 240 -
1120 nm region.
8. E. A. Lobikov, N. K. Odintsova and Emission spectrum of Cm I and
A. R. Striganov, "Emission Spectrum II 242 to 701 nm.
of Curium, Report IAE - 3210," Wavelengths, intensities
I. V. Kruchatov Institute self-reversal. 6771 lines
of Atomic Energy, Moscow, 1979. reported, no levels, some
spectrum assignment. List
contains over 800 impurity
lines of Pu and lanthanides
not found and eliminated by
the authors of the paper.
9. E. A. Lobikov, A. R. Striganov, Curium isotoQe shifts 246Cm_
V. P. Labozin, N. K. Odintsova 244Cm and 24BCm_ 246 Cm
and V. F. Pomytkin, opt. and for 97 lines 404 to 693 nm.
Spectrosc., 1979, 46, 596. Wavelengths and intensities
(Classifications taken from
papers 5 and 7).
242 244 246 248
1.10 ± 0.07 -1-·---1.000--~'-1-0.954 ± 0.012
- 0.35 2 ± 0.012
245
Fig. 5. Relative isotope shift for the atomic emission spectrum lines
of five isotopes of curium.
III. ACKNOWLEDGEMENTS
This work was supported in part by the U. S. Department of Energy
under Contract No. W-7405-ENG-48 at the Lawrence Livermore National
Laboratory, by the Director, Office of EnerflY Research, Office of
8asic Energy Sciences, Chemical Sciences Division of the U. S.
Department of Energy under Contract No. DE-AC03-76SF at the Lawrence
Berkeley Laboratory and in part by Centre National de la Recherche
Scientifique, France.
References
1. E. F. Worden and J. G. Conway, "Energy Levels of the First
Spectrum of Curium, Cm I," J. opt. Soc. Am., 1976, 66, 109-121.
2. J. G. Conway and R. D. McLaughlin, J. opt. Soc. Am., 1971, 46,
91.
SHIFTED HOMOLOGOUS RELATIONSHIPS BETWEEN THE TRANSPLUTONIUM AND EARLY
RARE-EARTH METALS*
John W. Ward
Materials Science and Technology Division
Los Alamos National Laboratory, Los Alamos, NM 87545
ABSTRACT. The physico-chemical properties of the late actinide metals

americium through einsteinium are compared with their rare-earth
counterparts. Localization of the 5f electrons beginning at americium
signals the appearance of true rare-earth-like properties, but the
homologous relationship is shifted to place americium below praseo-
dymium, einsteinium is then below europium. The comparison of crystal
structures, phase transitions, vapor pressures and heats of vaporiza-
tion reveals remarkable similarities, especially for Sm-Cf and Eu-Es,
where the stability of the divalent metal becomes established and di-
valent chemistry then follows.
There is of course a major perturbation caused by the half-
filled shell at curium, although it may be argued that americium is
the anomaly in the so-called second rare-earth series. However, the
response of americium, berkelium and californium under pressure re-
veals the true perturbation to be a thermodynamic one, occurring at
curium.
The onset of 5f electron localization in the actinides is probably

first seen in the higher temperature phases of plutonium'oparticu-
larly the fcc delta phase, with a metallic radius of 1.64A and a
rare-earth-like X-ray adsorption-emission response. Nevertheless,
no magnetism is observed, and the radius is still somewhat small com-
pared to the rare-earth metals. The return of 5f bonding is shown
dramatically in the epsilon and liquid phases, producing (as with nep-
tunium) a very low melting point and a liquid with extremely high vis-
cosity and a high boiling point.
The complexities continue with americium, where a major localiza-
tion and 6-band narrowing occurs but magnetism is again quenched by
by the 5f electronic configuration; this unusual non-magnetic ground- 2
state also allows americium to become superconducting, like lanthanum.
Chemically americium is clearly a trivalent metal. The divalent state
is orly stabilized by a large ligand such as 1-; tetravalency occurs
with strong oxidizing agents (02,F 2 ) because the Sf electrons, though
localized, are very close «2eVJ to the Fermi
*Work performed under the asupices of the U.S. Department of Energy.

135
136 J. W. WARD
level. Crystal structures are similar to those of the early rare-

earths - dhcp 3t room temperature and fcc at higher temperatures.
High-pressures transform the lattice first to an fcc structure (as
do the rare-earths), then to an exotic double body-centered mono-
clinic phase, and then finally to an ~-uranium-type type structure in
the re.nge 15-20 GPa, again sho~!ing the proximity of the 5f electrons
to the Fermi level.
The dhcp room temperature and fcc high temperature phases are
also found for curium and the elements berkelium and californium, in
marked contrast to the supposed homo logs directly above these ele- 4
ments in the periodic table. A suggestion first noted by Johansson
shifts the homologous relationship so as to place americium below
praseodymium, which then allows comparison of the t~.o series as
chemical and structural homologs. This is illustrated in Table 1.
The f-bonded early actinides are grouped for convenience under plu-
tonium, which becomes the homolog for (the f-bonded collapsed a-phase
of) cerium. It should be noted that cerium is often used as a stand-in
for plutonium, where radioactive contamination must be avoided.
Americium then becomes the homolog for praseodymium, as noted
above. Both metals can be oxidized to the dioxide, due to the prox-
imity of the f electron energies to the Fermi level. The heat of
vaporization for Pr is 85.0 kcal/mol which may be compared with
67.92~~al/mol ~~3 Am, as measured by Ward and coworkers (5,6) on both
the Am and Am isotopes; these data are shown in Fig. 1. A long-
standing controversy between the measured and theoretical values for
the heat of vaporization has recently been regol1ed by a new spec-
troscopic value for the lowest level of the f ds Am I configuration,
thus finally bringing the theoretical calcu~a7~~8s into harmony with
experiment. Various theoretical treatments' have had consider-
able success in predicting the cohesive energies (cvheat of vaporiza-
tion) for the rare-earths, failing for the early actinides because of
no viable model for the itinerant and bonding Sf-electrons. These
correlations are based on the spectroscopic values for the gas (free
atom) and the heat of solution of the metal; it might therefore be
expected that reasonable estimates would be made for the elements
americium and beyond, where f-bonding no longer is in the picture.
This indeed turns out to be true, with the resolution of the ameri-
cium calculation just discussed.
It can be seen immediately that a major perturbation in the ho-
mologous relationship in Table I occurs at curium, because of the
half-filled shell effect. Is curium like neodymium or gadolinium?
Comparing crystal structures the former is true; in terms of a heat
of vaporization (Cm = 92.2 kcal/mol, Gd = 95.0 kcal/mol,
Nd = 73.3 kcal/mol) the latter seems to be true. However, the "prob-
lem" is not really a problem at all; the argument is simply a thermo-
dynamic one, since the half-filled shell stabilizes the trivalent
Cm(Gd) gas. In terms of solid-state properties, the homologous re-
lationship remains Cm-Nd.
For the elements beyond plutonium, measurements of the heat ca-
pacity are difficult-to-impossible, due to the intense radioactivity
>-l
;;0
;..
z
."
'"t""'
c::
>-l
o
z
2
TABLE I :::
;..
z
o
t1l
;..
COMPARATIVE PHVSICOCHEMISTRV OF LANTHANIDES AND ACTINIDES ;;0
t""'
-<
;;0
;..
;;0
r--l t1l
M
La ICe t I Pr Nd Pm Sm Eu* ;..
;;0
I I Tb >-l
:t
I I
IG: half-filled shell :::t1l
I I >-l
;..
Ac I Pu I Am t""'
f L __ , c~ ____~~ ____ ~f_____~S:m cjm '";;0
t"'1
I __ t""'
;..
I II~ I half-filled shell >-l
Th I Pa U Npl oZ
'"
,~
~ ..I.
f-bonding
tf-bonding in the collapsed phase

*divalent
w
--.]
-
138 J. W. WARD
-3
10
:-MP1448K
I
I
I
,(3-y 1345K
I
-4
10
.,
Ul
Q;
.c
a.
III
o
oE
~IO
-5
LrJ
a:
::>
U)
U)
LrJ
a:
D..
-6
10
-7
10
Figure 1.
Vapor pressure data for americium. The heavier line represents
37 data points taken with the 241 isotope (Ref. 5); extent of
range is indicated by small arrows. Data points and the lighter
line represent values with the 243 isotope, extending into the
liquid range: 0 Los Alamos data; • Karlsruhe data (Ref. 6).
TRANSPLUTONIUM AND EARLY RARE-EARTH METALS RELATIONS 139
58
57
ed \7U
56 \7Np
55 ~-o ..... 0
T h ,I:;)'" "Am
III 54 ed'
\t/ "\ \1
0
01 \ /
0 53 • b" d'
0 Pu
v 52
(f)-
51 •
50 • •
49 II
Non-mag l i b ' (fIl
asellne 4 ) ___ --* -+ -+- +- .0
------~
48
47 d' ...c"'" -0--0. .
e.,...
Am / /
..I '"
v,~o curve
46
III / b
g, 45 9
as
~ 44
e d' •• •
dO
.
(f)
43
...--- "Nol'-m~" bose line (5f)
42 Pu
, .., ....
411~4-~"~~~~~~~~~~~
40~~--~-~--~~--~~--~~--~~~~-=~~~
Ba La Ce Lu
Figure 2,
Comparison of gaseous entropip-s for the lanthanides and actinides
at 298K and 1400K, 0: divalent (dO) curve for the lanthanides; •
trivalent (d S ) gases; \l fully magnetic actinide gas; • nonmag-
netic portion of entropy for each element.
...o
TABLE II
Comparative Values for the Actinides Am-Es and Lanthanides Pr-Eu

0 0
Metal Crystal H.P. B. P. Co 611 298

p S298
PairCs) Phases (K) P98K) (Ca l/K/Hol) (Cal/K/mol) (kcal/Hol) Ch~mistr~
Am dhcp, fcc 1449 "'2220 5.97 13.20 67.9 III III, IV]
Pr dhcp, fcc 1204 3785 6.56 17 .67 85.0 III IIV]
Cm dhcp, fcc 1618 3383 6.62- 17 .20· 92.2 III IIV]

Nd dhcp, fcc 1289 3341 6.55 16.99 78.3 I II [IV)
(Gd) (hcp, bee) (1585) (3539) (8.86) (16.24) (95.0) (III)
Bk dhcp, fcc 1323 2900 6.24- 18.68- 74.1 III

Pm dhcp, fcc(?) "'1350 2730(1) 1 III
Cf dhcp, fcc 1173 1745 6.70- 19.25- 46.9 III, II

Sm -Sm (dhcp un- 1345 2064 7.06 16.61 49.4 Ill, II
der pressure)
Es fcc 1133 1241 6.39- 21. 38 a 31.8 II

Eu bee 1090 1870 6.48 19.31 41.9 II
[ ) = other possible valence states

afrom the Entropy correlation, Ward & Hill (11)
'-<
;E
::;::
»
:;<l
ti
and/~l vanishingly small quantities for the experiment. Ward and

Hill have established a correlation relating the crystal entropy
S298 to metallic radius, atomic weight, magnetic properties and
electronic structure. This correlation permits estimates of re-
liable entropy values for metals for which no data are available,
based on comparison with a closely-similar metal for which there are
measured data. The early actinides cannot be assessed by this cor-
relation, because there is no model (as for the theoretical calcu-
lation) to account for the complex Sf-electron bonding. However,
success is expected and realized for the metals americium and be-
yond. The estimated value for the correlation for americium of
13.2 ca~4~mo1/K has brin precisely confirmed recently by experiments
on the Am isotope.
Noteworthy is the huge change of entropy (4.13 ca1/K/mo1) upon
vaporization of Am from the trbralent non-magnetic solid to the di-
valent magnetic gas. It should be noted that all of the actinide
gases are fully magnetic, like the rare-earths, as shown in Fig. 2.
Perhaps this should be obvious, but it is interesting that simple
subtraction of the magnetic entropies results in a good nonmag-
netic baseline, except for curium, where there are many low-lying
excited excited states.
The importance of the crystal entropy lies in the fact that the
S'Q8 value is the basis point for the free-energy functions for both
tne solid and gas. From a reasonably accurate estimate for the solid
entropy, the gaseous spectroscopic data, and precise vapor pressure
measurements, it is possible to calculate all the thermodynamic func-
tions for the metal up to the highest temperatures of measurement.
These values have been recently tabulated in the Metals Chf~ter of the
"Handbook for the Physics and Chemistry of the Actinides".
Unfortunately there exist as yet no data for the rare-earth ele-
ment promethium, so a comparison with berkelium cannot easily be made.
However, it is expected on the basis of the regularity seen elsewhere
that the comparison will be excellent. t~ the measurement of the va-
por pressure of pure berke1ium-249 metal neodymium was used as the
comparative element for the entropy correlation, (correcting for the
proper magnetic entropies) and the fit was excellent. The measured
heat of vaporization for berkelium of 74.1 kcal/mol may ~e compared
with that for neodymium of 78.3 kcal/mo1. The expectation is that
the the value for promethium, when finally measured, will be lower
than for neodymium.
The comparison at samarium/ ca1:i.fornium is especially revealing.
Incipient stabilization of the divalent state is seen in both metals,
with divalent chemical compounds easily fo~ed. The surface of sa-
marium metal has been shown to be divalent ,and there was some
question in the early stages of californium metal studie~6whether
the metal was dj_valent. However, the thermodynamic data clearly
establish californium to be a trivalent metal but with a heat of va-
porization of only 46.9 kcal/mol (as compared to 49.4 kcal/mol for
samarium) and with a vapor pressure midway between that for samarium
and europium, as shown in Fig. 3.
142 J.W. WARD
\ \
\ \
\ \
\ \
10 5 \ \
\ \
-'"
(l)
\ \
~
(l)
\ \
.s=.
a.
'"0E \ "U
_
\ \
--c 10 6
W
0:::
~m \
=>
en \
en
w
0:::
\
CL
T
boH =- 45.28 keel/mole
\
10-7 boS~ =25.97 e.u. \
0- TARGET DATA
0- MASS SPEC. DATA

\
\
\
\
10- 8
\
0.9 1.0 1.1 1.2 1.3
IOOO/T (kelvin)
Figure 3.
Vapor pressure of solid californium, compared to data for
samarium a.nd europium (Ref. 16). Target data (0) and mass spec-
trome2E~c data (0) were taken, starting with a 2 mg sample of
pure Cf (tailoff for the highest points was due to incipient
sample depletion).
600 M ( s, I) to M ( 9 )
140
500 120
0 100 0
E 400 E
......... .........
J t")
.::I! (.)
80 ~
300
60
200
40
20
Th U Pu Cm Cf
Po Np Am Bk Es
Figure 4.
Comparative plot of the cohesive energies of the actinide
metals, in kJ/mol (left ordinate) or kcal/mol (right ordinate).
Open data point at Pa represents a still-unresolved uncertainty
for this element. -
144 J. W. WARD
Recent Henry's-Law ~aY9rization studies of einsteinium-253 dis-

solved in ytterbium show' the metal to be clearly divalent, with a
heat of vaporization of only 31.8 kcal/mol (similar to strontium),
thus thus completing the homologotll'~ miniseries by analogy to divalent
europium.
Some comparative properties of the early lanthanides and late ac-
tinides are smmnari7.ed in Table II. Trends in cohesive energies are
illustrated by the measured heats of vaporization of the actinide
metals, plotted in Fig. 4.
Beyond einsteinium there is no corresponding half-filled shell in
the actini~e series, and the divalent state will continue to be the
preferred electronic configuration for the metals fermium and beyond.
At the moment, half-lives are too short and quantities too small for
meaningful bulk measurements beyond einsteinium.
Thus in su=ary, a shifted homologous relationship exists for the
transplutoniurr actinides, resulting in the miniseries Am-Es cor-
responding to the series Pr-Eu. The half-filled shell at curium in-
troduces a thermodynamic complication which is however not reflected
in the condensed phase properties of this element.
References
1. Bonnelle, C., Structure and Bonding (Berlin) 31 (1976) 23.
2. Smith, J. L., Haire, R. G., Science 200 (1978) 535.
3. Roof, R. B., Zeit. fur Kristall. 158 (1982) 307.
4. Johansson, B., Phys. Rev. R 11 (1975) 2836.
5. Ward, J. W., Muller, W., Kramer, G. F., Transplutonium 1975, Eds

~!. Muller and R. Lindner, North-Holland , Amsterdam/American
Elsevier, New York (1976) 161.
6. Ward, J. W., Kleinschmidt, P. D., J. Chern. Phys. 71 (1979) 3920.
7. Nugent, L., Burnett, J. L., Morss, L. A., J. Chern. Thermo,S

(1973) 665.
8. Samhoun, K., Ph.D. Thesis, Universite'de Paris-Sud, Centre

d'Orsay, Ser. A, No. 1727, 1976.
9. Kleinschmidt, P. D., Ward, J. W., Matlack, G. M., Haire, P. G.,

High Temperature Science (1985) - to be published.
10. Johansson, B., J. Less-Commons Metals 100 (1984) 49.
l1. Ward, J. W., Hill, H. H., Heavy Element Properties, Eds.

W. Muller & H. Blank, North-Holland, Amsterdam/American
Elsevier, New York (1976) 65.
12. Maller W., Schenkel, L., Schmidt, H. E., Spirlet, J. C.,

HcElroy, D. L., Hall, R. O. A., Mortimer, M. J., J. Low-
Temp. Phys. 30, 561.
13. ~Jard,J. W., Kleinschmidt, P. D., Peterson, D. E., Chapter

"Thermochemical Properties of the Actinide Elements and Selected
Actinide-Noble Metal Intermetallics," in the Handbook of the
Physics and Chemistry of the Actinides, Eds. A. J. Freeman,
G. Lander and C. Keller, North-HollAnd, Amsterdam (1984) - to be
published.
14. Ward, J. W., Kleinschmidt, P. D., Haire, R. G., J. Chern. Phys.

77 (1982) 1464.
15. Allen, J. W., Johansson, L., Bauer, R. S., Lindau, I.,

Hagstrom, S. B. A., Phys. Rev. Let. 41 (1978) 1499.
16. Ward, J. W., Kleinschmidt, P. D., Haire, R. G., J. de Physique

(Paris) ~Q (1979) C4-233.
17. Kleinschmidt, P. D., Ward, J. W., Matlack, G. M.,

Haire, R. G., J. Chem. Phys. 81 (1984) 473.
THERMODYNAMIC SYSTEMATICS OF OXIDES OF AMERICIUM, CURIUM, AND
NEIGHBORING ELEMENTS
L. R. Morss
Chemistry Division, Argonne National Laboratory
9700 South Cass Avenue
Argonne, Illinois 60439 USA
ABSTRACT. Recently-obtained calorimetric data on the sesquioxides and

dioxides of americium and curium are summarized. These data are com-
bined with other properties of the actinide elements to elucidate the
stability relationships among these oxides and to predict the behavior
of neighboring actinide oxides.
1. INTRODUCTION
The solid-state chemistry of metallic elements is centered on their

oxides. For the transuranium elements, the oxides were the first well-
characterized substances to be prepared and have been the most thor-
oughly studied class of compounds. For the elements beyond plutonium,
however, inaccessibility of adequate amounts of long-lived isotopes
inhibited the study of their solid-state properties until recently.
Thermodynamic measurements on transplutonium oxides before 1980
were limited to thermogravimetric and manometric studies (1-8) and one
solution-calorimetry investigation (9). This paper summarizes more re-
cent results and places these results in the perspective of other rele-
vant thermodynamic data for these and adjacent elements.
Table I shows the known binary actinide oxides, arranged by in-
creasing atomic numbers and oxidation states. Measured enthalpies of
formation and standard entropies at 298 K are shown to indicate those
oxides which have been thermodynamically well characterized. (Some
M0 2 _x phases have been omitted for clarity.)
Although this paper focuses only on oxides MOl.5 and M02, it should
be noted that there is a rich chemistry of higher actinide oxidation
states in complex oxides of protactinium through americium (10). These
complex oxides fill many of the blank regions in the lower right region
of Table I, and allow the study of spectroscopic, magnetic, electronic,
and thermodynamic properties of these oxidation states.
147
148 L. R. MORSS
TABLE 1.
Wcll-Chfrarterized Binary Actinide Oxides. Measured enthalpies of formation (kJ mol- 1 ) and standard entropies
(J mol- K- ) are shown beneath corresponding formulas.
An(IIl) An(IV) An(V) An(VI)
AcO I. 5
Th0 2
-1226.4 ± 3.5
65.23 ± 0.20
Pa02 Pa02.5
v0 2 VO Z • 25 V0 2 67 V03(Y)
-1085.0 ± 1.0 -1127.6 ± I.Z -114Z. 4V~Zo~~ -11~1.6 ± 0.8 -1223.8 ± Z.O
77.03 ± 0.20 83.53 ± 0.18 83.51 94.18 ± 0.17 96. II ± 0.40
Np02 NpOZ.5
-1074.0 ± 2.5
80.3 ± 0.4
PuOI.61 Pu02
~~~h1 -884.5 ± 16.7 -1056.2 ± 0.7
81. 51 ± 0.32 66.13 ± 0.26
AmOl.5 Am°1.6(?) Am°2

-845 ± 8 -932.2 ± 2.7
CmOI.5 Cm0t. 714 Cm02

-841.5 ± 6.0 -91l ± 6
BkO I. 5 Bk0l. 8 Bk0 2
Cfo l • 5 CfO l. 714 Cf0 2

-826 ± 5
References for Table I: References 10,11, and Morss, L. R.; Fuger, J. to be published (CfO l • S )·
2. AMERICIUM OXIDES
The enthalpy of formation of hexagonal Am203 was determined re-

cently by solution microcalorimetry (11). Although this measurement was
not the first thermodynamic property of an actinide sesquioxide to be
reported (12-14), Am203 represents the lightest actinide sesquioxide
suitable for solution calorimetry. (Although a large sample of pluton-
ium sesquioxide has been prepared (13) and still exists, its high tem-
perature of synthesis renders it so refractory that it is probably un-
suitable either for solution or combustion calorimetry. Lighter acti-
nide sesquioxides such as U203 and NP203 are unknown.) Since Am203
readily oxidizes in air, it had to be handled in an oxygen-free dry
box. Fortunately, its reactivity facilitated solution calorimetry in 6M
hydrochloric acid, in which it readily dissolves.
Unsuccessful efforts were made by this author to prepare multi-
milligram samples of monoclinic Am203, which may (3) have a narrow sta-
bility range (figure 1) or may be observed only when stabilized by a
lanthanide impurity (15). The hexagonal sesquioxide was observed upon
reduction of the dioxide in hydrogen at temperatures above 625°C, with
rapid or slow cooling; lower reduction temperatures yielded only the
body-centered cubic sesquioxide. Because of concern that the bcc ses-
quioxide might not be stoichiometric (3), solution-calorimetry measure-
ments were not undertaken on the bcc phase.
A few years earlier, the enthalpy of formation of Am02 was redeter-
mined (16). Although Am sesquioxide, as well as those of Cm, Cf, and
THERMODYNAMICS OF Am, Cu AND NEIGHBORING ELEMENT OXIDES 149
2000
1800
A
(hexagonal}
1600
1400
'G'
~
-e
1200
~
::'I
1000
Q)
a. 800
E
~ 600
400
Pu AmCm8k Cf
200 I II I I
O~~.-~~~-L-r~~~~~~-+~~
1.04 1.02 1.00 0.98 0.96 0.94 0.92 0.90 0.88 0.86
1.1 3 + Ionic Radius (A) [eNS. Shannon]
Figure 1. Phase diagram for • lanthanide and • actinide

sesquioxides (region above 2000°C omitted).
the lanthanides, dissolves readily in dilute hydrochloric acid (11) (the

most convenient calorimetric solvent), the dioxide requires stronger
acid to dissolve it. Am02 also has been observed to disproportionate
partially and nonreproducibly when dissolved in acid (16). Therefore,
it was necessary to carry out the solution calorimetry in a complexing
acid (H2S04) with a reductant (1-) to achieve adequate dissolution rates
and a well-defined reaction. An important result obtained from this
study was a thermochemical estimate of the standard aqueous electrode
potential EO(Am4+!Am3+) = 2.62 ± 0.09 V (16).
Ackermann and Chandrasekharaiah (17) correlated the behavior of
these oxides with other sesquioxides and dioxides and with the aqueous
ions. More recent investigators have refined such correlations in terms
of the functional dependence of enthalpy of solution upon ionic size and
crystal structure (11,16,18) and in terms of the energetics of gaseous
atoms in different electron configurations (18). Even more recently
Brewer's reassignment of the energy levels of Am I (neutral Am) (19) has
led to a much more consistent comparison (11) of the energetics of Am
metal, vapor, and trivalent species with other f elements (by means of
the correlation function P(M) ) than had earlier been calculated
(20,21). A refined treatment of the systematics of lanthanide atomic
energy levels (22) should further improve actinide metal!oxide!aquo-ion
systematics when it is applied to the 5f elements.
3. CURIUM OXIDES
Curium sesquioxide was the first actinide sesquioxide to be studied

by solution calorimetry (14). The determination of ~fH;(Cm203) was
150 L. R. MORSS
facilitated by the availability of multimilligram amounts of 248Cm, a

long-lived (half-life 3 x 105 y) isotope purified from its radiochemical
parent 2S2Cf in the transplutonium production program at Oak Ridge
National Laboratory, by the ease of reduction of CmOZ_x to CmOI.S, by
the relative stability of stoichiometric monoclinic sesquioxide
(figure 1) above 700°C, and by its rapid dissolution in hydrochloric
acid.
Curium dioxide, on the other hand, has proved to be much more in-
tractable than Am02. Early studies with 244Cm (half-life 18.1 y) showed
significant substoichiometry (4,5,Z3), especially as a function of time,
due to alpha-particle lattice damage. Despite the more recent avail-
ability of 248Cm, which appeared from thermogravimetric measurements and
X-ray powder diffraction lattice parameter to yield stoichiometric
Cm02.00 in oxygen at 1 atm pressure, recent magnetic susceptibility
determinations infer significant hypostoichiometry (x near 0.2 in
CmOZ_x) (24-27). Very careful annealing in pure oxygen for several days
at 1 atm pressure and even at 100 atm pressure (Z5,26) failed to elimin-
ate Curie-Weiss paramagnetism attributable to Cm(III). Since annealed
dioxide dissolves very slowly in acidic media, calorimetric solvents
required complexing (HS04-, BF4-) and reducing (1-) agents to accelerate
dissolution of Cm02. Typical data (Z4) (table II) show significant
scatter.
TABLE II.
Cm02 THERMOCHEMISTRY
Solution calorimetry in 0.5 M HZS0 4 - 0.1 M KI:
CmOZ(cr) + 4 H+ (aq) + 3/Z 1- + Cm 3+ + l/Z 13- + Z HZO(aq)
Sample A(Cm02.00): ~ -223.6 ± 2.1 kJ mol- 1

(5 experiments, 95% confidence)
Sample B(Cm01.93): ~ = -225 ± 6 kJ mol- 1

(3 experiments, 95% confidence, corrected to Cm02.00)
Solution calorimetry in 6M HN0 3 - 0.1 M NaBF4:
Cm02(cr) + 3 H+(aq) + Cm3+ + 3/2 H20(aq) + 1/4 02(g)
Sample C(Cm01.986): ~ -160.5 kJ mol- 1 (1 experiment)
Sample D(CmOl.982): 6H -153.0 kJ mol- l (2 experiments)
These experimental data, combined with currently accepted

auxiliary data and small corrections to standard states, yield
6fHO(Cm02,cr) = -911 ± 6 kJ mol- 1 (95% confidence).
The thermochemical measurements on curium oxides have been utilized

systematically in a manner parallel to those on americium oxides: cor-
relation of entha1pies of solution with ionic size (18,22), correlation
(P(M) ) with energetics of gaseous ato~s (18), and thermochemical esti-
mation (24) of the aqueous EO(Cm~+/Cm3 ) = 3.0 ± 0.1 V. The steps in
the latter calculation are shown in table III. Similar thermodynamic
behavior is found in the lanthanides praseodymium (aqueous EO(Pr~+/Pr3+)
= 3.2 ± 0.2 V) and terbium (aqueous EO(Tb~+/Tb3+) = 3.1 ± 0.5 V (28) or
3.3-3.4 V, see below). These tetravalent lanthanides have been stabil-
ized in comp1exed form in carbonate solutions (29), but, unexpectedly,
Cm(IV) has not yet been stabilized in this medium (30).
TABLE III.
For the reaction

Cm02(cr) + 4H+(aq) + Cm 4+(aq) + 2H 20(1)
we predict ~o = -40 ± 7 kJ mo1- 1 from data on other

M02 and M4+ (see fig. 3).
-1
Since we have calculated ~fHO(Cm02,cr) = -911 ± 6 kJ mol ,
we may calculate ~fHO(cm4+,aq) from the above data:
~fHO(Cm4+,aq) = ~fHO(Cm02,cr) - 2 ~fHO(H20) + (-40 ± 7)

= -911 ± 6 - 2(-285.83) - 40 ± 7 = -379 ± 9 kJ mol-I.
Thus for the reaction
Cm4+(aq) +V2H2(g) + Cm3+(aq) + H+(aq)

~o = -615 ± 5 - (-379 ± 9) = -236 ± 10 kJ mol-I.
From estimated entropies

~SO = 170 ± 21 J K- 1 mo1- 1
Hence E O(Cm4+/Cm3+) = -~Go/nF = +2.96 ± 0.12 V

(compared with literature estimates of 3.1 and 3.2 V).
4. RELATIONSHIPS TO OTHER THERMODYNAMIC MEASUREMENTS
There are high-temperature calorimetric measurements on the incre-

mental oxidation of cerium (31) and plutonium (12) oxides. For cerium
(32), praseodymium (33), terbium (34), and all actinides thorium through
152 L. R. MORSS
californium (2,5-8,35) there are oxygen-pressure dissociation data as a

function of temperature and composition. Each of these methods leads to
H(02), the partial molal enthalpy of oxygen in these systems. High-
temperature solid-state EMF measurements also yield thermodynamic infor-
mation on these oxides (36).
Chikalla and Turcotte (37) compared log P(O~) data at 1173 K for
the composition MOl.9 with the aqueous EO(M4+/M3 ), since both of these
parameters are proportional to the free energy change of M(IV)-M(III)
species. They predicted P(02) for other oxides MOl.9. The
EO(Am4+/Am 3+) has been reassessed as 2.62 V (16) and a data point for
CeOl.9 is available; the revised plot (figure 2) still predicts only
slightly more stability for CmOl.9 than for CfOl.9' Isobars
for 24BCm02_x show P(02) = 0.72 atm for CmOl.9 at 723 K (6);
measurements are lacking for the CfOx system above x = 1.72. Neverthe-
less, CmOx and CfO x isobars (6,8) (1.50 < x < 1.72) show CmOx to lose
oxygen at ~ temperatures than CfO x ' These contradictory interpre-
tations need to be reconciled.
60
50
40
30
-
20
'E'
.s.. 10
0
0
0-
m -10
..Q
-20
-30
-40
-50
-60
0 1 2 3 4 5
EO(M4+ jM3+) (Volts)
Figure 2. Correlation of log P(02) for MOl 90 at 1173 K

(refs. 32,35, and 37) with aqueous EO(M4+/M3~) (ref. 28).
Ackermann and Rauh (35) tabulated G(02) for MOl.96 (M = Th-Am) at

1875 K. There are insufficient data to extrapolate G(02) for CmOl.90 at
1173 K for comparison with Chikalla and Turcotte's plot (37). The stoi-
chiometry of Cm02 must still be established by new thermogravimetric or
analytical measurements.
Enthalpy-of-solution correlations of sesquioxides and dioxides as a
function of ionic size lead to interesting conclusions. Such a plot for
lanthanide and actinide dioxides shows a single straight line with the
exception of terbium (figure 3). This plot permits the prediction of

the enthalpies of formation of Bk02 (-1020 kJ/mol) and of Cf02
(-858 kJ/mol) using accepted EO(An 4+/An 3+), estimated entropies, and new
thermochemical data on Cf 3+(aq) (38). Since there is no reason to doubt
the reliably determined enthalpy of formation of TbO~, we must suspect
that the estimated (28) enthalpy of formation of Tb 4 is too exothermic
by ca. 20-30 kJ/mol. Consequently, the estimated aqueous potential
EO(Tb 4+/Tb 3+) must be revised from 3.1 (28) to 3.3-3.4 V.
A more practical conclusion that may be reached from figure 3 is
that the tetravalent lanthanides and actinides in eightfold oxide coor-
dination are similarly stable with respect to the tetravalent aquo-
ions. Thus Ce(IV) is a good model for either Pu(IV) or Np(IV) in
nuclear waste isolation studies.
-30
-40
c-
o
o Tb
-50
I--, -60
0
'? -70
0
:;::
::J
"0 -80
~
0
:::c -90
<l
-100
-110 Th
5.2 5.3 5.4 5.5 5.6

M0 2 Unit Cell Length (A)
Figure 3. Enthalpy of solution of M02 as function of unit
cell size.
When a similar plot (figure 4) is examined for the sesquioxides,

which have three structure types, it is noted that the enthalpies of
solution of actinide sesquioxides of each structure type are ca.
20 kJ/mol less exothermic than those of structurally similar lanthanide
sesquioxides. Similar differences are seen for structurally similar
hexagonal trichlorides. These systematic trends permit one to predict
enthalpies of formation for unstable sesquioxides (for U and Np) as well
as for PU203 and Bk203 (table IV). Carrying the comparison one step
farther, we have calculated free energies of solution from enthalpy
differences and from measured entropies for a lanthanide and actinide
ion of similar size in table IV. Not only do figure 4 and table IV show
that lanthanides may be used to model trivalent actinide behavior in
nuclear waste matrices, but that the lanthanide models provide a
conservative safety margin -- the actinide(III) ions in sixfold oxide
154 L. R. MORSS
o A-type (hexagonal)
a a-type (monoclini c)
-"·1
~ °l - '6 Pu01.,, (lAEA. 1967) .
IJ C-type (cubic)
~ ~u
~
C-
-'60l Pu01.:;(Chercu1L 1977) .
n Q
!!I
IPuOl. ~ (ORNr.., 198.~) Ln0l.~
u-'lt-n
.Q
:2 -200
~
1C 0
-o-£J<-IJ-
Am0l.'; . ' C-mO _ O""D'~
(cubic)
1
1. >
:r: /
- 220 Ln0 1.S ~
<I
0",,-
1
(monoclinic) /
-
240
~~)~g) 0,
-: ---.---, I I ii' i ------,.----, ~~r-l~-'-1~--'1-
2.76 2.78 2. 8 0 2.82 2. 84 2.86 2.8 8 2.90 2.92 2.94 2.96
(Molar Volume)V;; (em)
Figure 4. Enthalpy of solution of lanthanide (open symbols) and acti-
nide (filled symbols) sesquioxides as function of interatomic distance.
Data from refs. 11 and 12; IAEA Tech. Report 79 (PuOl 5' 1967); Besmann,
T. M., Lindemer, T. B., J. Am. Ceram. Soc. 1983, 66, '82-5 (PuOl.s,
ORNL); and Morss, L. R., et al., to be published (Cf0 1 • s )'
TABLE IV.
Differences in Enthalpies of Formation of Trivalent Actinide Species (kJ moC I ).
M°1.5-M3+ MC1 3 -M 3+
M M3+(aq)a Diff. MO I • 5 (s)a Diff. MC13(cr,hexag)a
U -489 (-239) (-728)[ hexag] -377 -866

Np -527 (-234) (-761)[hexag] -371 -898
Pu -592 (-236) (-828) [hexag] -368 -960
Am -617 -228 -845 [hexag] -361 -978
Cm -615 -226 - 841 [monoel] -355 (-970 )
Bk -601 (-246) (-847) [cubic] (-350) ( -951)
Cf -577 -249 -826 [cubic] (-345) (-922 )
aFrom solution calorimetry; entries in parentheses are estimates.
Lanthanide-Actinide Comparison (kJ mol-I)
llH(soln) llG(soln)
NdOI.S(s) + 3H+(aq) + Nd 3+(aq) + 3/2 H20(1) -221 -169
PuOI.5(s) + 3H+(aq) + Pu 3+(aq) + 3/2 H20(1) -193 -145
coordination are ca. 20 kJ/mol more stable than structurally similar

lanthanides in comparison with aqueous ions.
Enthalpies of solution represent differences between lattice
enthalpies and hydration enthalpies. We hypothesize that actinide
sesquioxides have enhanced covalent stabilzation compared to lanthanide
sesquioxides because of their more extended 5f orbitals, whereas the
actinide dioxides do not manifest a significant stabilization. This
conclusion can be conveniently tested (39) for the trivalent ions by
comparing enthalpies of solution of similar hydrated salts; fortunately,
a suitable pair is available in the trichoride hexahydrates. The en-
thalpy of solution of NdC13-6H20 (corrected to infinite dilution) is
-38 kJ/mol (28), and the enthalpy of solution of PuC13·6H20 is
-35 kJ/mol (40). These nearly identical values reflect the similar
coordination in the hydrated salts and hydrated aquo-ions: In the tri-
chloride hexahydrates, the trivalent ion is coordinated to six water
molecules and two chloride ions (41) and in the aquo ions the coor-
dination is believed to be ninefold (42).
TABLE V.
Americium and Curium Oxides
Trivalent
Am° 1• 5 Cm01.5
LiAm02
SrAm204, BaAm204
Ba2Am(Nb,Ta,Pa)06
AmV0 4
AmNb0 4 CmNb0 4
AmTa04 CmTa04
AmPa04 CmPa04
AmA10 3 CmA10 3
Tetravalent
Am02 Cm02-x
Na2Am03
SrAmO 3
BaAm03 BaCm03
aS ee also paper by F. Weigel, this volume.

156 L. R. MORSS
5. COMPLEX OXIDES OF AMERICIUM AND CURIUM
There are known complex oxides of Am(III), Am(IV), Am(V), and

Am(VI) (table V) (10). As is the case with the lighter actinides U-Pu,
the higher oxidation states are stabilized in complex oxides. There are
no quantitative values for this stabilization, even in the case of
BaAm03 (or even for BaPu03) (43). As of the time of writing, only a
few complex oxides of Cm(III) and one of Cm(IV) are known (table V).
[Note added in proof: see paper by F. Weigel, this symposium.) Although
the perovskites BaM03 are significantly more stable than the binary
oxides (43), the perovskite BaCm03 still showed significant Cm(III) from
magnetic measurements (27). Quantitative results on the enthalpy of
stabilization of numerous uranium, neptunium, and most recently plu-
tonium complex oxides should guide efforts to synthesize new complex
oxides of Am and Cm (44,45).
6. ACKNOWLEDGEMENT
This work was carried out under the auspices of the U. S. Depart-
ment of Energy, Office of Basic Energy Sciences, Division of Chemical
Sciences, under contract number W-31-109-ENG-38.
7. REFERENCES
1. Asprey, L. B. ; Cunningham, B. B. USAEC Report UCRL-329, Berkeley,

CA, 1949.
2. Chikalla, T. D. ; Eyring, L. J. Inorg. Nucl. Chern. 1967, 29,
2281-2293.
3. Chikalla, T. D. ; Eyring, L. J. Inorg. Nucl. Chern. 1968, 30,
133-145.
4. Mosley, W.C. J. Inorg. Nucl. Chern. 1972, 34, 539-555.
5. Chikalla, T.D.; Eyring, L. J. Inorg. Nucl. Chern. 1969, 31, 85-93.
6. Turcotte, R. P.; Chikalla, T.D.; Eyring, L. J. Inorg. Nucl. Chern.
1973, 35, 809-816.
7. Turcotte, R. P.; Chikalla, T. D.; Eyring, L. J. Inorg. Nucl. Chern.
1971, 33, 3749-3763; Turcotte, R. P.; Chikalla, T. D.; Haire,
R. G.; Fahey, J. A. J. Inorg. Nucl. Chern. 1980, 42, 1729-1733.
8. Turcotte, R. P.; Haire, R. G. in Transplutonium Elements, ed.
W. Muller and R. Lindner, North-Holland, 1976, pp. 267-276.
9. Eyring, L.; Lohr, H. R.; Cunningham, B. B. J. Am. Chern. Soc.
1952, 74, 1186-1190.
10. Morss, L. R. in Actinides in Perspective, ed. Edelstein, N.,
Pergamon, Oxford, 1982, pp. 381-407.
11. Morss, L. R.; Sonnenberger, D. C. J. Nucl. Mater., in press.
12. Chereau, P.; Dean, G.; DeFranco, M.; Gerdanian, P. J. Chern.
Thermodyn. 1977, 9, 211-219.
13. Flotow, H. E.; Tetenbaum, M. J. Chern. Phys. 1981, 74, 5269-5277.
14. Morss, L. R.; Fuger, J.; Goffart, J.; Haire, R. G. Inorg. Chern.
1983, 22, 1993-1996.
15. Berndt, U.; Tanamas, R.; Maier, D.; Keller, C. Inorg. Nucl. Chern.
Lett. 1974, 10, 315-321.
16. Morss, L. R.; Fuger, J. J. Inorg. Nucl. Chern. 1981, 43, 2059-2064.
17. Ackermann, R. J.; Chandrasekharaiah, M. S. Proc. Symp. on
Thermodyn. of Nucl. Materials, Vol. 2, IAEA, Vienna, 1975,
pp. 3-26.
18. Morss, L. R. J. Less-Common Metals 1983, 93, 301-321.
19. Brewer, L. High Temp. Science, 1984, 17, 1-30.
20. Nugent, L. J.; Burnett, J. L.; Morss, L. R. J. Chern. Thermodyn.
1973, 5, 665-678.
21. David, F.; Samhoun, K.; Guillaumont, R.; Edelstein, N. J. Inorg.
Nucl. Chern. 1978, 40, 69-74.
22. Johansson, B.; Munck, P. J. Less-Common Metals 1984, 100, 49-70.
23. Kanellakopulos, B.; Muller, W. Report AED-Conf-78-074-002; AED:
Berlin, 1978; INIS Atomindex 1979, 10, 425659.
24. Morss, L. R.; Fuger, J.; Goffart, J.; Haire, R. G. Abstracts,
"Actinides-1981," Rept. LBL-12441, 1982, p. 263.
25. Goffart, J.; Edelstein, N.; Morss, L. R. Unpublished measurements
on Cm02_x' 1982.
26. Kanellakopulos, B.; Peterson, J. R. Unpublished measurements on
Cm02_x' 1983.
27. Nave, S. E.; Huray, P.; Haire, R. G. Phys. Rev. 1983, B28,
2317-2327.
28. Morss, L. R., "Yttrium, Lanthanum, and the Lanthanide Elements;"
Martinot, L.; Fuger, J. "The Actinide Elements," in Oxidation-
Reduction Potentials in Aqueous Solutions, ed. Bard, A. J.;
Jordan, J.; Parsons, R., in press, Marcel Dekker (1985).
29. Hobart, D. E.; Samhoun, K.; Young, J. P.; Norvell, V. E.;
Mamantov, G.; Peterson, J. R. Inorg. Nucl. Chem. Lett. 1980, 16,
321-328.
30. Hobart, D. E.; Varlashkin, P. G.; Samhoun, K.; Haire, R. G.;
Peterson, J. R. Rev. Chim. Minerale, 1983, 20, 817-827.
31. Campserveux, J.; Gerdanian, P. J. Chern. Thermodyn. 1974, 6,
795-800.
32. Bevan, D. J. M.; Kordis, J. J. Inorg. Nucl. Chem. 1964, 26,
1509-1523.
33. Hyde, B. G.; Bevan, D. J. M.; Eyring, L. Trans. Roy. Soc. London
1966, A259, 583-614.
34. Lowe, A. T.; Lau, K. H.; Eyring, L. J. Sol. St. Chern. 1975, 15,
9-17; Hyde, B. G.; Eyring, L. Rare Earth Research III, Gordon &
Breach, New York, 1965, pp. 623-624.
35. Ackermann, R. J.; Rauh, E. G. Rev. Internat. Hautes Temps.
Refract. 1978, 15, 259-280.
36. Lott, U.; Rickert, H.; Keller, C. J. Inorg. Nucl. Chern. 1969, 31,
3427-3436.
37. Chikalla, T. D.; Turcotte, R. P. Proc. 5th Mat. Res. Symp., U. S.
Nat. Bur. Stand. Spec. Pub. 364, 1972, pp. 319-330.
38. Fuger, J.; Haire, R. G.; Peterson, J. R. J. Less-Common Metals
1984, 98, 315-321.
39. The author is indebted to Professor R. Connick (University of
California, Berkeley) for suggesting this comparison.
158 L. R. MORSS
40. Fuger, J.; Parker, V. B.; Hubbard, W. N.; Oetting, F. L.; The
Chemical Thermodynamics of Actinide Elements and Compounds,
Part 8: The Actinide Halides, International Atomic Energy Agency,
Vienna, 1983.
41. Habenschuss, A.; Spedding, F. H. Cryst. Struct. Commun. 1980, 9,
71-76.
42. David. F. "Redox and Thermodynamic Properties of Cm and
Transcurium Elements," to be published.
43. Williams, C. W.; Morss, L. R.; Choi, I-K. in "Geochemical Behavior
of Disposed Radioactive Waste," ed. Barney, G. S.; Navratil,
J. D.; Schultz, W. W. American Chemical Society Symposium Series
246, Washington, D. C" 1984, pp. 323-334.
44. Gens, R.; Fuger, J.; Morss, L. R.; Williams, C. W. J. Chern.
Thermodynamics, in press.
45. Fuger, J. J. Nucl. Mater., in press.
PREPARATION AND PROPERTIES OF SOME NEW CURIUM COMPOUNDS
F.WEIGEL AND R.KOHL

Radiochemische Abteilung des Instituts fUr Anorganische
Chemie der Universitat MUnchen
Meiserstr. 1
8000 MUnchen 2
F.R.G.
ABSTRACT. The following compounds of element 96, Curium, have been pre-
pared and studied using ultramicrochemical techniques: CmP04·H20,
Cm(Re04)3·xH20, Cm(Re0 4 )3, Cm2(Mo04)3, CmV04, CmCr04, CmAs0 4 , CmSc03,
CmV03, CmCr03, CmFe03, Cm2(Cz04)3·10H20, Cm(HCOO)3, CmOF, CmOCI, CmOBr.
A new compound of tetravalent curium, Li2Cm03, and, what we believe to
be the first representative of pentavalent curium, Na3Cm04' have also
been prepared. A new synthesis for CmF3 has been developed, and some
thermodynamic properties of CmCl 3 have been studied.
1. INTRODUCTION
Even though element 96, Curium, was discovered no less than 40 years
ago, in July 1944 (1)(2), and was isolated as the isotope 242 Cm in 1948
(3)(4)(5), only relatively few solid compounds have been ch~racterized
- - - 242
to date. In the earliest time, when only short-lived Cm (T 1 / 2 =
162.5 days, S = 3320 Curies/g = 7.4 X 10 dpm/~g) was available ~n suffi-
9
cient quant~t~es, it was possible only in a few exceptional cases to
obtain X-ray data of curium compounds. Asprey and Ellinger (6) were the
first ones to obtain lattice constants of CmF3 and Cm203 using 242Cm in
the preparation of these compounds.
The situation became somewhat better, when in August 1953, weighable

quantities of Z44Cm became available by irradiation of "napkin rings"
in the MTR (2). 244 Cm (T1/2 = 17.9 years, S = 82 Curies/~ = 1.82xl0 8
dpm/~g) was much better suited for chemical work than 24 Cm, and a num-
ber of compounds were prepared and characterized by X-ray crystallo-
graphy.
Besides the fluoride, CmF3, which had been known from the earlier pre-
paration (6), Asprey, Keenan, and Kruse (8) prepared the halides CmCI 3 ,
CmBr3, and-CmI3. The only oxyhalide known-as early as 1955 was CmOCI,
which was also obtained by Weigel et al (9) in a study of the vapor
phase hydrolysis of CmC13. Asprey, Ellinger, Fried and Zachariasen (10)
prepared CmF4. Keenan reported the prep.lration of complex fluorides of
159
N. M. Edelstein et at. (eds.), Americium and Curium Chemistry and Technology, 159-191.
160 F. WEIGEL AND R. KOHL
tetravalent curium: LiCmFs (11), Na7Cm6F31 (12), K7Cm6F31 (13), and

Rb2CmF6 (14). Damien (15)(16~prepared the chalcogenides, Charvillat et
al (12) the pnictides,'Weigel et al (~) the silicides.
Quite a few papers deal with the curium oxygen system. The phase diagram
was established by Chikalla and Eyring (19)(20). Some phase transforma-
tions of this system were studied by Mosley (21), Haug (22), and by
Sudakov and Kapshukov (23). The melting point-of Cm203 was determined by
Smith (24), the radiation-induced structural change of C-Cm203 into A-
Cm203 was reported by Wallmann (25), and by Noe (26).
Relatively few tepnary compounds of Cm have been studied, using 244 Cm.
These include CmP0 4 (27)(28)(29), CmNb0 4 (28), CmTa04(28), and Cmo.sPao.502
(28). - - -
A few papers have also been published using the rare isotope 248 Cm,
which is the daughter of 252 Cf and is particularly well-suited for che-
mical work because of its long half life (T 1/ 2 = 3.5xl0 s years, S =
4.24 x l0- 3 Curies/g = 9.42xl0 3 dpm/~g). Compounds of 248 Cm, which have
been studied, include CmCl3 (30), CmOCI (31), Cm02 (32)(33), Cm02.~ (34)
CmF 4 (~), BaCm03 (35), and Cm203 (~~). - - - -
Because we have been supplied with a total of 40 mg of 244 Cm by courtesy

of the US Department of Energy, Isotopes Distribution Office, Oak Ridge,
TN,we decided to contribute to the solid state chemistry of curium by
synthesis and characterization of additional, hitherto unknown compounds,
and by restudying some of the known compounds using more advanced tech-
niques. This work is reported in this paper.
2. EXPERIMENTAL
2.1. Safety Precautions.
A~l work with 244 Cm was carried out in a Berkeley standard glove box,
which was shielded with 2 mm lead on its front side. Even though 244 Cm,
despite its short half life, has no serious radiation hazard due to
penetrating gamma radiation, and its fission yield is so small so that
even several milligrams pose no neutron hazard, we found it suitable to
use the well established techniques of Cunningham (37)(38), and those of
Fried and Davidson (39) because of their elegance, and because they
allow the preparation-of individual compounds inside the X-ray capillary
or in its vicinity without difficult manipUlation. The amount of 244 Cm
used in an individual preparation was limited to less than 100 ~g, be-
cause such an amount still gives a good pattern without any film-fogging
due to radioactive background radiation.
2.2. Recovery and Purification of Curium.
The curium, which was used in this work had the isotope composition
shown in Table 1. It was supplied in two batches by the Isotope distri-
PREPARATION AND PROPERTIES OF SOME NEW CURIUM COMPOUNDS 161
Table 1. Isotopic Composition of Curium

used in this work (8.)
2""Cm 92.42 %
2"SCm 1.162 %
2'+6 Cm 6.26 %
2"7 Cm 0.101 %
2"8 Cm 0.057 %
(a) Data supplied by ORNL
Table 2. Conditionsfc:>r X-ray diffractiGn work
X-ray generator; Seifert Iso-Debyeflex 2002

Cameras: Seifert Debye-Scherrer Cameras
with 57.5 mm and 114.6 mm dia-
meter
X-ray tube: Cu 2000 W 1x10 mm 2 F-60-10, AEG
High voltage: 50 kV
Current: 35 rnA
Radiation: Cu K
a.
Filter: 0.02 mm Ni foil in front of
film, unfiltered primary beam
Collimator: 0.6 mm ID
Exposure times: 57.5 mm camera: 20 min, 40 min,
1 hour
114.6 mm camera: up to 10 hours
Film: 57.5 mm camera: OSRAY M3
114.6 mm camera: DuPONT MRF 31
Cm-Silicides in Resiuues of
X-Ray Capillaries Stock Solution
crushed conc.HN0 3
evaporate
fume severa] times

with HF and a small
amount of conc.HNO]
Fig.l. Flow sheet for

the recovery of 244Cm
from curium silicide
cone. HN03 residues
wi th
Volumetric Flask
ml
Cm(l!l) Stock Solution

2~ItCm Product
0\°
r-3
::0
;p
Z 3+
Cm
w.
3::
......
w.
w.
......
0
Z
WAVELENGTH (nm)
Fig.2. Absorption spectrum of curium(III)

in eluate from Dowex 1 column, 8 M Hel
HEATING COIL THERM COUPLE
~_________~~
__~.~~o~o~o~~~_______~
O 2- -
-\~!---~~::--
QUARTZ- OR
GOLD BOAT
Fig.3. Decomposition apparatus for the

pyrolysis of mg quantities of curium(III)-oxalate
to curium(IV)-oxide.
bution Office, Oak Ridge National Laboratory, Oak Ridge, TN.The first
batch had been used in work on curium silicides (~). The combined resi-
dues of this work consisted of
a) mixed curium silicide residues from X-ray capillaries,

mixed with debris from the quartz capillaries
b) an assortment of residues in strong sulfuric acid, con-

taining both, small amounts of dissolved curium, and sus-
pended undissolved curium silicides.
c) the dried residue of an old stock solution
The second batch of curium consisted of virgin curium oxide, as supplied

by ORNL.
The combined materials from the first batch were worked up in the manner
described by the flow sheet shown in Fig.1. The 240 pu , which had been
retained on the ion exchange column, was recovered by dissolving the
resin in H2S0 4- H202 followed by precipitatiau:_ of the Pu by gaseous
ammonia. The purified 24UpU hydroxide was set aside for preparation of
a stock solution.
An aliquot of the curium stock solution prepared by the process shown in

Fig.1 was counted in a low-geometry counter and was found to contain
2.44 mg 244 Cm. This stock was used in the preparation of compounds by
precipitation from aqueous solution.
The virgin curium oxide was purified by the following procedure: The
Cm02 was dissolved in a small quantity of 8M.ilICL. ~_drop_oLconc.entrated
HN03 was added, and the solution was loaded-on the top of a Dowex 1x 10
column (100-200 mesh), precnnditionedwith .8M He!. The curium was eluted
with 8M HCI. Fe and Pu are retained on the column under these conditions.
The absorption spectrum of the resulting pale-yellow curium solution
showed the absence of other actinides (Fig.2)
From the curium product solution in HCI, the Cm was precipitated as the
hydroxide. The Cm(OH)3 was washed several times with distilled water,
dissolved in dilute HN03 , and precipitated as the oxalate. The oxalate
was transferred to the quartz reaction tube of a Fried Davidson appa-
ratus (~), and was ignited to the oxide using the following procedure:
The oxalate was first ignited in air at 750°C for 30 minutes. The tem-
perature of 750°C was maintained for another 15 minutes, then, the oxide
product was slowly cooled to 330-350°C in an atmosphere of oxygen. Large
quantities of curium (2-3 mg) were treated in the same manner using the
apparatus shown in Fig. 3. The black reaction product was characterized
by its X-ray powder pattern. It was found to be cubic with a = 5.369 ±
0.003 A, in good agreement with the value reported by Nave et al (35).
The curium oxide purified by this method was used either directly in
solid state experiments, or a weighed aliquot of it was dissolved in a
:e --+ 1
\
ll ': ---
PLA TINUlVl OR IRIDIUlVl
--. J
--~\---~+---------~,~
, I
SPIRAL
\ I \: SPOT-WELDED TO ELEC-
-----~...,,/ TRODES
TUNGSTEN ELECTRODES
SEALED INTO GLASS OF
29 mm 'I CAP
Fig.4. Ground joint cap with tungsten

electrodes and platinum (iridium) spi-
ral crucible
FUNNEL
14.5 mm
29 mm
14.5 mm
~ TO
--~~ FRIED-
't~
- DAVIDSON
APPARATUS
~ PT (IR) SPIRAL
TUNGSTEN E L E : : : ' I --1

L ________
SEALED INTO GLASS OF
29 mm CAP / -
MIRROR
Fig.5. Apparatus for work with platinum and/or

iridium spiral crucibles
small amount of concentrated HCI or HN0 3 , and HCI, or HN0 3 added to 1 mI.
The glass of the vessels, in which such curium stock solutions were kept
for some time, became crazed after a while due to the attack of the a-
radiation onto the glass surface. Prior to most preparative experiments,
the silica accumulated in the solutions by this effect was removed by eva-
porating the solution to dryness, and taking up the residue in water.
2.3. Microchemical Preparation Techniques
The microchemical preparation techniques used in this work were essenti-

ally the same as those developed by Cunningham (37)(38), but modified to
fit our requirements. Dry chemistry work was usuarly~one in a Fried-
Davidson apparatus (39). The version used in our work was modified in
such a way that the apparatus was set up outside the glove box, but the
capillary or reaction tube was located inside, to prevent spread of con-
tamination.
High temperature experiments, such as solid state reactions between

oxides were carried out in an iridium spiral furnace as shown in Figs. 4
and S. The Pt- or Ir-spiral served both as the crucible and .as ·.t:he.heat-
ing~element, and were spot-welded to the tungsten electrodes.
The spiral furnaces were charged by means of a drawn-out glass funnel,

which guided the charge material into the interior of the spiral (Fig.S).
The spiral temperature was regulated by means of a variac. Temperatures
were measured by means of a Haase micropyrometer. The Pt spirals allowed
to attain temperatures up to 1300°C, the Ir-spirals up to 1700°C *).
X-ray capillaries and quartz reaction tubes used in microwork were

heated by means of small, self-built quartz-kanthal or quartz-platinum
microfurnaces, which are in routine use in our laboratory.
Weighings of radioactive material were made with a Sartorius electronic

microbalance Type 4401 having a sensitivity of 0.1 ~g/scale division on
the digital indicator. This balance was calibrated using a Rodder ultra-
micro quartz fiber torsion balance **). Accuracies of ±1 ~g were easily
to attain.
Thermal and caloric effects in solid state reactions and phase trans-
formations (melting points, heats of fusion) were measured with a
*) Not every iridium wire was found to be suitable for spiral winding.
We found that the w~re supplied by Alpha Inorganics was the one
best suited because of its ductility
**) Sensitivity 85 Nanograms/scale division

Linseis Micro DTA apparatus ***), which allowed the measurements of sam-
ples weighing less than 1 mg.
2.4. X-Ray Work
All X-ray data were taken under conditions, and with the equipment spe-
cified in Table 2. X-ray capillaries used were in all cases 0.3 rum
quartz capillaries, which were drawn out to an OD of 0.1 - 0.2 rum, and
were sealed with their tips to little quartz rods (0.2 rum OD, S - 7 rum
long to facilitate handling. Capillaries were filled and sealed inside
the glove box using the techniques described by Haug (40).
To save space, the detailed evaluations of the individual X-ray patterns

are not reported here, they will be submitted to the ASTM card catalog
for general availability.
2.S. Preparation of Key Compounds
The compounds, which are called key compounds in this context, are the
ones, which are used as starting materials for other compounds. They
are themselves easily accessible from stock solutions. In this connec-
tion, they include curium(III)-oxalate-decahydrate, curium(III)-oxide,
curium(III)-formate, and curium(IV)-oxide.
For the preparation of a well-defined curium(III)-oxalate-decahydrate,

100 ~l of 0.1 ~ oxalic acid solution were added to 3.6x10- 3 M curium(III)-
solution in HN03. (HCl or HZS04 should be avoided, because chloro- or
sulfato-oxalates may be formed.) On .addition of 7 M NH40H solution to
neutralize excess acid, pale greenish-yellow curium oxalate decahydrate
Cmz(CZ04)3'10HzO precipitates according to the following equation:
A small quantity of the compound was sealed in an X-ray capillary and

the powder pattern was taken immediately after preparation.
Cmz(Cz0 4)3'10HzO is monoclinic, space group P21/c - C~h (No.14) with

the following lattice constants: a = 11.23±0.06 A, b = 9.60±O,OS A,
c = 10.22±O.OS A, S = 114.64°.
In the dark, CmZ(CZ04)3'10HzO shows a strong orange luminescence, which

is probably due to radiation-induced transition of the first excited
state to the ground state of Cm(IV). Cm(III)-oxalate-decahydrate is
isomorphous with the corresponding oxalates of actinium (41), pluton-
ium (42), and americium (43). --
***) Manufactured by Linseis MeBgerate GmbH, Vielitzer Str. 43

8672 Selb, Ofr. W.-Germany.
2.5.2. Curium(III)-formate, Cm(HCOO)3.

Curium(III)-formate was obtained by reacting Cm(OH):; or aged Cm2(C204)3
·10H 20 with formic acid. 50 ~g Cm(OH)3 or aged Cmz(C204)3·10H20 were
suspended in 20 ~l distilled water, and 50 ~l 98% formic acid were
added. In the case of the oxalate, a gas evolution (probably CO 2 ) was
observed, The mixture was heated under an IR lamp to approx. 70°C for
1 hour. It reacts to form Cm(HCOO)3 by the following equation:
Cm(OH)3 + 3 HCOOH Cm(HCOO)3 + 3H 2 0
The resulting white precipitate was centrifuged, the supernatant re-

moved, and the precipitate washed three times with absolute methanol.
From the dried, coursely crystalline curium(III)-'formate, an X-ray
sample was prepared.
Cm(HCOO)3 is hexagonal or rhombohedral, respectively, with the follo-

wing lattice constants:
hexagonal R3m - C~v (No.160) rhombohedral
(10.606 ± 0.017) A aR (6.272,± 0.011) A
_.
(4.069 ± 0.007) A a 115.46 0
396.3 A vR 132.1 A
ZR
D 4.76 gcm- 3
x
Curium(III)-formate, on ignition at BOO°C for 4 hours yields cubic
C- Cm 2 0 3·
2:5.3. Curium(III)-nitrate, Cm(N03)3·xH20.

30 ~g Cm(OH)3 or 30 ~g aged CmL(C204)3·10H20 were placed into a micro-
cone and 15 ~l conc. HN03 or 8M HN03 were added. The solution was eva-
porated to near-dryness under the IR lamp, and completely dried with a
stream of air.
The pale-yellow, nonhygroscopic nitrate was sealed ln a ql;.drtz X-ray

capillary, and the powder pattern was taken.
The powder diagram of Cm(N03)3·xH 0 turned out to be very complicated.

We have measured 30 lines, but were not able to interpret this diagram.
It appears that Cm(N03)3·xH 0 is either monoclinic or triclinic, and
that it is isomorphous with with Arn(N03)3·6H20.
The thermal decomposition of Cm(N03)3 in oxygen atmosphere at 780°C for

4 hours yields a cubic oxide, possibly C-Cm203, or, more likely, the
a-phase (CmOi.6). Pyrolysis for 6 hours at 330°C yields in Cm02.
2.6. Ternary Oxides of Cm(III)
There are numerous compounds, which may be described as ternary oxides.

They include compounds of the following types: cmX0 3 , cmX0 4 , Cm2(X04)3
and Cm(X0 4 )3. Most of the compounds we prepared could be characterized
by their X-ray powder data.
2.6.1.Curium(III)-perrhenate, CmtRe04),·xH20.
70 ~l of a 3.6xl0- 3M Cm(N03)3-Solution was precipitated ~ith gaseous

ammonia to form pale-yellow Cm(OH)3. This was washed several times with
distilled water, and 80 ~l of a 0.01 M HRe0 4-solution was added. The
mixture was continuously heated under-an IR lamp, and the resulting
pale-yellow solution evaporated under the IR lamp.
+ 3 Re04
Cm(Re04)3·xH20 is a white, hygroscopic solid. The X-ray powder pattern

could be interpreted with an orthorhombic lattice with a = 5.636±0.026 A,
b = 7.674±0.036 A, c = 15.401±0.072 A. It is isomorphous with the
corresponding Pu-compound, which had been prepared by J.P.Silvestre (44)
2.6.2. Anhydrous Curium(III)-perrhenate, Cm(Re04)a

This compound was prepared by two different roads, as shown below:
350°C
The dehydration of Cm(Re04)3·xH20 is carried out in a quartz tube,which

was pre-degassed in vacuo and attached to a Fried-Davidson apparatus.
The hydrated compound was slowly heated in air to 350°C, and maintained
at this temperature for 5 hours. The white reaction product was identi-
fied by its X-ray powder pattern.
In the second method of preparation, 35 ~g Cm02 and 70 ~g Re metal *)

were intimately mixed **) and placed into the quartz reaction tube of
a Fried-Davidson apparatus and heated in air for a period of 20 hours.
*) The Re metal was prepared by reduction of Re207 in dry hydrogen at

600°C. The reaction product was identified as Re metal by its pow-
der pattern.
**) For mixing, a mortar and pestle set (Cat.No. 6230, Sierra Misco Co.
1825 Eastshore Highway, Berkeley, CA. 97410) or a tungsten wire,
ground to a small ball, together with an A~03 microcone were used.
The powder pattern of the white reaction product was the same as that
obtained with the reaction product of the dehydration experiment.
A~ int~x~§ting qspect in the preparation of Cm(Re04)3 is the reduction

'of' InrtL3.ICni(IV) to Cm(III). This reduction is in agreement with the
observations of Silvestre in the synthesis of Am(Re04)3 and PU(Re0 4)3
at 400°C.
Cm( Re0 4)3, at 650°C, decomposes to CmZ03 and volatile ReZ07; it is thus
less stable than PU(Re0 4)3 (decomposition at 700 0 e) and Am(Re04)3 (de-
composition at 850°C).
Cm(Re04)3 crystallizes in the hexagonal system, B-Eu(Re04)3-type, with

a ~ 10.065±0.059 A, c ~ 6.294±0.034 A.
2.6.3. Curium(III)-molybdate, Cm~(Mo04)3
30 )Jg CmOz and 29 )Jg (NH4) 6M070Z'" 4HzO (commercial "ammonium molybdate")
are intimately mixed, and reacted with each other in the quartz tube of
a Fried-Davidson apparatus by heating at 750°C for 3 hrs; then at
930°C for 6.5 hrs. The brownish-yellow curium molybdate, which is formed
according to the reaction
was identi~ied by its X-ray powder pattern. It crystallizes in the

Scheelite type lattice, tetragonal, space group I41/a - c2h (No. 88)
with a ~ 5.250±0.007 A, c = 11.496±0.016 A, Z = 4, and by assuming
Cm2/3[Jl/3)Mo04, its density was calculated to be 6.76 gcm- 3 .
The intensity calculations in Cmz(Mo04)3 were done with the SHELX 76

program and comparing with the results of a-Nd2(Mo04)3 (45), using iso-
tropic temperature factors, an R-value of 0.072 was obtained. There is
good agreement between calculated and observed intensities. By assuming
4 formula 7nits of the type (Cm2/3[J1/3)Mo04 in the unit cell, the
atomic positions of Cmz(Mo0 4)3 given in Table 3 were calculated. Each
Cm atom is surrounded by a distorted oxygen dodecahedron. The
Cmz(Mo04)3 compound prepared in our work is isomorphous with
a-Nd2(Mo04)3 and a-Am2(Mo04)3. A curium molybdate corresponding to
B-Am2(Mo04)3 could not be prepared so far.
2.6.4. Curium(III)-tungstate, Cm2(W04)3
80 )Jg Cm02 and 88 )Jg W03 are weighed on the microbalance, intimately
mixed, and transferred to the quartz tube of the Fried-Davidson appa-
ratus. The mixture was heated at 890°C for 24 hours. It reacted accord-
ing to
2 CmOz + 3 W03
24 hrs
Table 3. Atomic coordinates in curium(III)-molybdate
Atom Wyckoff Paramet.ets

notation x y z
2/3 Cm 4 b 0.0 0.250 0.625

Mo 4 a 0.0 0.250 0.125
0 16 f 0.138 0.997 0.198
Table 4. Atomic coordinates ~n curium(III)-tungstate
Atom Wyckoff Parameters

notation x y z
Cm 8 f 0.334 0.377 0.407

W1 8 f 0.145 0.394 0.051
W2 4 e 0.0 0.132 0.250
01 8 f 0.161 0.045 0.221
O2 8 f 0.132 0.208 0.388
8 f 0.222 0.320 0.195
°3
8 f 0.359 0.450 0.038
°4
8 f 0.053 0.459 0.423
°5
8 f 0.448 0.241 v.OS8
°6
The resulting, pale-yellow reaction product was X-rayed immediately

after its preparation.
CrnZ(W04)3 was found to be monoclinic, a-EuZ(W04)3 type, space group

C2/c (No.15) with the following lattice constants: a = 7.714±0.031 A,
b = 11.556±0.046 A, c = 11.450±0.045 A, B = 109.14°, V = 964.3 A •
With Z = 4 formula units in the cell, the density was calculated to
be Dx = 8.48 gcm- 3 . The intensities were calculated using the LAZY
PULVERIX program and the atomic parameters used by Templeton and
Zalkin (65). Good agreement between measured and calculated intensities
was foun~ One has to keep in mind that the position of the oxygen atoms
cannot be determined from the measured intensities of the powder diagram,
because the scattering power of each oxygen atom is only 4% of the
scattering power of a curium atom.
2.6.5. Curium(III)-phosphate hydrate, CmP04·0 •.. 0.5H20
Attempts to prepare and to unequivocally characterize CmP0 4 ·O ..• O.5H 20

have been made at earlier times by Weigel (29), Kohl (46) and by
Walter (47). In all these earlier attempts,-Uo crystalline product was
obtained-rn the precipitation of Cm3 + with P04 3-. We succeeded in pre-
paring crystalline CmP04·O ... O.5H20 by a hydrothermal synthesis method
in a similar manner as described by Weigel and Scherer in the case of
promethium(III)-hydroxide (48).
To 50 ~g of a 3.6 10- 3M Cm(N0 3 )3 solution in a microcone, 30 ~l of O.lM

(NH4)HzP04 solution were added. In order to precipitate the CmP04, the-
acid in the solution was carefully neutralized with ammon~a. The yellow-
is white precipitate, which formed according to
was washed with distilled water to neutral reaction. The phosphate pre-
cipitate was slurried with distilled water into a quartz capillary tube
(ID 1.5 mm, length 40 mm). The tube was filled halfways with distilled
water and sealed with a hydrogen oxygen torch. The quartz tube, together
with some water, was sealed into an outside Duran tube, which was also
sealed. The whole assembly was placed into an autoclave, which was main-
tained for 16 hours at 150°C. After cooling and opening, the pale-yellow
curium compound was transferred to a glass centrifuge cone, the super-
natant was pipetted off and the CmP0 4 ·0 .•• O.5H20 was washed with acetone
and dried in a current of air. X-ray data were taken immediately after
preparation.
CmP04·0 .•. 0.5H20 was found to be hexagonal, isomorphous with ~he corres-
ponding phosphates of Nd, Ac, Pu, and Am, space group P6 2 22-D Q (No.180)
with a = 7.00±0.08 A, c = 6.39±0.07 A, V = 271.1 A3. For a un~t cell
with Z = 3, the density was calculated to be 6.39 gcm- 3 . The monoclinic
CmP0 4 , which was observed by Weigel and Haug (27)(29) was not observed
under the conditions of preparation used here.-- --
2.6.6. Curium(III)-arsenate, CmAs04 .
20 ~l 0.1 M (NH4)2HAs04solution in distilled water were added to 30 ~l

of 3.6x10-™ Cm3+stock solution in a microcone. On neutralization of
the free acTd with ammonia, a white, voluminous precipitate was formed
according to
Cm3+ + HAs0 2-
4 + CmAs0 4 +
The precipitate was washed with acetone and dried under the IR lamp. It
was then transferred to the quartz reaction tube of the Fried-Davidson-
apparatus, and slowly heated in air. Within a period of 90 min, the tem-
perature was raised to 950°C, and maintained at that temperature for 4
hours. After cooling, the brownish-yellow reaction product was stu~ied
by X-ray diffraction.
CmAs04, just as PUAS04 or AmAS04, was found to be monoclinic, monazite

:ype, space ~roup p:
1/n - C~4 (~o.14) w~th a_= 6.823±~.009.A,
_0.009 A, c - 6.621-0.009 A, B - 105.19 , V - 306.7 A Wlth
b = 7.036
Z = 4 mole-
cules in the unit cell, the density was found to be Dx = 8.29 gcm- 3 .
This shows an interesting aspect in the structure systematics of the

lanthanide and actinide arsenates. In the lanthanide series, LaAs04
through NdAs04 exhibit the monoclinic monazite type structure, PmAsO,+
through LuAs04 have the tetragonal zircone type structure. It appears
that curium is rather to be considered the chemical homologue of Nd than
that of Pm. It van be expected that BkAs0 4 probably will have the zir-
cone type structure.
2:6:7. Curium(III)-vanadate(V) , CmV0 4 .
74 ~g Cm02 were intimately mixed with 31 ~g NH,+VOs, and placed into the
the quartz reaction tube of the Fried-Davidson apparatus. The mixture
was heated to 650°C. After a period of 7 hours, the reaction temperature
was raised to 930°C and maintained at this temperature for 8 hours. The
brownish to honey-yellow reaction product of the reaction
was X-rayed immediately after preparation.
It was found to be isomorphous with AmV04 and with the lanthanide vana-
dates, LnV04, in particular, it agrees well with NdVO,+ (56). CmV0 4 is
tetrragonal,zircon type structure, space group I4 1/amd - D~h (No. 141)
with a = 7.290±0.013 A, c = 6.417±0.012 A, V = 314.0 A3. For Z = 4
formula units in the unit cell, the density was calculated to be 6.99
gcm- 3 .
°
Good agreement between observed and calculated intensities was found
with 4 Cm in 4 (a), 4 V in 4(b), and 16 in 16 (h) with the parameters
x = 0.437 and z = 0.212, origin at 4m 2 at 0, 1/4, 1/8 from center (2/m).
<D 0(1)
o 0(2)
• Cm
Fig.6. CmOs-coordination polyhedron in CmV04,

where the distances are Cm-O(1) = 2.347 A,
and
Cm-O(2) = 2.560 A.
KANTHAL WIRE\
"CHISEL" ---4
I'1,---____ PT- (lR)- WIRE SPIHAL
PULLED APART, WITH
ADHERING SAMPLE
\ i'I
\ \I
1\)11
J:
~.?-.-- QUARTZ X-RAY
CAPILLARY
I !
I j
Fig.7. Charging of materials prepared in the

Pt- or Ir-spiral furnace into the X-ray capil-
lary
2.6.8. Curium(III)-chromate(V), CmCr04.
19.5 ~l of 0.01 M Cr(N03)3-solution were added tQ 50 ~l of 3.6 x l0- 3M

Cm3 + solution. By
addition of an excess of 7M NHUOH and heating, the
hydroxides were precipitated. The light green hydroxide prec~p~tate
was washed several times with distilled water and methanol, and dried
under the IR lamp. The dried hydroxide mixture was placed into the
quartz reaction tube of a Fried-Davidson apparatus, and was heated at
610°C in an atmosphere of oxygen. The dark green reaction product, which
was formed according to the reaction
2(Cm,Cr) (OH) 3 + 02
was identified by its X-ray diffraction pattern.
The powder diffraction data of CmCr04 showed that the compound contained
Cm203 as an impurity. So far, we were not yet able to prepare pure
CmCr04' From the reflexions assigned to CmCr04, it was found that
CmCr04 is isomorphous with NdCr04' It has a tetragonal ZrSi0 4 lattice,
space group I41/amd - Dl~ (No. 141) with a = 7.242±0.024 A, c = 6.353±
0.021 A, V = 333.2 A3. W~th Z = 4 formula units in the cell, the cal-
culated density is Dx = 7.18 gcm- 3 .
2:6.9. Curium(III)-scandium oxide, CmSc03
300 ~l of 1.16xl0- 3 M Cm3+ stock solution were carefully evaporated

under the IR lamp, and were mixed with 35 ~l of 0.01 M SC(N0 3)3 solu-
tion. 35 ~l of 7 M NH40H were added, and the resulting pale-yellow
hydroxide precipitate was washed several times with water, and was then
transferred to the Pt-spiral furnace (Figs. 4 and 5). The reaction reci-
pient was evacuated twice, and was flushed with purified argon. The Pt-
spiral was heated to 1160°C and maintained at this temperature for 30
minutes. Then, the reaction temperature was raised to 1275°C, main-
tained at this latter temperature for 15 minutes, and cooled.
After the Pt-spiral had cooled, it was carefully pinched off from the
tungsten electrodes of the furnace, and the windings of the spiral were
pulled apart under the stereomicroscope inside the wide part of the X-
ray capillary. The part, which stuck to the wire was chipped off by
means of a micro "chisel" consisting of a kanthal wire (Fig. 7). All
these operations required extreme cleanliness to prevent contamination
of the samples and great dexterity to prevent losses of material, be-
cause the chipped-off material tended to jump away.
The CmSc03waS X-rayed immediately after preparation. It was found to

have a perowskite type structure,GdFe03 type, space group Pbnm - Di~
(No. 62) with an orthorhombic lattice with a = 5.532±0.014 A, b = 5.753
±0.015 A, c = 7.987±0.020 A, V = 254.2 A . With Z = 4 formula units in
the unit cell, the denisty is Dx = 8.81 gcm- 3
Intensities were calculated using the atomic positions of space group

Pbnm : Cm in 4 (c) with x = 0.015, Y = 0.059 , 0(1) in 4 (c) with

x = 0.109 and y = 0.452, and 0(2) in 8 (d) with x = 0.664, y = 0.327,
and z = 0.059. These data are based on those published for EuScO, (52).
Experimental and calculated intensities are in good agreement.
2.6.10. Curium(III)-vanadate(III) , CmV03
Starting from 53 ~g Cm02 and 23 ~g NH4VO" brownish-yellow CmV04 was pre-

pared in the manner described on page 174. This was reduced with hydrogen
at 890°C in the quartz reaction tube of the Fried-Davidson apparatus for
a period of 15 hours. Every 15 minutes,. the Fried-Davidson apparatus was
evacuated, and the hydrogen was replaced by fresh hydrogen. The resulting
dark-green solid, which was obtained according to the reaction
890°C ... CmV03 + H20

15 hrs
X-ray powder patterns of CmV03 were taken immediately after preparation.
The powder pattern of CmVO j shows close resemblance with the patterns of
PUV03 (53) and of AmV03 (47). CmVO j has a Eerowskite type lattice, ortho-
rhombic GdFeOg type, space group Pbnm - Dih (No. 62) withga =.5.428±0.019
A, b = 5.571±O.020 A, and c = 7.766±0.028 A, V = 234.8 A . W~th Z = 4,
the density was calculated to be Dx = 9.70 gcm- g .
2.6.11. Curium(III)-chromate(III), CmCrOg
CmCrOg has been prepared by solid state reaction between Cm20g and Cr20g
and by ignition of mixed hydroxides of Cm(III) and Cr(III), which had
=>
been precipitated by ammonia from a mixture of Cm3 +- and Cr 3 + solutions:
Cm20g + cr 20 g 8 50 0 C-900 ° C ~ CmCr03

(Cm,Cr) (OH) 3-
a) 135 ~g CmOz and 38 ~g Cr20g were weighed on a microbalance, were

intimately mixed, and charged into the quartz reaction tube of a Fried-
Davidson apparatus. The mixture was heated in air for 33 hours at 700°C.
After 15 hours, the heating was interrupted and the reaction product was
ground again to insure homogeneity. The resulting light-green reaction
product was identified by its X-ray powder pattern.
b) 100 ~l of a 3.6 x lO- 3M Cm3+ solution was mixed with 38.8 ~l 0.01 !! Cr 3+
solution. The dark green hydroxide mixture was precipitated from the
heated solution with 7 M NH40H. The precipitate was washed, dried, and
transferred to the quartz reaction tube of the Fried-Davidson apparatus,
and ignited at 900°C. The reaction product was X-rayed immediately after
preparation.
In both preparations, unreacted Cr20gWaS found besides CmCr03' This also

applied to a preparation, which was carried out at 1250°C in the Pt-spiral
furnace, and which was also contaminated with Cr203. This, on the other
hand, had the advantage that the Cr20g-lines could be used as an internal
CmCr03 has a perowskite type structure, orthorhombic GdFe03 type, space

group Pbnm - D1g (No. 62) with the following lattice constants: a
5.403±0.021 A, b = 5.508±0.021 A, c = 7.669±0.030 A, V = 228.2 A3. With
Z = 4 formula units per cell; the calculated density was found to be
Dx = 10.01 gcm- 3 •
2:6.12. Curium(III)-Iron(III)-oxide, CmFe03
The preparation of this compound was done by ignition of the mixed

hydroxides in the same manner as in the preparation of CmSc03' 200 ~l
1.16xl0- 3 M Cm3+ solution were mixed with 34 ~l 6.95xl0- 3 M Fe 3+ solu-
tion, and the hydroxides were precipitated with ammonia. The resulting
hydroxide mixture was washed, dried, and transferred to the Pt spiral
furnace. It was reacted to CmFe03by ingition at 1160°c and 1275°C, re-
spectively. The dark brown reaction product was identified by its X-ray
powder pattern.
CmFe03 is also a perowskite tYEe compound, GdFe03 type. I t is ortho-

rhombic, space group Pbnm - Dih (No.62) with the lattice constants
a = 5.414±0.010 A , b = 5.579 ±0.015 A, c = 7.739±0.015 A, V = 233.8 A~
With Z = 4 formula units in the cell, the caculated density is D
-3 x
9.88 gcm .
2.7. Oxyhalides of Curium(III), CmOX.
Until recently, only very little information was available on the oxy-
halides of curium(III)4 CmOX, where X = F, Cl, Br, or I. In 1971 Pe-
terson (31) prepared 2 aCmOCl and determined its lattice constants, in
1977, Weigel, Wishnevsky, and Hauske (9) have studied the vapor phase
hydrolysis of CmC13 and determined the-heat of formation of CmOCl. We
therefore thought it of interest to prepared and characterize some of
the oxyhalides.
2.7.1. Curium(III) oxyfluoride, CmOF
In preliminary mockup experiments, we had found that ~he thermal decom-

position of gadolinium monofluoroacetate, Gd(FCH2COO)3, yielded pure
GdOF. It was therefore assumed that curium monofluoroacetate,
Cm(FCHzCOO) 3 , would react in the analogous manner.
An excess of freshly precipitated Cm(OH)3 or aged Cm2(C204)3 was added

to 50 ~l of 0.01 M monofluoro acetic acid in a microcone. After the acid
had reacted with the curium hydroxide, or the oxalate, the mixture was
centrifuged, and the supernatant separated from the solid residue. The
clear supernatant solution was rapidly evaporated to dryness. The re-
naiuing pale yellow amorphous residue was transferred to the quartz re-
action tube of the Fried-Davidson apparatus. It was then heated slowly
to 730°C, and maintained at this temperature for a period of 4 hours.
The greyish-yellow reaction product was X-rayed immediately after pre-
paration. It was identified as CmOF, isomorphous with EuOF and PuOF.
The powder pattern of curium oxyfluoride was indexed in terms of a he-

xagonal-rhombohedral lattice, space group R3m - D~d(NO. 166) with the
following lattice constants:
hexagonal rhombohedral
aH 3.864±O.007 A aR 6.843±0.011 A
cH 19.408±0.034 A aR 32.80°
VH 2S0.S A3 VR 83.6 A3
ZH 6 ZR 2
D = 11.08 gcm- 3
x
An intensity calculation was carried out using the LAZY PULVERIX pro-
gram and the parameters determined for YOF by Mann and Bevan ~O).
With Zc = 0.241, z = 0.372, and Zo = 0.117, good agreement between
observe~ and calcula~ed intensities was obtained. The Cm-O distances
were found to be 2.34 A and 2.41 A, the Cm-F distances 2.49 A, and
2.54 A. The observation that Cm-O distances were smaller than Cm-F
distances was also observed for the corresponding distances in YOF and
EuOF.
2.7.2. Curium(III) oxychloride, CmOCI
For the preparation of CmOCI, the reagent vessel of the Fried-Davidson

apparatus was charged with concentrated HCI. Apporx. 50 ~g of curium
(III)-oxalate (2.S.1, p. 5) was.charged into the quartz reaction tube.
The oxalate was slowly heated to SOO .•. S20°C, and was reacted for 8
hours in a gaseous mixture of HCI and H 0 vapor. Every 15 minutes,the
gas mixture was evacuated, and was replaced with fresh mixture. The
resulting pale-yellow reaction product was sealed in an X-ray capillary
for identification.
In accordance with the study of Peterson on 248 CmOCI (31), the :.!44CmOCI
studied in our laboratory showed the same symmetry, space group and
lattice constants within the limits of error. 244CmOCI, like the 248 Cm_
compound, is tetragonal, PbFCI structure, space group P4/nmm - DIh
(No.129) with the following lattice constants: a = 3.983 0.003 A,
c = 6.738 O.OOS A, V = 106.9 A3. With Z = 2 formulas in the cell, the
calculated density is Dx = 9.18 gcm- 3 •
The preparation of :.!44CmOCI offered an opportunity to study the change

of lattice constants as a function of time. If a solid undergoes ex-
ternal or internal irradiation with heavy particles. such as a-partic-
les, a change of the lattice constants is frequently observed. As a
rille, they become larger, Le. the lattice expands.
This effect, so far, has only been studied in cubic compounds, such as
CmOz (26)(32), or CmAIOg (51)(58). So far, no studies of compounds with
lower symmetry had been made. The availability of tetragonal CmOCI
dCA)
11.00
Fig.B. Change of lattice constants in CmOCl with time

(244 CmOCl)
---
tuc
lCo
(lo·SA) ~
Co
,
(;
14
5 10
--T (H)
Fig.9. Relative change of lattice constants ~n CmOCl with time

e"4 CmOC l)
offered us a chance to study the behavior of two different lattice con-

stants if the lattice was subjected to self-irradiation.
We have therefore taken the powder pattern of a CmOCl sample at 3 hour

intervals for a total time of 30 hours. The observed change of the CmOCI
lattice constants is shown in Fig.8 • Fig.9 shows the relative change
of the same constants with time. It was not possible to continue the
measurements beyond a time period of 40 - 50 hours, because the X-ray
patterns become increasingly diffuse and more and more difficult to
evaluate.
The interesting observation is, that the a-axis approaches a limiting

value of a = 3.995 A after a few hours, whereas the c-axis continues
to grow. This behavior may be understood:from the layer structure of
CmOCI, which had been studied by Peterson and Burns (30) on 248CmOCI.
Each curium atom is surrounded by 4 O-atoms, 4 Cl-atoms from one neigh-
bouring layer, and 1 CI atom from the next layer. The layers stacked in
the c-direction in the sequence CI-Cm-O-Cm-CI ...• have most certainly
a smaller bond strength between each other than the CI-O- or Cm-atoms
within one layer. The observed behavior is best explained by the assump-
tion that a Cm atom, in its decay, is hardly ruptured from its position
relative to its nearest neighbours, but that the whole layer close to
the decaying atom is dislocated.
After a period of 80 - 90 hours, no more X-ray reflexions can be ob-: c~.·-,

served in a CmOCI powder pattern. The order of the lattice may be re-
stored, however, by heating the sample in a mixture of HCI and H20.
The lattice parameters of 244 CmOCI extra~olated to t = 0 hours were

compared with the corresponding data of 2 8CmOCI. It was found that the
two sets of lattice constants for the two isotopic compounds were in
almost complete agreement with each other, i.e., within the margin of
error, it is of no influence, if a 244 Cm atom is exchanged for a 248 Cm
atom.
The dependance of lattice parameters on time is taken into account for

all other Cm compounds studied. In all cases, X-ray patterns were taken
immediately after preparation, at the utmost, a period of 15 - 30 minu-
tes after preparation is allowed.
2.7.3. Curium(III)-oxybromide, CmOBr
CmOBr was prepared from aged Cm2(C204)3'10H20 in the reaction tube of an

available vapor phase hydrolysis apparatus. 35 ~g of curium oxalate de-
cahydrate were charged into a micro platinum boat (6X1.5~1.5 mm 3), which
was placed onto a quartz slide, and was carefully introduced into the
reaction tube (Fig.10). The sample was heated to 360°C, and a stream of
Nzwas passed over it. At the same temperature, the N2 was replaced by
HBr gas, and the curium sample was heated for a period of 40 minutes in
the HBr to form CmBr3. The CmBr, was hydrolyzed for another 40 minutes
at 360°C in a stream of HBr/H20/N2.In the same gas stream, the tempera-
ture was raised to 600°C, and maintained for 1 hour. The pale-yellow re-
action product was X-rayed after cooling. The reason for the complicated
preparation technique is the low melting point of CmBr3, which is ap-
prox. 400°C (46). The melting of the CmBr3 must be avoided to prevent
that the hydrolysis stops at a too early time.
CmOBr is isomorphous with AmOBr ~~O). It crystallizes in the tetragonal

symmetry, space group P4/nmm - D4~(NO. 129) with a = 3.956±0.008 A,
and c = 7.936±0.015 A, V = 124.4 A3. With Z = 2 formula units in the
cell, the density is calculated to be Dx = 9.09 gcm- 3 • Intensities were
calculated with 2 Cm in 2 (c), 2 Br in 2 (c), and 2 0 in 2 (a), and with
the parameters zl = 0.192, and z2 = 0.610, with the origin located in
the center of symmetry (21m).
2.7.4. Curium(III)-fluoride, CmF 3
Curium(III)-fluoride was one of the first two curium compounds, which

were prepared in the solid state, and were characterized by their X-ray
powder patterns (6). The standard preparation procedure for this com-
pound involves the treatment of Cm02 with anhydrous hydrogen fluoride
at 500°C, or the precipitation of Cm3+ with F- in aqueous solution,
followed by dehydration of the precipitate in high vacuo. In both cases,
vacuum equipment made of monel or Ni is required.
We have observed that the thermal decomposition of curium(III)-trifluoro-

acetate, Cm(CF 3COO)3, yields anhydrous CmF3, probably by a reaction such
as
Cm(CF3COO)3 + CmF3 + 3COF2 + 3CO
The same is true for the preparation of GdF3 and AmF3 from the corres-
ponding trifluoroacetates. The procedure for the preparation of CmF3 is
as follows:
To 80 ~l of 0.01 M trifluoroacetic acid, excess Cm(OH)3 is added. After

a reaction time of 15 minutes, the supernatant is separated from undis-
solved curium(III)-hydroxide and is cautiously evaporated to dryness
under the IR lamp. The isolated pale-yellow residue, which is amorphous
to X-rays, is placed into the quartz reaction tube of a Fried-Davidson
apparatus and is heated in vacuo, or in argon atmosphere to a tempera-
ture of 550°C within 3 hours. The reaction temperature is maintained
for another 3 hours, then the product is sealed in an X-Ray capillary,
and a powder pattern is taken immediately.
In agreement with earlier results (8), CmFg was found to be hexagonal

LaF3 -type, space group P6 3 /mcm - DIh (No.193) with a = 6.992±0.013 A,
c = 7.177±0.013 A, V = 303.9 A Witn Z = 6 formula units in the cell,
the density was calculated to be Dx = 9.87 gcm- 3 .
GAS EXIT THERMOCOUPLE WELL
GAS INLET QUARTZ TRAY WITH

PLATINUM BOAT
Fig.l0. Reaction tube of vapor phase hydrolysis

apparatus, modified for preparation of CmOBr
STOPCOCK
JOINT TO
FRIED DAVIDSON-
APPARATUS
mm OD QUARTZ TUBE
Fig.11. Quartz reaction tube for Fried-Davidson-

apparatus for preparation of AmC1 3 and CmCls.
2.7.5. Curium(III)-chloride, CmCl3, and Americium(III)-chloride, AmCls
Curium(III)- and americium(III)-chlorides, both well-known compounds,

were prepared for supporting research in connection with work on the
determination of the vapor pressure of americium(III)-chloride.
For preparation of CmCls, approx. 1.2 mg Cm02 were placed into the
quartz reaction tube of 4 mm OD (Fig.11), which was equipped with a
stop cock. This stop cock is necessary to prevent the entry of moisture
into the tube, when-. it is transferred into a different glove box.
The reagent vessel of the Fried-Davidson apparatus was charged with
CCh dried over P20S. The Cm0 2 was slowly heated to 400°C, then, the
reaction tube was evacuated, and filled with CClt. vapor. In the course
of the reaction, the temperature was slowly raised to 800 .•. 850°C, and
the gas in the reaction tube was changed in 10 minute intervals. The
sublimation of the CmCl 3 can be easily observed; after a while, it
starts to collect outside of the furnace zone as a pale-yellow ring.
After a period of 3 hours, the Cm02 starting material has been almost
completely converted to CmCls. By carefully moving the furnace over the
reaction tube, the CmCl 3 sublimate could be concentrated in a narrow
zone inside the quartz reaction tube. The stopcock was then closed, and
the tube transferred to an inert gas glovebox. A small quantity of the
CmCls was sealed in a quartz X-ray capillary, and was X-rayed immediate~
ly after preparation. The major part of the CmCl3 was sealed in a quartz
sample tube (2 mm OD) for the DTA apparatus. The AmCl3 sample was pre-
pared in exactly the same manner as the curium compound, except that
2.5 mg Am02 were used as the starting material.
The X-ray data of CmCl s were in agreement with earlier work (8)(30).
CmCl s was found to be hexagonal, space group P6 3 /m - C~h (No.-176) with
a = 7.366±0.020 A, c = 4.204±0.011 A, V = 197.5 AS. Witli Z = 2 formula
units in the cell, the density was calculated to be Dx = 5.89 gcm- s •
The determination of the melting points, heats and entropies of fusion

in the DTA apparatus yielded the values summarized in Table 5.
2.8. Compounds of Curium(IV) and Curium(V)
Only very few examples of curium compounds having another valency than
+3 are known, such as Cm02, CmF4, complex curium(IV)-fluorides, and the
oxo compound BaCm03 (48) (36). Incthe course of thisvlOrk, we decided
to attempt the preparation of other. hitherto unknown compounds of
curium(IV) and, possibly, of curium (V). We succeeded in preparing di-
lithium-trioxo-curiate(IV) , Li2Cm03, and trisodium-tetraoxocuriate(V),
Na 3Cm0 4.
2.8.1. Dilithium-trioxo-curiate(IV), Li2Cm03.
The preparation of Li2Cm03 was done in an apparatus similar to that

shown in Fig. 3, except that a gold boat was used instead of a quartz
Table 5. Melting points and thermodynamic data

for fusion of AmCl 3 and CmCl 3
AmC l 3 CmCI~
melting point °C a) 718 704

(715) (695)
K 991 997
(988) (968)
toR f (kcal/mol) 11 . S±O. 1 11. S±O. 4

(kJ/mol) 48.1±0.4 47.9±1.6
tos f (cal/mol·K) 11. 6±0. 1 11.7±0.4
(J/mol·K) 48.S±0.4 49.0±1.6
a) melting point values in parentheses are

from Peterson and Burns (30)
or alumina boat. A slow stream of oxygen, which had been purified from
CO 2 and H20 was passed over the gold boat, which had been charged with
a mixture of Li 20 and Cm02 in the ratio 2:1. The gold boat was heated
at 550°C for 30 minutes. The black, slightly hygroscopic reaction pro-
duct was immediately sealed in an X-ray capillary, and its powder
pattern was taken.
The compound Li2Cm03 was only stable in the presence of excess Li 20, but
did not combine with the latter to form higher oder compounds, In the
Li2Cm03 pattern, the Li20 lines were clearly discernible and could be
used as internal standard.
The observed powder pattern could be interpreted in terms of a tetra-

gonal lattice, unknown space group, with a = 8.300±0.022 A, and c =
8.611±0.023 A. Li 2CmO, is isomorphous with Li2Am03' (47).
The compound is insoluble in CsF- and in 5 M LiOH solution. The insolu-

bility is probable due to the reduction of Cm(IV), because Cm(VI} is
most likely been stabilized in concentrated CsF solution. Li 2Cm03 dis-
solves in 1 N HCIO~. The brief appearance of an olive green color in the
solution indicates the transient presence of Cm(IV) in the dissolving
solvent.
Despite our attempts in this direction, we were not able to prepare com-
pounds such as LisCm06,Li7Cm06, or Li6CmOs by reacting Li2Cm03 with cor-
responding amounts of LizO. On the other hand, it is surprising
that Li2CmOs, in the presence of LizO, is stable up to 650°C, as is
demonstrated by high temperature X-ray;qifftaction data.
2.8.2. Trisodium-tetraoxo-curiate(V), Na,Cm04.
For the preparation of Na,Cm04, Na202 and CmOz were mixed in the ratio
3:1 and were reacted with each other in an atmosphere of oxygen. In ana-
logy to the preparation of LiaCm03, an excess.of Na202 was necessa:ry.;;,_
The mixture of Na202 and Cm02 was charged into the gold boat, and heat-
ed at 450°C for 30 minutes in a stream of oxygen, which was free of H20,
and C02. The reaction product was transferred to the inert gas glove box
in a desiccator filled into an X-ray capillary, and the powder pattern
was taken immediately after sealing the X-ray capillary.
The dark brown, extremely hygroscopic reaction product showed the pre-
sence of Na3Cm04besides Cm02' The reflexions assigned to Na3Cm04 could
be interpreted in terms of a cubic NaCI structure, space group Fm3m -05
(No. 225). The lattice constant was 4.8207±0.0026 A, V = 112.0 A; with h
Z = 1 formula unit in the cell, the density was calculated to be D
5.59 gcm- 3 • The compound was found to be isomorphous with Na,U04 x(47).
Assuming 1 formula unit in the cell, the curium and sodium atoms are
distributed statistically on the position 4 (a), the oxygen atoms occupy
the 4 (b) positions. I.e. the Na3Cm04_structure~.consists oftwo~f.dc
lattices, where the oxygen atoms and the metal atoms form one of these
Table 6. Summary of compounds prepared in the course of this work
Compound Syrnm. a(A) b(A) cOt) a (0) B(0) Color
CmOz (c) 5.369 black

CmSc03 (0) 5.532 5.753 7.987 pale yellow
CmV03 (0) 5.428 5.571 7.766 dark green
CmCr03 (0) 5.403 5.508 7.669 pale green
CmFe03 (0) 5.414 5.579 7.739 dark brown
C1uP04 ·O.5HzO (h) 7.00 6.39 pale yellow
CmAs04 (m) 6.823 7.036 6.621 105.19 pale yellow
CmV0 4 (t) 7.290 6.417 honey ye 11 ow
CmC r0 4 (t) 7.242 6.353 dark green
Cm2(MoO,+)3 (t) 5.250 11 .496 brown yellow
Cm2(WO,+)3 (m) 7.714 11.556 11.450 109.14 light yellow
Cm(ReO,+) 3 'XH20 (0) 5.636 7.674 15.401 white
Cm(Re0 4)3 (h) 10.065 6.294 white
CmOF (r) 6.843 32.80 greyish-yellow
CmOCl (t) 3.983 6.738 pale yellow
CmOBr (t) 3.956 7.936 pale yellow
CmF3 (h) 6.992 7.177 white
CmC 1 3 (h) 7.366 4.204 pale yellow
Cm(HCOO)3 (r) 6.272 115.46 pale yellow
Cmz(C204)3'10HzO (m) 11.23 9.60 10.22 114.64 pale green
Li 2CmOg (t) 8.300 8.611 dark brown
NagCmOIt (c) 4.821 dark brown
Symmetries: (c) cubic

(t) tetragonal
(h) hexagonal
(r) rhombohedral
(0) orthorhombic
(m) monoclinic
two individual lattices. An intensity calculation was carried out using

the atomic positions given above, and the LAZY PULVERIX program. The
calculated intensities are in good agreement with the observed values.
The lattice constant is compared with the lattice constants of the corre-
sponding lattice constants of Na3U04 (54) and Na3Am04(47). The structures
of the compounds Na 3 Np04 (59) and Na3Pu04 (59) are not-Yet evaluated.
F,om X-ray data, for these-ratter compounds-,-a lattice of lower symmetry
with NaCI superstructure is suspected. It is still unknown, why Na3Np04
and Na3Pu04 have another structure than Na3U04,NajAm04 and Na3CmO~. This
behavior warrants a systematic X-ray study of the oxometallates (V) from
uranium through curium.
It is remarkable that, even though~Na3Cm04 has a NaCl type structure,

the expected formation of CmO! , the linear "curyl" configuration in the
solid, is not observed. Rather, the 6 oxygen atoms located in the corners
of an octahedron around each curium atom have all the same distance to
this actinide central atom.
3. DISCUSSION
A number of hitherto unknown cur1um compounds have been synthesized.Also,

some well-known compounds have been prepared in order to study specific
physical properties, or novel methods of synthesis,
Most of the compounds prepared involve trivalent curium. In this valency

state, the curium behaves in no way different from other trivalent ac-
inides. A new type of tetravalent curium compound, and, what we believe
the first compound of pentavalent curium have been identified.
It has been observed that monofluoracetic acid and trifluoroacetic acid

form curium(III)salts, which pyrolyze to form CmOF and CmF, respectively.
These reactions are the basis for a new synthesis for the trifluoride,
and for the oxyfluoride.
The availability of more sophisticated X-ray diffraction programs allowed

the improvement of many X-ray data of curium compounds. It was possible
to make intensity calculations to determine the atomic positions of the
heavy atoms. One has to keep in mind, however, that the atomic positions
of the light atoms are uncertain, because of their low contribution ( a
few percent in most cases) to the intensities. They should therefore be
treated with reservation. A summary of all compounds prepared is given in
Table
4. ACKc\l8WLEDGMENTS
We wish to express our thanks to the US Department of Energy, Washing-

ton, D.C. for supplying us with the curium used in this work. To Mr.A.
Dchs, we wish to express our gratitude for his masterful glass- and
quartz blowing work.
To the Bundesministerium fur Forschung und Technologie, Bonn Bad Godes-

berg, we wish to express our thanks for the financial support of this
work. We also express our thanks to the Deutsche Forschungsgemeinschaft
for financial support (Grant We 324/34).
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THE ELECTRONIC AND MAGNETIC PROPERTIES OF Am AND Cm
Norman Edelstein
Berkeley, California 94720 U.S.A.
ABSTRACT. A review of the present status of the analyses of the optical

spectra of Am and Cm in various oxidation states will be given. From
these analyses, the magnetic properties of the ground states of these
ions can be determined. These predicted values will be compared with
the various magnetic measurements available.
1. INTRODUCTION
The optical and magnetic properties of Am and Cm have now been studied
for over 30 years. The common oxidation state for these elements is the
trivalent one, and their lanthanide analogues in this oxidation state
have magnetic properties which differ from the rest of the lanthanide
series. This fact has made the study of the magnetic properties of the
Am3+ and Cm 3+ ions of special interest in order that the differences (or
similarities) between the 4f and 5f series could be determined. In this
paper the optical properties of the various accessible oxidation states
of these two elements will be briefly reviewed, followed by a review of
their magnetic properties. The optical properties of the atoms in the
gaseous phase or as free ions will not be covered.
2. Optical Spectra
The optical spectra for AmX 3 (X = C~, Br, I) and Am3+ and Cm 3 + in single
crystals of Lac~3 have been measured and analyzed [1-4J. The free ion
193
194 N.EDELSTEIN
energy levels of Cm 3+ (aquo) have also been assigned on the basis of the
correlation between obs~rved and calculated band intensities [5J. Other
oxidation states of both Am (divalent, tetravalent to hexavalent) and Cm
(tetravalent) are known and low resolution spectra of the tetravalent
state in solids and solution have been obtained [6-9J. Recently,
4+ 2+
calculated free ion spectra for Am and Am have been published [10J.
Selective laser excitation experiments on Cm 3+ in D20 have also been
carried out [11J.
3. Magnetic Properties
Magnetic properties of materials determined by bulk magnetic
susceptibility or electron paramagnetic resonance (epr) measurements are
usually determined by the energy levels of the materials which are
populated at the temperatures of the measurement. Most epr spectra of
actinide ions are measured at 4.2 K so usually only the magnetic
properties of the ground crystal field state are determined. Magnetic
susceptibility measurements are performed in a range of temperatures
(-2-300 K) so the splittings of lowest J level may sometimes be
determined [12,13J. If the ground state is a singlet (non-magnetic),
the magnetism of the material is determined by the mixing of the higher
lying magnetic states into the ground state by the magnetic field. This
type of magnetic behavior is independent of temperature (if the magnetic
state lies much higher than kT). Table 1 lists the configurations of
various oxidation states of Am and Cm for which magnetic data have been
measured. Each of these configurations will be discussed individually.
4. 5f 5 - Am4+
The ground term for the Am4+ ion is a nominally 6H5 / 2 However because
of the strong spin-orbit coupling for actinide ions, this state is less
than 66% pure. This number comes from calculations on pu 3+ [14J. Table
3+ 3+ 4+
2 shows the eigenvector components for Sm and Pu free ions. Am
has a larger spin-orbit coupling constant than pu 3+, thus the pu 3+
eigenvector represents a lower limit for an Am4+ intermediate-coupled
THE ELECTRONIC AND MAGNETIC PROPERTIES OF Am AND Cm 195
Table 1. Accessible Oxidation State for Am and Cm
Am Cm Ground State
4+
5f 5 Am J 5/2
4+
5f 6 Am3+ Cm J 0
5f7 2+ Cm 3+
Am J 7/2
Table 2. Largest Eigenvector Components for Sm 3+ and pu 3+

Ground J = 5/2 State (Ref. 14)
644
96.0% H + 2.3% G4 + 1.4% G1 +
pu 3+
66.0% 6H + 14.3% 4G4 + 9.6% 4G1 + 1.7% 4F3 + 1.2% 4G3 + 1.0% 2F6
+ 1.0% 6F + 1.0% 2F2 +
eigenvector. Since most of the calculations have been done for pu 3+

4+
systems, these will be summarized, but the same arguments hold for Am
in sites of the same symmetry.
4+ .
Electron paramagnetic resonance has been reported for Am diluted
in Th02 and Ce0 2 single crystals [15,16J. The site symmetry for the
Am4+ ion is cubic. For a J = 5/2 state in cubic symmetry the crystal
196 N. EDELSTEIN
field will split this term into two states, a r7 doublet and r8 quartet
state. For this symmetry "the splitting of these two levels depends on
two crystal field parameters 86 and 8~, and angular factors which depend
on the intermediate coupled wavefunction. These angular factors have
been calculated for Sm 3+ and pu 3+, and it has been shown that the sign
of °
86
(which is the dominant term) for pu 3+ (or Am 4+) 1S
. opposite to
that for Sm 3+ [14J. This sign change is due to the large admixture of
higher L-S states by the spin-orbit coupling interaction. The net
result is that for Sm 3+ the r8 state would be lowest, but for pu 3+ or
4+
Am ,the r7 state is the ground state. This is illustrated in Fig. 1.
For an isolated r7 state the calculated g value should be equal to
r 6' E + 14 b'4 20 b I
6
J = 7/2 r'8 E + 2 b'4 + 16 b'6

- r'7 E - 18 b'4 12 b'6
::wa~""'~
-
{
ra 2 b4
J = 5/2
r7 -4b 4
Figure 1. Schematic energy level diagram for pu 3+/caF 2 and Am 4+/Th0 2 •

Ce0 2 • For Sm 3+ (the 4f analogue), the r7 and r8 energy level ordering
for the ground J = 5/2 state is reversed.
4+
-0.700. The measured values for Amin Ce0 2 and Th02 are as shown in
Table 3. Note that these two values are different with Am 4+/Th0 2
being larger. For pu 3+ the first excited state is a J=7/2 which is
-1
calculated to be at -3200 cm • In the actinide series, crystal field
Table 3. Measured g values for 5f5 Ions in Various Hosts (Ref. 16)
IAI
(10- 4 em -1 ) B,a
4
Matrix Igl
239 pu 3+ 241pu3+ (cm-1 )
Ce0 2 1 .333 ± 0.001 22.4 ± 0.2 -5400
Th0 2 1.3124 ± 0.0005 65.4 ± 0.2 -5130
46.1 ± 0.6
CaF 2 1.297 ± 0.002 1)6.95 ± 0.03 -4945
48.07 ± 0.10
SrF 2 1.250 ± 0.002 84.6 ± 1.0 -4440
BaF 2 1 .187 ± 0.004 102 ± 3 -3820
SrC1 2 1.1208 ± 0.0005 127.9 ± 0.4 -3190
IAI
(10- 4 cm -1 )
Matrix 241Am4+ 243 Am 4+

Igl
Ce0 2 1 .3120 ± 0.0005 22.1 ± 0.2
Th02 1.2862 ± 0.0005 45.7 ± 0.1 45.3 ± 0.1
a
Values of B4 were calculated assuming that B'/B'
6 4
- 0.2.
198 N. EDELSTEIN
effects are large and this interaction can mix excited states into the
ground state. Using a model which considered only the mixing of these
two states, Edelstein, et al. fit a series of g values for pu 3+ in CaF 2 ,
SrF 2 , and BaF 2 showing that the crystal field interaction decreased as
the lattice parameter increased [14J. This same model has been applied
4+ .
to fit the g values for Am In Th02 and ce0 2 [16J. The results are
consistent with Ce0 2 (the smaller lattice) having a larger crystalline
field interaction at the Am4+ site than Th0 2 • A plot of the g values
vs. the crystal field parameter is shown in Fig. 2. A more complete
-OJOr---r---.---~--.---'----r---r---.--~---'
-0.80
-0.90
=0
-1.00
g
-1.10
/"
./
./
-1.20 ./
./
./
./
-1.30 ./
./
-lAO
-1.50
o -2 -4 -6 -8 -10 -12 -14 -16 -18 -20

8' X 10- 3
4
Figure 2. Plot of calculated g value vs. B4• The solid line describes
the calculated values for B6 = O. The dotted line describes the values
for B6/B4
-0.2. The arrows show where the experimental g values are
=
located for pu 3+/caF 2 , SrF 2 , BaF 2 . A similar plot may be drawn for
4+
Am ICe0 2 ,Th0 2 .
calculation for pu 3+ in cubic lattices has been given by Lam and Chan
[17J.
The magnetic susceptibility of 243Amo2 as a function of temperature
has been reported [18J. An antiferromagnetic transition was found at
8.5 ± 0.5 K. This transition was not found in a neutron diffraction
study on 243Amo~ at 20 K and 6.5 K nor was a hyperfine field detected
for Am0 2 by a Mossbauer study [19J. The ground state g value of Am0 2
4+
was found to be 1.51 which is 17% larger than for Am in Th0 2 , and the
excited r8 state was determined to be at -35 K [18J.
6 3+ 4+
5. 5f - Am , Cm
The 5f 6 configuration has a nominally 7Fo ground term. Spin-orbit

coupling will mix in other J = a states, but this state must be a
singlet in all crystal fields. Consequently all magnetic effects will
come from second order interactions and will result in temperature
independent paramagnetism (TIP). The measured susceptibilities will be
small in magnitude and impurities in the sample could drastically affect
the measured values. With small radioactive samples (100 ~g - 10 mg)
. 241 or 243 244 or 248 C
containing the Isotopes Am and m, contamination of
samples either with chemical impurities, or by radiation damage is a
major problem. It is not surprising that the few results available vary
2
greatly. If we assume the BO crystal field parameter does not change
much from one compound to another (this is the only parameter which will
split the J 1 first excited state in compounds with C3 or higher
=
symmetry) then all Am3+ compounds should have about the same value for
their temperature independent paramagnetism. Table 4 lists the values
for a number of Am3+ compounds [20-25J. Am metal is the first actinide
metal to exhibit a localized trivalent moment. Table 4 lists the
magnetic susceptibility for Am, and whose value is in the range of
trivalent Am compounds.
4+
Cm compounds show an anomalous temperature dependence [22,26-28J.
Theoretically they should be similar to the Am3+ compounds and show
200 N. EDELSTEIN
Table 4. Magnetic Susceptibility of Am3+ Compounds and Am Metal

-6 emu/mole)
Compound TIP (10 Reference
Am 20 3 640 ± 40 20
CS 2NaAmC1 6 5400 ± 400 21
AmF 3 714 ± 1%a 22
AmF 3 566 ± 25 b 23
AmF 3 1040 ± 300 b 24

Am3+ on bead 716 ± 100b 23
Am3+ in solution 720 25
Am metal 881 ± 46 23
Am metal 675 25a
Calculated -500 c 20
a
bTemperature dependent ~eff = 0.63 BM.
Slightly temperature dependent.
c From op t·lca1 da t a on Am3+/ La Cl 3. The J--l level l·S 2720 cm- l
above the ground J=O level.
temperature independent paramagnetism. However they are temperature

dependent and have effective magnetic moments between 2-4 Bohr
magnetons. Kanellakopolus has followed the magnetic susceptibility of a
244 cmo2 sample as function of time and found the magnetism increases
linearly [26J. He proposed that this increase was due to the formation
of Cm 3+ (a 5f7 ion with ~eff - 7.9 BM) caused by the radiation damage
due to the alpha particles from the decay of 244Cm nuclei. He was able
to fit his data by assuming a rate of production of Cm 3+ of 2.09% per
month. Goffart found a similar time dependence in his magnetic
measurements on 244 cmo2 [27J. Presumably compounds synthesized with
248 5 244
Cm ('1/2 = 4.7 X 10 Y compared with '112 = 18.1y for Cm) should be
much less sensitive to these effects. Hurray et al. have reported
. 248 4+
temperature dependent behavior for variOUS Cm compounds. Goffart
et al. and Morss et al. also found temperature dependent behavior for
248 cmo2 [27,28J. The lattice constants of these samples obtained by x-
ray powder diffraction techniques showed no indication of an expanded
4+
structure [27,28J. Further studies are necessary for the Cm
compounds.
7 2+ 3+
6. 5f , Am , Cm
The half-filled shell configuration, 4f7, in the lanthanide series gives
a ground state wavefunction for Gd 3+ which is approximately 98% 8 S7/2
(see Table 5). This state will not be split by the crystalline field.
Table 5. Leading Terms in the Wavefunctions for Gd 3+ and Cm 3+,
J = 7/2 (Ref. 35)
866
97.4% s + 2.6% P + .01% D + •••
866
79.4% S + 17.1% P + .81% D +
Nevertheless from epr measurements, splittings on the order of .1 to 1

cm- 1 are observed for Gd 3+ in various crystalline environments. These
splittings arise from various higher order mechanisms which have been
202 N" EDELSTEIN
proposed [29J. The first report of the epr of Cm 3+ was made by a group
a t Ber ke1 ey wh 0 "
f oun d a group 0 f seven I lnes a t 4 . 2 K l"n 244cm3+/LaC13
characteristic of a J 7/2 level with g = 1.991 [30J. This observation
was confirmed by a group at Argonne National Laboratory [31J. The
ground state of Cm 3+ was supposed to be analogous to its 4f7 counterpart
Gd 3+, and these data confirmed this similarity.
As more information became available about the electronic structure
of the actinides, it became increasingly clear something was wrong with
the above observations. The AmI (5f 7 7s 2 ) g value was measured by atomic
beam methods, and it was found to be 1.937 [32J. Runciman [33J obtained
wave functions for Cm 3+ and from these wavefunctions the g value of the
ground state was calculated to be 1.913 [34J. These deviations from g
2.00 were due to the large extent of intermediate coupling for Cm 3+.
Abraham, Judd, and Wickman [34J reexamined the cm 3+/LaC1 3 epr spectrum
and found a strong single line with gil = 1:925 ± 0.002 and g = 7.67 ±
0.02. A similar spectrum was found for cm 3 diluted in lanthanum
ethylsulfate. These spectra were readily explained on the basis of the
zero field splitting for Cm 3+ being large with respect to the microwave
frequency. Thus the initial reports were spurious and the cm 3+ epr
spectrum was consistent with other actinide data and theory.
The leading terms in the wave functions for Cm 3+ and Gd 3+are shown
in Table 5. Cm 3+ is only about 79% pure 8 S7/2 The three leading terms
will not split in a cubic crystalline field. An approximate calculation
using the complete 50 term wavefunction for Cm 3+ showed qualitatively
that the effects of intermediate coupling can account for the much
larger splitting in cm 3+ than in its 4f7 counterpart, Gd 3+.
The crystal field splittings for Cm 3+ in cubic compounds are of the
order of 5-50 cm- 1 The ground state is an isotropic r6 state and the
first excited state is an anisotropic r8 state. If the splitting
between these two states is of the order of magnitude of the magnetic
splittings, these two states can be mixed by the magnetic field in an
epr experiment [35J. This will result in the ground r6 state showing
some anisotropy. From the magnitude of the anisotropy, the r 6-r 8

splittings can be deduced. Some of the results are shown in Table 6.
Table 6. Zero-field Spli t tings of the 5f 7 Ions in Various Crystals

(Ref. 36)
-1 (cm -1 )
Crystal Ion (cm ) gJ
SrC1 2 Cm 3+ 5.13 ± 0.05 15.3 ± 0.4 1.928 ± 0.002
SrF 2 Cm 3+ 11.2 ± 0.4 1 .9257 ± 0.001

CaF 2 Cm 3+ 13.4 ± 0.5 1.926 ± 0.001
Th02 cm 3+ 15.5 ± 0.3 1.9235 ± 0.002

2+
SrC1 2 Am 5.77 ± 0.48 1. 9283 ± 0.0008
2+
SrF 2 Am 15.2 ± 0.4 1.9254 ± 0.001
2+
CaF 2 Am 18.6 ± 0.5 1.926 ± 0.001
For Cm 3+ in SrC1 2 , both the r6 and the r7 resonances were observed.

Both were anisotropic as shown in Fig. 3. Both the r7 - r8 and r6 - r8
splittings for cm 3+ in SrC1 2 are shown in Table 6 [36J. Finally, in
Table 7 the zero field splitting for Gd 3+ and Cm 3+ in a number of cubic
crystals are listed [38J. Note that the splitting for Gd 3+;ce0 2 is
smaller than for Gd 3+;Th0 2 . Based on an electrostatic model one would
expect the crystal field splitting to be inversely proportional to the
lattice constant (for anions of the same charge). The higher order
mechanisms must predominate for Gd 3+ in Th02 and Ce0 2 . However for Cm 3+
with its larger splitting the electrostatic mechanism appears to be the
predominant one.
204 N. EDELSTEIN
5.79
5.78
5.77
4.50
Q)
-0:J
> 4.40
0'>
4.30
4.20
4.10
Magnet angle (deg)

Figure 3. The measured g value as a function of the rotation of the dc
magnetic field for srC1 2 :cm 3+. The data were obtained at -35 GHz and
-5500 G. The smooth curves are calculated values. Note the change in
scale for the r7 (upper curve) and r6 (lower curve) states. The error
bars for the r6 state are ±0.005, for the r7 state ±0.002.
Table 7. Zero-field Splittings for Gd 3+ and Cm 3+ in Various Host

Crystals at 4.2 K (Ref. 37)
Lattice
Constant Gd 3+ Cm 3+
-1 -1
( A) (cm ) (cm )
Ce0 2 5.41 0.0653 ± 0.0004 17 .8 ± 0.3
Th02 5.60 0.06645 ± 0.00008 15.5 ± 0.3
CaF 2 5.46 0.0578 ± 0.0001 13.4 ± 0.5
SrF 2 5.80 0.0501 ± 0.0002 11.2 ± 4
BaF 2 6.20 0.0448 ± 0.0002
SrC1 2 7.00 0.01979 ± 0.0004 5.13 ± 0.5
The epr spectra of Cm 3+ in a number of tetragonal crystals have

been reported [38,39J. In D2d symmetry the crystal field states will
have eigenfunctions of the type
a I ± 7/2> + b I + 1/2>
or
cl ± 5/2> + dl + 3/2>
From the measured g values the admixture coefficients may be evaluated
and, from measurements at different temperatures, it can be determined
if the state observed is the ground state. For the system cm 3+/ThSi0 4 ,
no epr spectrum was observed [40J. In the hosts for which both Cm 3+ and
Gd 3+ epr signals have been observed, the dominant crystal field term has
had the same sign. For Gd 3+/ThSi0 4 , B; is the dominant term with a sign
< O. Assuming that B~ < 0 and dominant for the cm 3+/ThSi0 4 system, the
206 N. EDELSTEIN
state with al±7/2> + bl~1/2> would be the ground state with the values
a - and b - O. Some recent data of the various crystal field levels
for the tetragonal system cm 3+/LuP0 4 are shown in Table 8. The g values
Table 8. g Values for the Crystal Field Levels of cm3+/LuP04 (Ref. 39)
Eigenvector Calculated Measured

gil gl gil gl
0.9837 I± 1/2> - 0.1798 I~ 712> 1 .424 7.436 1.424 7.436
0.9463 I± 3/2> - 0.3233 1+ 5/2> 4.155 4.07 4.15 4.07

77K
0.9463 I± 5/2> + 0.3233 1+ 3/2> 8.0 4.07 8.0 4.07
0.9837 I± 7/2> + 0.1798 1+ 1/2> 12.95 0.25
0.98205 I± 1/2> - 0.1886 I~ 712> 1.373 7.402 1.373 7.402
0.9455 I± 3/2> - 0.3255 I~ 5/2> 4.13 4.096 4.12 4.10

4.2K
0.9455 I± 5/2> + 0.3255 I~ 3/2> 7.976 4.086 7.98 4.096
0.98205 I± 7/2> + 0.1886 1+ 1/2> 12.9 0.27
measured at 77 K and 4.2 K are slightly different due to the change in

the crystal field as a function of temperature. The net result of this
change is a small difference in the energies and composition of the
eigenvectors of the system as a function of temperature which is
reflected in the g values. All the intensities of the epr lines for
cm 3+/LuP0 4 showed decreases as the temperature was lowered. This
2
observation may be explained by again assuming that BO < 0 and is the
dominant term. Thus the state with a - -1.0 must be the ground state.
Magnetic susceptibility measurements for various trivalent Cm
compounds and AmI 2 are shown in Table 9 [21,22,41-44J. For a free ton
Table 9. Summary of magnetic data for Cm compounds

a
T ].Jeff e
Compound (K) BM (K) References
CmF 3.112 H20 77-298 -5 41
CmOCl 77-298 7.6 -22 41
CmF 3 in LaF 3 77-298 7.7 -6 41

Cm 3 + in 7.5-25 7.9 -4 21
25-45 7.5 -1 21
20-80 8.20 -149 42
100-300 7.89 -130 42
CmN 140-300 7.02 +109 43
CmAs 100-300 6.58 +88 43
-30-280 7.67 3.6 22

c
Cm 20 3 50-300 7.74 -130 22
d
Cm 20 3 4.2-300 7.51 -110 22
AmI 2 37-180 6.7±.7 e 44
a = 2.828 (T-e)1/2 BM .
].Jeff
b. . ..
Antiferromagnetic transition at T 13±2K.
cMonoclinic phase.
d
bce.
enot given in Ref. 44.
208 N. EDELSTEIN
~eff = 7.9BM. Thus most of the data at high temperatures agree with the
expected theoretical value. Cm metal exhibits a localized moment
characteristic of rare earth metals and the heavier actinide metals
(starting at Am). Various magnetic measurements have been made on Cm
metal with 244cm and 248cm [45J. The values given vary widely, and
these measurements should be repeated. A transition to an
antiferromagnetic phase has been reported below 52 K [46J.
7. Conclusion
The magnetic properties of the elements Am and Cm, and their compounds
can be explained on the basis of the wavefunctions obtained from optical
spectra or from wavefunctions obtained from extrapolated parameters.
4+ .
For Cm data the experlmental data show an anomalous temperature
dependence. Further work is needed on these compounds. There is a
large scatter in the data for Cm metal, and this system should also be
reexamined.
8. Acknowledgements
I would like to thank M.M. Abraham and L. Boatner for allowing me to
quote their cm 3+ data before publication, and L. Soderholm and L.R.
Morss for helpful comments about the manuscript. This work was
supported by the Director, Office of Energy Research, Office of Basic
Energy Sciences, Chemical Sciences Divison of the U.S. Department of
Energy under Contract No. DE-AC03-76SF00098.
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DELOCALISATION OF 5f ELECTRONS IN AMERICIUM METAL
UNDER PRESSURE: RECENT RESULTS AND COMPARISON WITH
OTHER ACTINIDES
U.Benedict, J.P.ltie, C.Dufour, S.Dabos, J.C.Spirlet

Commission of the European Communities, Joint Research Centre
Karlsruhe Establishment, European Institute for Transuranium
Elements, Postfach 2266, D-7500 Karlsruhe 1, Federal Republic
of Germany
ABSTRACT. The high pressure behaviour of americium metal was re-

investigated by x-ray diffraction to 52 GPa. Phase Am III cannot be
indexed in the monoclinic structure assigned to it previously. The
resulting volumes are too large and would correspond to an expansion
of the lattice by an increasing-pressure phase transition. This contra-
diction is lifted when Am III is indexed as a trigonal distortion of
the cubic close packed Am II. A 6% volume decrease was observed on
transition from Am III to Am IV. These findings complete the systema-
tics of the high pressure transitions of the group of heavy actinide
metals Am to Cf.
INTRODUCTION
Locating americium metal in the actinide series means first discussing

the two main subgroups which are observed in the actinide metals. These
subgroups can be defined on the basis of the dualism between the loca-
lised and the itinerant configuration of the 5f electrons which con-
trols the solid state properties of these metals.
The first subgroup, protactinium to plutonium, has its 5f elec-
trons in an itinerant (delocalised) state. This means they are of
band type, hybridise with the conduction electrons and thus contribute
to the metallic bonding. Magnetic order, which in the lanthanide metals
is limited to the presence of localised 4f electrons, is consequently
not observed in this subgroup. The strengthening of the metallic bond
by the 5f participation leads to small atomic volumes (Fig.1), a high
cohesive energy and low compressibility (Fig.2). Low symmetry (ortho-
rhot'lbicand monoclinic) crystal structures are found whose formation
is probably related to the particular directional properties of the
hybridised orbitals which include a contribution from 5f electrons.
The second subgroup, americium to californium, is characterised
by localised 5 f electrons. In terms of electron energy, this means
that these electrons have sharp energy levels and do not contribute to
the metallic bond. In a spatial sense, it means that a particular 5f
213
N. M. Edelstein et at. (eds.), Americium and Curium Chemistry and Technology, 213-224.
214 U. BENEDICT ET AL.
30
25
20
Ac Th Po U Np Pu Am Cm Bk Cf Es
Fig.l - Atomic volume of actinide metals.
o
0...
~
-
o
m
100
~---
Ln
Ac Th Po U Np Pu AmCm Bk Cf Es
Fig.2 - Bulk moduli of the actinide metals,

compared to those of the lanthanide
metals.
DELOCALISATION OF 5fELECTRONS IN AMERICIUM METAL UNDER PRESSURE 215
electron is fixed ("localised") to a particular actinide atom. In

contrast to the first subgroup, the localised 5f electrons contribute
to the appearance of magnetic order in curium, berkelium and califor-
nium. The atomic volumes are larger (Fig.1), thus closer to those of
the trivalent lanthanide metals. The cohesive energies are in general
lower than those of the "itinerant" 5f metals.
The compressibilities are also of the same order as those of the
trivalent lanthanides (Fig.2). The crystal structure of the four metals
of the second subgroup is double-hexagonal close-packed (dhcp), thus
of relatively high symmetry.
THE EFFECT OF PRESSURE
The most remarkable effect of pressure on the actinide metals is that

due to closer contact between the lattice atoms, localised 5f electrons
can become itinerant, hybridise with the conduction electrons, anJ
participate in the metallic bond. The subgroup with localised 5f
electrons can thus under pressure acquire properties which, at ambient
pressure, are characteristic for the subgroup Pa to Pu. In the lighter
actinides the 5f electrons participate in the bond at normal pressure;
thus moderate pressure will not change their configuration and very
high pressures are required to induce structural changes by other
mechanisms.
In contrast with the lighter actinides, americium undergoes three
phase transitions in the pressure range below 25 GPa. One of these is
a consequence of the participation of the 5f electrons in bonding
owing to the effects of pressure in this metal. The behaviour of ame-
ricium under pressure is believed to be an important clue to the
understanding of the properties of actinides.
The results of x-ray diffraction studies of Am metal up to 18 GPa
were published in 1979-1982 by the Lawrence Livermore National Labo-
ratory (LLNL) and by the Los Alamos National Laboratory (LANL 1n
collaboration with the Oak Ridge National Laboratory (ORNL).
The two groups of researchers agree that with increasing pressure,
the dhcp phase (Am I) transforms to a cubic close-packed (ccp) phase
(Am II). But they give different structural descriptions for the low-
symmetry phases Am III and Am IV. Both the LANL and the LLNL groups
report a monoclinic structure for pressures between 10 and 15 GPa.
The LANL group assigned to this structure space group no. 11 (P21/m)
(1,2) but LLNL (3) proposed a c-centred structure with different lattice
parameters. Roof (4) showed that these two structures are related. A
similar situation exists for the allotrope described for the pressure
range 15-18 CPa. The LANL group reported it (5) to have a structure of
the a-U type. The data obtained by LLNL do not correspond to that
structure type but are similar to it (6).
A preliminary x-ray diffraction study of Am under pressure was
made in 1982 (17) using the energy-dispersive equipment of the
European Institute for Transuranium Elements in Karlsruhe, FRG (7).
Angular dispersive diffraction equipment with photographic film as the
detecting device had been used in the preceding studies at LLNL and
---
280 Am
---- -
111
260
~-
- ----
---- -
240
~
220
104
200
dhcp I ccp I 1lI IV
180
170
---
----
-----
160 ~
~
--
150
~
----
140 311~
~
130
0 10 20 30 40 50 p,GPa
Fig.3 Interplanar distances in americium metal as a function

of pressure. Miller indices hkl are indicated for the
dhcp and ccp phases.
DELOCALISATION OF 5f ELECTRONS IN AMERICIUM METAL UNDER PRESSURE 217
LANL. The Karlsruhe work yielded supplementary information, in part

confirming the results of the preceding investigations,but did not
yet allow definite conclusions on the structures of phases Am III and
Am IV to be drawn.
The volume of Am as a function of pressure has been calculated
using the atomic sphere approximation-LMTO (ASA-LMTO) method (8). If
the relativistic, not spinpolarised volume calculated by Brooks (9) is
employed for the lower limit of the volume collapse, which according
to these calculations should occur when the Sf electrons go itinerant,
a volume change of - 22% is obtained. None of the three above-mentioned
experimental investigations confirmed such an important volume change
upon formation of phases Am III or Am IV.
These differences between experimental results of different
authors, on one hand, and between calculated and experimentally ob-
served volume changes, on the other hand, led us to initiate further
study of americium metal under pressure. Another important aim of this
study was to obtain information on the structural behaviour of Am in
the range 18-50 GPa, for which no data had been previously reported
in the literature.
EXPERIMENTAL
The material studied was Am-243 containing 3.7% of Am-241. Am02 was
reduced by lanthanum metal, the Am metal formed was distilled off and
deposited on a tantalum surface. A second distillation was made to
purify the metal. Small particles were scratched from the deposit in
a pure argon atmosphere and loaded into a pressure cell of the Syassen-
Holzapfel type. Silicone oil was used as a pressure medium. The pres-
sure was determined by the ruby fluorescence method. Details of the
experimental method were previously described (7,10). No chemical
analysis could be carried out on the thin Am metal deposit. Material
prepared by the same method was found to have about 5000 ppma non-
metallic (mainly a and N) and about 140 ppma metallic impurities (11).
RESULTS
The variation of interplanar distances of Am with pressure is shown in

fig.3. This variation was studied up to 51.7 GPa. Diffraction spectra
at 41 different pressure steps could be obtained in a reasonable time
due to the use of the fast energy-dispersive, conical-slit method (7).
4 pressure ranges corresponding to 4 different crystallographic struc-
tures can be distinguished from this figure. The double-hexagonal
close-packed (dhcp) phase (Am I) is stable up to 9 GPa and transforms
at about 9.5 GPa to a cubic close packed structure (Am II). This in
turn transforms to Am III at about 13.5 GPa. Am IV forms at about
23 GPa and remains stable up to the highest pressure applied in this
experiment (51.7 GPa).
The relative volumes calculated from the d-spacings of Fig. 3 are
plotted vs. pressure in Fig. 4. No major volume change occurs when
the dhcp phase transforms to the ccp phase.

For Am III, the volumes were first calculated using the mono-
clinic indexing of Roof (2). The volumes thus obtained (dashed curve
in Fig. 4) are too large with respect to the volumes of the ccp phase,
indicating that this indexing cannot be 1l-pplied to our data. In
addition two of the strongest lines - (040) and (130) / (101) - of
the monoclinic phase reported by Roof were not observed in our dif-
fraction spectra.
Indexing Am III in the trigonally distorted ccp structure des-
cribed by Vohra et al. (12) for Pr and other lanthanide metals gives
a relatively good fit for line positions and intensities. The best
intensity fit is obtained for x = 0.5, y = 0.33, Z = 025. The volumes
based on this indexing (full curve for Am III in Fig.4) are approxi-
mately in line with those of the ccp phase. This supports the view that
Am III is indeed a trigonal distortion of the ccp structure, formed
from Am II in a second order phase transition.
The volumes of Am IV were calculated on the basis of the ortho-
rhombic a-uranium type structure which was reported for Am IV by
Roof et al. (5). Indexing in this structure must be considered as
provisional, because no line of our spectra could be fitted to hkl's
(021) and (002), which theoretically correspond to intense diffraction
lines. In addition, a shoulder on the high-d side of line (111), which
is observed in all spectra, does not find a correspondence in the
a-uranium structure. Further work will have to show whether another
structure gives a better fit to the present data. The volume decrease
on transition from the trigonally distorted ccp structure to Am IV
is approximately 6%. This volume decrease probably corresponds to the
onset of itinerancy of the Sf electrons.
By fitting the V (p) data for the dhcp phase with the Birch and
Murnaghan equations (7), a bulk modulus Bo of 45 (1) GPa and a pressure
derivative of B~ = 6 (1) were determined (Fig.5). These values repre-
sent averages between the data for the Birch fit (B 44.76, B~ = 6.1,
GB = 1.21) and for the Murnaghan fit (Bo = 45.14, B% = 5.6, GB = 1.24).
DISCUSSION
Significantly higher transition pressures were measured in this work,

compared with work by LLNL and LANL. To exclude any doubt, the tran-
sition pressure of NaCI was measured under identical conditions and
determined to be 31 + 1 GPa, which is in good agreement with the values
reported in literature. Good agreement was also observed between pres-
sures determined by the ruby fluorescence method and from the lattice
parameters of the NaCI sample using Decker's (18) equation of state.
The differences in transition pressures seem too large (8 GPa in
the case of the transition Am III - Am IV) to be accounted for by the
differences in impurity content which exist between the samples used
in the three independent investigations. But such differences in im-
purity content can explain why different groups of workers report
different crystallographic structures for the same pressure range. It
is likely that several low symmetry structures have quite similar
DELOCALISATlON OF Sf ELECTRONS IN AMERICIUM METAL UNDER PRESSURE 219
1.0
Am
(monoclinic)
~
~
~ ....
0.8 ccp ~.... ~ .......
disto~ ....
ccp ....... I!N/y_ S'I,
0.6
Am I IAm II I Am III Am IV
0.4
o 10 20 30 40 50 P. GPo
Fig.4 Relative volume of americium metal as a function of pressure.

1.00
VJv.o
*
*
0.95
*
*
0.90
0.85L---------------------------~--------------------------~
o 5 P, GPa 10
Fig.5 Fit of the Birch and Murnaghan equations to the

experimental data for dhcp Am I. B=45 GPa, B~ = 6.
The curve represents the (coincident) Birch and
Murnaghan equations.
DELOCALISATION OF 5fELECTRONS IN AMERICIUM METAL UNDER PRESSURE 221
30 -
28
a)
20
b)
15 c)
Am Cm Bk Cf
Fig. 6 Atomic volumes of Am, Cm, Bk and Cf.
a. at ambient pressure
b. ccp or distorted ccp phase at delocalisation pressure
c. a-U phase at delocalisation pressure
Volume decrease on delocalisation is indicated between

curves band c. (Volume in curve b taken as 100%).
thermodynamic stability, in a given pressure range, and that relatively

small changes in conditions, such as differing impurity content,
alternatively favor one or the other of these structures. Indications
for this type of behaviour also exist for cerium metal. An a-uranium -
type phase was reported as the main phase for Ce in the pressure range
5-12 GPa (13). Recent study, using cerium of different origin, did not
furnish clear evidence for the a-uranium type structure (a'Ce), but
revealed the existence of the monoclinic a'-Ce in the same pressure
range (14).
The data of fig.4 exclude a major volume collapse as it was ex-
pected from theoretical considerations, and in this respect confirm
the previous experimental work. It must be kept in mind that the theo-
retical calculations which predicted an important volume decrease on
beginning itinerancy (8,9) were made for T = O. The example of pluto-
nium shows that the atomic volume varies considerably with temperature
in such calculations. A correct comparison could thus only be made to
calculations for room temperature (15). The present results also
indicate that the itinerancy of 5f electrons in Am sets in at 23 GPa,
a pressure much higher than that predicted from theoretical calcula-
tions (8).
The results obtained allow us to complete the systematics
established in previous work on Cm (16,19), Bk (20,21) and Cf (20,22)
for the pressure behaviour of this group of heavy actinides.
The transition pressures of Am, Cm, Bk and Cf are compared in
Table 1. The transition pressures increase in
Table 1. Transition pressures of actinide metals which

have localised 5f electrons at ambient pressure (16,19-22)
Am Cm Bk Cf
dhcp_ ccp 9.5 23 9-10 17
ccp
- distorted ccp
onset of itinerancy
13.5
23 43 32
ru 30
41
principle with increasing 5f occupation. Curium is an exception,

having higher transition pressures than the other three metals. The
high spin polarisation energy of curium (5f7) possibly contributes to
the fact that particularly high pressures are needed to delocalise the
5f electrons in this metal. But the reasons for curium to transform
from dhcp to ccp at considerably higher pressures than its neighbours
of lower and higher Z are not clear (16).
Fig. 6 compares the atomic volumes of the four metals at different
pressures. Curves band c give the volume immediately before and imme-
diately after the onset of itinerancy. Curve a,volume at ambient pres-
sure,has a maximum at curium. This maximum corresponds to a minimum in 5f
DELOCALISATION OF 51' ELECTRONS IN AMERICIUM METAL UNDER PRESSURE 223
participation in the metallic bonding, curium having the most

stable localised configuration among the actinide metals. It is
seen that in the itinerant configuration (curve c) the maximum is
at americium, re-establishing the trend of volumes decreasing with
increasing Z ("actinide contraction").
The absolute volume of Am in the assumed a-uranium type structure
at 46 GPa is 17.6 . 10-3 nm 3 • A volume of ~ 18.10-3 nm 3 was recently
estimated by Johansson (15) for Am at 46 GPa.
LITERATURE CITED
1. Roof R.B., Z. Kristallographie 1982 (158) 307-312.
2. Roof R.B., J. Appl. Crystallography 1981 (14) 447-450.

3. Smith G.S., Akella J., Reichlin R., Johnson Q.,
Schock R.N., Schwab M., Actinides 81, Asilomar, CA,
September 1981.
4. Roof R.B., 1982, personal communication.
5. Roof R.B., Haire R.G., Schiferl D., Schwalbe L.A.

Kmetko E.A., Smith J.L., Science 1980 (207) 1353-1355.
6. Akella J., 1982, personal communication.
7. Benedict U., Dufour C., High Temp., High Press, 1984,

in press.
8. Johansson B., Skriver H.L., Andersen O.K., in Schilling

J.S. and Shelton R.N., eds., Physics of Solids under
High Pressure, North-Holland, Amsterdam, 1981, pp.245-262.
9. Brooks M.S.S., J. Phys. F., 1983 ~ 103-108.
10. Bellussi G., Benedict U., Holzapfel W.B., J. Less-Common

Metals 1981 (78) 147-153.
11. Spirlet J.C., in "Actinides in Perspective", Edelstein N.,

ed., Pergamon 1982, pp. 361-380.
12. Vohra Y.K., Vijayakumar V., Godwal B.K., Sikka S.K.,

submitted to Phys. Rev. B., 1984.
13. Zachariasen W.H., Ellinger F.H., Acta Cryst. 1977, (A33)

155-160.
14. Benedict U., Gerward L., Staun Olsen J., Acta Cryst. 1984,
(A 40) C-413.
15. Johansson B., J. Magn. Magn. Mat., 1984, in press.
16. Benedict U., Haire R.G., Peterson J.R., ltie J.P.,

J. Phys. F.: Metal Phys. 1985 (15) 29-35
17. Peterson J.R., Haire R.G., Benedict U., Spirlet J.C.,

Dufour C., Birkel I., Asprey L.B., p. 9 of: Rep. Workshop
"Actinides under Pressure", Karlsruhe, April 21-22, 1983,
Eur. lnst. Transuranium Elements Karlsruhe.
18. Decker D.L., J. Appl. Phys. 1971 ~ 3239-3244
19. Haire R.G., Benedict U., Peterson J.R., Dufour C.,

ltie J.P., J.Less-Common Metals, submitted.
20. Benedict U., Peterson J.R., Haire R.G., Dufour C.,

J. Phys. F: Metal Phys. 1984 (14) L43-L47
21. Haire R.G., Peterson J.R., Benedict U., Dufour C.,

J. Less-Common Metals 1984 (102) 119-126
22. Peterson J.R., Benedict U., Dufour C., Birkel I., Haire R.G.,
J. Less-Common Metals 1983 (93) 353-356.
PREPARATION, CHARACTERIZATION AND SOLUBILITY PRODUCT CONSTANT OF AmOHC03
Robert J. Silva*
Lawrence Livermore National Laboratory
P.O. Box 808
Livermore, CA 94550
USA
ABSTRACT. An investigation into the nature and solubility of a

stable solid phase formed by a trivalent actinide, 243Am 3+, in dilute
aqueous carbonate solutions was conducted. The compound exhibited an
x-ray powder diffraction pattern which was nearly identical to that
reported for NdOHC03 - type A. The pattern could be indexed in the
orthorhombic s¥stem with unit cell parameters a = 4.958, b = 8.487,
and c = 7.215 A. The steady state solubility of the compound was
determined from the results of both dissolution and precipitation
experiments. The average solubility product quotient for 0.1~1
ionic strength, 25 ~ 1°C and 1 atmosphere pressure was found to be
583 + 206. The solubility product constant for zero ionic strength
was estimated to be 335 + 120.
1. INTRODUCTION
Computer calculations indicate that the actinides U-Am will be the

major contributors to the radioactivity of high-level nuclear waste
after storage periods of several hundred years or longer [1, 21, the
design criteria for the lifetime of the metal canisters [31. In the
event that the waste packages fail to contain the radioactive materials,
they will enter the local groundwater system and, if moving, the ground-
water is expected to provide the most likely mechanism by which the
radionuclides could be transported. from an underground storage facility
to the accessible environment [41. The actinides can react with various
components in the altered groundwater to form insoluble phases that
can control their solution concentrations and, thus, their migration
rates. The exact nature of the solid phases will depend on a number
of factors, e.g., the composition and redox properties of the ground-
water system and the oxidation states of the actinides. Therefore, a
knowledge of the nature and solubilities of actinide compounds that
could form in groundwater is one of the pieces of information that is
needed to predict migration rates.
225
226 R. J. SILVA
Thermodynamic data on trivalent lanthanide elements [5], good

analogs for actinides in the 3+ state [6], suggest that carbonate
compounds of the latter may be quite insoluble in carbonate bearing
groundwaters; however, no thermodynamic data have been reported. The
object of this work was to investigate the nature and solubilities of
compounds of a trivalent actinide, Z43 Am 3+, in an aqueous carbonate
system.
Z. EXPERIMENTAL PROCEDURES
Z.l. Preparation and Characterization of Solid Phase
The preparation of rare-earth carbonates via the formation and sub-

sequent hydrolysis of the trichloroacetate complex in aqueous solution
is a well established method for producing a pure, easily filterable
and crystalline material [7, 8]. The exact nature of the rare-earth
carbonate depends on the atomic number of the rare earth and is quite
sensitive to the preparative conditions, e.g., temperature, COZ
pressure and the washing procedure. The octahydrate, RZ(C03)3,8HZO,
is usually formed by the first members of the rare-earth series, e.g.,
La, while the dihydrate, RZ(C03)·ZHZO, is usually formed by the middle
and end members of the series, e.g., Nd-Yb [9]. Charles has also
reported that, even using the same procedures and conditions, some
rare earths form the dihydrate, e.g., Nd, while others form the basic
carbonate, ROHC03, e.g., Pr [10]. The compounds are, however, usually
pure. Because of these complications, it seemed prudent to first test
the preparative method and the stability of the resulting solid phase
with neodymium, a good analog element for americium.
Approximately 10 mgs of neodymium carbonate were prepared by the
trichloroacetate method. An x-ray powder diffraction pattern of the
material was obtained with a Debye-Scherrer camera using CuKa radiation
(A = 1.5418 A) and a Ni filter. The d-spacings and relative intensities
derived from the powder pattern are given in Table I under Nd Solid (I).
Head and Holley have investigated the preparation and thermal decompo-
sition of the rare-earth dihydrates [8, 9]. These elements were stated
to form dihydrates that were isostructural and that had similar x-ray
powder diffraction patterns. Unfortunately, these patterns were not
published. However, an original x-ray film containing the powder
diffraction pattern of the NdZ(C03)3,ZHZO (assigned from the results
of chemical analysis) was recently obtained from C. E. Holley of LANL
and analyzed. The d-spacings and relative intensities are given
in Table I. Our material appeared to be pure, microcrystalline
Nd2(C03)3,ZHZO.
The NdZ(C03)3' ZHZO solid was placed in a polypropylene cell
containing an aqueous solution composed of 0.1~ NaCI0 4 and Zxl0-4~ HC0 3
at a pH of 6.12. After a contact time of three weeks, an x-ray powder
diffraction pattern was again obtained on the solid. The resulting
powder pattern is given in Table I under Nd Solid (II). The pattern
was distinctly different from that of the Nd Solid (I) but nearly
identical to the powder pattern reported for NdOHC03 - Type A [11],
;l>
a::t"O
TABLE I. X-RAY POWDER DIFFRACTION PATTERNS OF Nd SOLID PHASES ~
n
E
Nd2(C03)3'2H20 Nd Solid (1) NdOHCO/ Nd Solid (II)
a::
:r:
d(A) Ib d(A) Ib d(A) IC d(A) Ib -<
0
~
0
~
7.563 70 7.694 70 5.500 30 5.500 25 -<
n
;l>
5.680 85 5.800 85 4.280 100 4.283 100 ~
til
4.665 100 4.726 100 4.235 15 0
Z
3.934 85 3.991 85 3.675 35 3.673 50 ...,;l>
t"O
3.834 25 3.875 25 3.650 25
3.615 50 3.659 70 3.315 35 3.308 25
3.092 25 3.129 25 2.940 25
3.015 85 3.046 85 2.910 50 2.921 50
2.976 10 2.748 3
2.873 10 2.630 30 2.634 25
2.751 25 2.767 25 2.475 25 2.482 25
2.582 70 2.607 50 2.400 10 2.404 10
2.249 10 2.323 40 2.324 50
2.170 10 2.310 18
2.082 10 2.138 7
2.016 50 2.031 35 2.122 9
1.982 25 1.994 25 2.097 1
1.872 35 1.882 35 2.050 40 2.050 35
1.825 35 1.835 35 2.030 13
1.779 35 1.789 35 1.984 40 1.988 35
1. 737 25 1. 745 35 1.925 25 1.929 10
1.562 35 1.566 25 1.880 10 1.885 10
1.830 19 1.828 25
(a) Reference 11; (b) relative intensities visually estimated; (c) relative intensities by diffractometer.
N
N
-.J
228 R. J. SILVA
There was no longer any evidence in the pattern for Nd2(C03)3"2H20.

The starting material had converted to the basic carbonate during the
three week contact time.
An attempt was· made to prepare Am2(C03)3"2H20 by the same procedure
as was used to prepare the Nd2(C03)3"2H20. However, the x-ray powder
diffraction pattern of the resulting Am compound was very similar to
that of the NdOHC03 and not Nd2(C03)3"2H20. The preparation of the
solid was repeated with the Am, and the x-ray diffraction analysis
of the solid gave a pattern again similar to the Nd basic carbonate.
The d-spacings and relative intensities obtained from the pattern are
given in Table II under Am Solid (I). Since the results with Nd sug-
gested that the basic carbonate is more stable than the dihydrate
in our aqueous carbonate system, no further attempts were made to
produce the normal carbonate of Am.
2.2. Solubility Measurements
The solubility studies with trivalent amerlClum were conducted in two

parts. The first involved following to steady state the concentration
of Am in a solution initially free of the element, i.e., undersaturation
with respect to precipitation, but which had been placed in contact with
the solid phase AmOHC03' The second involved following to steady state
the concentration of Am in a solution initially supersaturated in Am
with respect to the precipitation of a solid phase but with no solid
initially present. Much of the equipment and techniques used in these
measurements have been described elsewhere [12].
In order to obtain a reliable value for the solubility product
quotient for the reaction,
the pH range available for measuring the solubility was somewhat

limited. It was necessary to hold the pH to less than about 6.5 to
avoid significant hydrolysis of the Am3+ ion but greater than about
5 to avoid possible dissolution of all of the available starting solid
(8 mgs). In addition, the C0 3 2- concentration was set sufficiently
low so as to avoid significant carbonate complexation of the Am3+ ion,
i.e., ~10-8M. A pH of 6.12 was selected as it is within a reasonably
well buffer;d region where the concentrations of H2C0 3 and HC0 3- are
equal. A computer controlled pH-stat was used to maintain a pH near
this value. The bicarbonate, and thus carbonate, ion concentration
was fixed by maintaining a gas mixture of 0.792 ~ .010% C02 and 99.3%
Ar over the aqueous phase. The equilibrium concentrations of bicar-
bonate and carbonate ions in the aqueous phase under these conditions
were calculated to be 2.05xl0- 4M and 2.25xl0- 8M, respectively, using
reported carbonate equilibrium quotients for O:IM ionic strength [13,
14]. To fix the ionic strength, an aqueous solution of O.lM NaC104
was used as supporting electrolyte. Two titrations of 50 mls of the
aqueous phase at a starting pH value of 6.14 with O.100M HCl to the
end point of the HC0 3- to H2C0 3 conversion were made prIor to the
initiation of the solubility experiments. From the results, the
;I>
TABLE II. X-RAY POWDER DIFFRACTION PATTERNS OF AMERICIUM SOLID PHASES s::
m
:;tl
Pi
Am Solid ill Am Solid (II) Am Solid (Ill) Average (I, II, Ill) Calculated 2
s::
d(A) Ia d(A) 18 d(A) 18 d(A) d(A) hkl :I:
-<
t1
:;tl
0
5.500 25 5.503 25 5.505 25 5.503+0.003 5.497 011 ;><
- -<
n
4.283 100 4.279 100 4.281 100 4.281+0.002 4.281 110 ;I>
:;tl
to
3.673 50 3.671 50 3.666 50 3.670+0.004 3.682 111 0
Z
;I>
3.658 021 >-l
m
3.308 25 3.314 35 3.326 35 3.316+0.009 3.320 012
2.942 25 2.9«3 121
2.921 50 2.919 50 2.912 50 2.917+0.005 2.917 102
2.634 25 2.636 25 2.635 25 2.635+0.001 2.634 031
2.482 25 2.480 25 2.475 25 2.479+0.004 2.479 200
2.398 10 2.402 10 2.406 25 2.402+0.004 2.404 122
2.324 50 2.335 35 2.331 50 2.330:+:.0 •006 2.326 131
2.322 10 2.314 013
2.134 10 2.132 25 2.133+0.002 2.141 220
2.050 35 2.054 35 2.051 50 2.052+0.002 2.052 221
1.988 35 1.986 25 1.985 25 1.986+0.002 1.986 212
1.929 10 1.929 25 1.924 25 1.927+0.003 1.928 123
1.885 10 1.889 10 1.887+0.003 1.883 141
1.828 25 1.835 10 I. 832+0.005 1.832 033
(a) Relative intensi~ies visually estimated. tv

tv
""
230 R. J. SILVA
bicarbonate ion concentration was calculated to be 2.67 + .16x10- 4M.

This value is_kn reasonable agreement with the concentration of
2.15 + .17x10 M calculated for the CO 2 partial pressure in the gas
mixture at this pH.
2.3. Solubility Measurements from Unsaturation
Approximately 8 mgs of the crystalline AmOHC03, Am SO.lid (I), were

placed in a polypropylene cell with 50 mls of the aqueous phase at
25 + 1°C and 1 atmosphere pressure. Two 1 ml aliquots of the aqueous
phase were taken after 1, 3, 7, 14, 21, and 30 days equilibration time.
After centrifugation at 15,000 RPM for 15 minutes, the Am concentra-
tions were determined from the results of liquid scintillation counting
of the supernates. The beta-emitting daughter 239Np, was found not
to be in nuclear decay equilibrium with the 243Am in solution at the
times of sampling. Because the 239Np added to the measured total count
rates of the aliquots, the samples required counting periodically for
3-4 weeks to allow secular equilibrium to be established so the
appropriate counting corrections for the Np could be made.
At the end of the 30-day period, two additional 5 ml aliquots of
the aqueous phase were taken. After centrifugation, the aliquots were
split into two fractions. One fraction, 2 mIs, was passed through a
a 0.2~m acrodisc polysulfone filter while the other fraction, 3 mIs,
was passed through a 0.015~m Nuclepore polycarbonate filter. The
first one-half of the fraction through the filters was discarded and
a measured portion of the remaining filtrate analyzed for Am by liquid
scintillation counting.
Also, at the end of the 30 day period, the solid phase remaining
in the cell was subjected to x-ray diffraction analysis. The results
obtained from the powder pattern are given in Table II under Am
Solid (II). The powder pattern was identical to that of the starting
material, Am Solid (I). There was no change in the solid phase during
these dissolution measurements.
2.4. Solubility Measurements from Supersaturation
At the conclusion of the first part of the studies described above, the
aqueous phase in the cell was made 0.1~ in HCl04 to dissolve the solid
AmOHC03. The volume of the aqueous phase was adjusted to 50 mls by the
addition of water and solutions of NaHC03 and NaOH in ~gch a manner as
to again produce an aqueous phase 0.1~ in NaCl0 4 , 2x10 ~ in HC0 3 and
at a pH of 6.12. The remainder of the experiment proceeded as in the
first part of these studies.
Aliquots of the aqueous phase were taken after 1, 3, 7, 14, 22, 31,
37, 44 and 51 days equilibration time in order to follow the Am solution
concentration to steady state. At the 51 day period, in addition to
separation of phases by centrifugation, aliquots were filtered as
before. At this time, the solid phase that had precipitated was sub-
jected to x-ray diffraction analysis. The information obtained from
the powder pattern is given in Table II under Am Solid (III). The
powder pattern was identical to that of Am Solid (I) and Am Solid (II).
AMERICIUM HYDROXYCARBONATF 231
3. RESULTS
3.1. Crystal Data
The corresponding d-va1ues obtained from the x-ray powder diffraction

patterns of the three solids, Am Solid I, II and III, were least square
averaged; the results are given in Table II. Guided by the work on
NdOHC03 type A [Ill, the averaged values could be indexed in the orthor-
hombic system with the unit cell parameters a = 4.958, b = 8.487 and
c = 7.215A. The calculated d-va1ues and Miller indices are also given
in Table II. The values of the parameters agree to within two decimal
places with those given for NdOHC03 - type A [Ill. Thus, the Am solid
was identified as AmOHC03 and it is isostructura1 with NdOHC03 - type A.
3.2. Solubility from Undersaturation
The results of the measurements of the solubility of the crystalline

AmOHC03 are given in Table III. The pH values given are the average
values observed during each equilibration period. The errors in the
pH values were estimated from the inherent reproducibility of measure-
ments with the pH meter and electrodes, both on the dissolver solution
and buffers, and from the root mean square deviations of pH values
(measured every two hours) from the averages. No corrections were
made for liquid junction potential differences.
The values and errors assigned to the Am solution concentrations
are the average and deviations from the average of the two a1iquots
taken at each sampling period. The values of the bicarbonate concen-
trations were calculated from the partial pressure of C02 over the
aqueous phase, i.e., 0.00792 ~ .0004 atmospheres and the average pH
value during the period.
Since the Am solution concentrations did not vary appreciably
after the 7 day equilibration time, it was assumed that steady state
had been achieved in the dissolution reaction. Some variation in the
Am concentrations between equilibration times is due to differences
in the pH. The Am concentrations of the solutions passed through the
two different pore size filters at the 30 day period agreed to within
experimental error. However, these values are only about 65% of the
Am concentration of the centrifuged sample. Whether this difference
was due to insufficient separation of solid and aqueous phases by our
centrifugation system or due to loss of Am via absorption of soluble
species by the filters was not determined. Since the source of this
discrepancy was not known, the three values were given equal weight in
subsequent data analysis.
3.3. Solubility from Supersaturation
The results of the measurements of the solution concentrations of Am

as a function of equilibrium time during the precipitation of AmOHC03
are given in Table IV. The values for the average pH, the Am concentra-
tions and bicarbonate concentrations and their associated errors were
obtained as described in the previous section.
w
'"
'"
TABLE III. RESULTS OF SOLUBILITY MEASUREMENTS BY DISSOLUTION OF AmOHC03'
EquU. Time pH Cone. Am Cone. flC03 Sol. Prod. log Qsp

(days) (moles/I) (moles/I) Quat., Qsp
6.13+.03 2.86+.25xI0- 5 2.09+.18xlO-4 6.32+.IOx10 3 3.80±..06
3 6.13+.03 1.19+.04xI0- 5 2.09+.18xI0- 4 2.63+.36xI0 3 3.42+.06
6.15+.03 2.17+.54xI0- 6 2 .19±.. 19x10-4 5.51±.1.56x0 2 2.74+.11
14 6.13+.03 2.39+.2IxI0- 6 2.09+.18xlO-4 5.28+.85xI0 2 2.72+.06
21 6.14+.03 2.02+.04xI0- 6 2.14±..19xI0-4 4.79+.65xI0 2 2.68+.06
30 6.14±..03 2.29±..03xI0- 6 (a) 2.14+.19xI0- 4 5.43+.73xI0 2 2.73+.06
1.54±..13xI0-6(b) 3.65+.58x10 2 2.56+.06
I. 40±..13xl 0-6( c) 3.32+.55xI0 2 2.52+.07
(a) Centrifugation; (b) centrifugation plus 0.2 ~m filtration; (c) centrifugation plus 0.015~ filtration.
1"
~
Vl
~
;..
;J>
E::
t'1
TABLE IV. RESULT OF SOLUBILITY MEASUREMENTS BY PRIlCIPITATION OF AmOHC03' ~
n
2
Ilquil. Time pH Cone. Am Cone. HC03 Sol. Prod. log Qsp E::
( days) (moles/l) (moles/I) Quat., Qsp :r:
-<
0
~
0
0 .009 6.61+.21x10- 4 ><
-<
()
;J>
~
6.09.:t. 03 3.66+.13x10- 4 1.91.:t.17x10-4 6.14+.82x10 4 4.79+.06 0;
0
Z
;J>
3 6.11+.03 3.15+.05x10- 4 2.00+.18x10-4 6.07+.82x10 4 4.78+.06
...,
t'1
7 6.12+.03 3.56+. 13x1 0-4 2.05.:t.18x10-4 7.35+l.02x10 4 4.87+.06
14 6.10+.03 7.86+1.67x10- 5 1.95.:t.17x10-4 1.41+.35x104 4.15+.10
22 6.13+.03 7.67+.72x10- 6 2.09+.18x10-4 1.70+.28x10 3 3.23+.07
31 6.14+.03 3.21+.14x10-6 2.14+.19x10- 4 7.60+1.07x10 2 2.88+.06
37 6.13+.03 4.42+.17x10- 6 2.09+.18x10-4 9.77+1.36x10 2 2.99+.06
44 6.13+.03 4.71+.30x10- 6 2.09+.18x10-4 1.04+.15x10 3 3.02+.06
51 6.11+.03 4.88.:t.11x10-6(a) 2.00+.18x10- 4 9.40+l.33x10 2 2.97+.06
3.65.:t.06x10-6(b) 7.03+.95x10 2 2.85+.06
3.2D±.32x10-6 (c) 6.16+l.03x10 2 2.79+.07
(a) Centrifugation; (b) centrifugation plus 0.2 um filtration; (c) centrifugation plus 0.015 um filtration.
w
'"
w
234 R. J. SILVA
As can be seen in Table IV, the Am concentrations decreased during the

first month of the measurements but then remained relatively constant
for the following 20 days. Therefore, it was assumed that steady state
had been achieved.
As in the dissolution experiments, the Am concentrations measured
for the filtered samples at the 51 day equilibration time agreed
reasonably well but were only about 60% of the value measured for
the centrifuged sample. The three values were given equal weight in
subsequent data analysis.
3.4. Evaluation of the Solubility Product Quotient and Constant
Solubility product quotients, Qsp' were calculated from the measured

concentrations given in Table III and IV for the following reaction
(1)
The concentrations of hydrogen ion were derived from the measured pH

values using an activity coefficient of 0.78. This value was estimated
from trends in mean activity coefficients for 0.1~ HCl [15], 0.1~ HCl04
[15] and HCl in O.IM NaCl [16].
Since the Am 3+ ion can undergo a small amount of hydrolysis and
carbonate complexation under the solution conditions of the experiment,
estimates of the degree of these reactions were made. The first hy-
drolysis constant for Am 3+ has not been measured in a noncomplexing
medium at O.IM ionic strength; however a log value of -7.7 + 0.3 has
been reported-for Cm 3+ [17]. Since An3+ and Cm 3+ are adjacent actinides
of similar ionic radii, that of Am being slightly larger, a value of
-7.8 + 0.3 was assumed for Am3+. From this quotient, the AmOH2+ to Am 3+
concentration ratio for a pH of 6.12 was calculated to be 0.016 + 0.012.
A log value of 5.81 + 0.04 has been reported for the formation
constant, 6
1, of the first carbonate complex of Am 3+ in 1~ NaCl0 4 [18].
Unfortunate y there are no data on mean activity coefficients of
appropriate Am salts in mixed electrolyte systems which could be used
to correct the quotients obtained in 1~ NaCl04 to 0.1~ NaCl04. As
the next best approximation, it was decided to use mean activity coef-
ficients of LaC13-HCl mixtures that have been measured experimentally
[1"9]. The mean activity coefficient for appropriate carbonate species
in a mixed electrolyte were estimated using Pitzer's equations [201.
Ion interaction parameters used in the calculations for carbonate
species [21] and NaCl04 [22] are reported in the literature. The
single ion activity coefficient for AmC0 3+ was taken to be equal to
that of Na+. The resulting estimate for log ~1(0.1~) was 6.1L ~ 0.04.
This quotient leads to a value of 0.027 ~ 0.003 for the AmC0 3 to
Am3+ concentration ratio.
From the above ratios, the concentration of free Am3+ was calcu-
lated as 95.9 + 1.3% of the measured Am in solution. The total Am
solution concentrations given in Tables III and IV were reduced by
this percentage before calculation of the Qsp's given in the tables.
AMERICIUM HYDROXYCARBONATE 235
The Qsp values calculated from the data obtained by the three
different solid-solution separation schemes at the 30-day equilibration
time for the dissolution experiment and the 51-day equilibration time
for the precipitation experiment were averaged by the least squares
method. The resulting mean and standard deviation of the solubility
product quotient for O.lM ionic strength was 583 + 206. Estimates for
the activity coefficient~ of Am 3+, HC0 3 - and H+ at 0.1~ ionic strength
were used to obtain an approximate value for the solubility product
constant, Ksp, at zero ionic strength from the solubility product
quotient given in the preceeding paragraph. The sources of the
estimated activity coefficients were given prev~~usly i~ this ~aper.
Values of 0.46, 0.76, and 0.78 were used for Am , HC0 3 and H ,
respectively. The resultant value for Ksp was 335 + 120.
4. CONCLUSIONS
The basic carbonate of amer~c~um, AmOHC03, was found to be a stable

solid phase in dilute aqueous carbonate solutions at near neutral pH.
The compound is isostructural with NdOHC03 - type A and its x-ray
diffraction pattern can be indexed in the orthorhombic system. The
solubility product quotient for O.lM ionic strength, 25 + 1°C and 1
atmosphere pressure was found to be-583 + 206. The solubility product
constant for zero ionic strength was estimated to be 335 + 120.
5. ACKNOWLEDGEMENTS
The author wishes to thank C. E. Holley, Jr., of the Los Alamos

National Laboratory for making available the x-ray film of the
powder diffraction pattern of Nd2(C03)3·2H20. The help of A. Zalkin
of the Lawrence Berkeley Laboratory in the interpretation of powder
patterns is gratefully acknowledged. Thanks are due J. J. Bucher (LBL)
for helpful advise on estimating activity coefficients and H. Nitsche
(LBL) for calculations involving Pitzer's equations. This work
was supported by the office of Nuclear Regulatory Research, U.S.
Nuclear Regulatory Commission, while the author was employed by the
Lawrence Berkeley Laboratory.
*Work supported by the Division of Health, Siting and Waste Management,

Office of Nuclear Regulatory Research, U.S. Nuclear Regulatory
Commission under contract FIN No. B 3040-0 at Lawrence Berkeley
Laboratory, and by the U.S. Department of Energy under Contract
No. W-740S-Eng-48 at the Lawrence Livermore National Laboratory.
236 R. J. SILVA
6. REFERENCES
1. Little, A. D., 1977. Technical Support of Standards for High-

Level Waste Management, Vol. A, Source Term Characterization.
EPA Report 520/4-79-007A. United States Environmental
Protection Agency, Office of Nuclear Waste Isolation,
Washington D.C., 20460
2. NRC, 1983. Staff Analysis of Public Comments on Proposed Rule

10CFR Part 60, Disposal of High-Level Radioactive Wastes in
Geologic Repositories. U.S. Nuclear Regulatory Commission
Report, NUREG-0804, Washington, D.C., p. 467.
3. U.S. Nuclear Regulatory Commission, 1983. 10CFR Part 60, Disposal

of High-Level Radioactive Wastes in Geologic Repositories,
Technical Criteria. Section 60.113, Performance of Particular
Barriers after Permanent Closure, Federal Register, Vol. 48
(No. 120), p. 28224. --
4. Klingsberg, C., and J. Duguid, 1980. Status of Technology for

Isolating High-Level Radioactive Wastes in Geologic
Repositories, DOE/TIC-11207, U.S. Department of Energy,
Washington D.C., p. 15.
5. Smith, R. M., and A. E. Martell, 1976. Critical Stability Constants,

Vol. i, Inorganic Complexes, Plenum Press, New York, p. 37.
6. Kutz, J. J. and G. T. Seaborg, 1957. The Chemistry of the Actinide

Elements, Wiley and Sons, New York, p. 406-475.
7. Salutsky, H. L., and L. L. Quill, 1950. 'The Rare-Earth Metals and

their Compounds. XII. Carbonates of Lanthanum, Neodymium and
Samarium', J. Amer. Chem. Soc., ~ p. 3306-3307.
8. Head, E. L., and C. E. Holley, Jr., 1963. 'The Preparation and

Thermal Decomposition of Some Rare-Earth Carbonates'. Rare-
Earth Research III, Gordon and Breach, N.Y. pp. 51-63.
9. Head, E. L., and C. E. Holley, Jr., 1964. 'The Preparation and

Thermal Decomposition of the Carbonate of Tb, Dy, Ho, Er, Tm,
Yb, Lu, Y and Sc.', Rare-Earth Research IV, Gordon and Breach,
N.Y., pp. 707-718.
10. Charles, R. G., 1965. 'Rare-Earth Carbonates Prepared by Homo-

geneous Precipitation', J. Inorg. Nuclear Chemistry, ~
pp. 1489-1493.
11. Dexpert, H. and P. Caro, 1974. 'Determination de la Structure

Crystalline de la Variete a des Hydroxycarbonates de Terres
Rares LnOHC03', Mat. Res. Bull., ~ pp. 1577-1586.
AMERICIUM HYDROXYCARBONATE 237
12. Silva, R. J., and A. W. Yee, 1982. Geochemical Assessment of

Nuclear Waste Isolation, 'Testing of Methods for the
Separation of Solid and Aqueous Phases - a Topical
Report', NUREG/LBL-14696, Lawrence Berkeley Laboratory,
Berkeley, CA.
13. Harned, H. S. and R. Davis, Jr., 1943, 'The Ionization Constant of

Carbonic Acid in Water and the Solubility of Carbon Dioxide in
Water and Aqueous Salt Solutions from 0 to 50°'. J. Am. Chern.
Soc., 65, pp. 2030-2037.
14. Phillips, S. L., 1982. Hydrolysis and Formation Constants at 25°C.

Lawrence Berkeley Laboratory report LBL-14313, Berkeley, CA,
p. 50.
15. Robinson, R. A. and R. H. Stokes, 1959. Electrolyte Solutions,

Appendix 8.10, Butterworth, London, pp. 491-492.
16. Harned, H. S. and B. B. Owen, 1958. The Physical Chemistry of

Electrolyte Solutions. Table 14-2-1A, Reinhold, N.Y., p. 748.
17. Edelstein, N. J. Bucher, R. Silva, and H. Nitsche, 1982.

Thermodynamic Properties of Chemical Species in Nuclear Waste:
Topical Report. ONWI/LBL-14325, Office of Nuclear Waste
Isolation, Battelle Memorial Institute, Columbus, Ohio, p. 50.
18. Lundquist, R., 1982. 'Hydrophilic Complexes of the Actinides. I.

Carbonates of Trivalent Americium and Europium', Acta Chern.
Scand., A36, p. 741-750.
19. Khoo, K. H., T. K. Lim and C. Y. Chan, 1981. 'Activity

Coefficients in Aqueous Mixtures of Hydrochloric Acid and
Lanthanum Chloride at 25°C'. J. Sol. Chern., 10, pp. 683-691.
20. Pitzer, K. S., 1973. 'Thermodynamics of Electrolytes. I.

Theoretical Basis and General Equations'. J. Phys. Chern., 77
(No.2), pp. 268-277.
21. Pitzer, K. S., and G. Mayorga. 1973. 'Thermodynamics of

Electrolytes. II. Activity and Osmotic Coefficients for
Strong Electrolytes With One or Both Ions Univalent',
J. Phys. Chern., 77 (No. 19), pp. 2300-2308.
22. Peiper, J. L. and K. S. Pitzer, 1982. 'Thermodynamics of Aqueous

Carbonate Solutions Including Mixtures of Sodium Carbonate,
Bicarbonate and Chloride', J. Chern. Thermodynamics, ~
pp. 613-638.
238 R. J. SILVA
IlISCLAI\IER
This document "3-' prepared as an account of \,\ork ."ipon<t;ored h.\' an agency of

the lnited States Go>ernment. :"either the lnited States Go,ernment nor the
LniH~rsity of California nor any of their emplo}'ees. makes any "arrant}. t':\-
press or implied. or assumes an}' legal liability or re~ponsibility for the ac-
curacy, completeness, or usefulness of an} information, apparatus. product, or
process disclosed, or represents that its use \\ould not infringe prhately fmned
rights. Reference herein to any specific commercial products. process. or sen ice
by trade name, trademark, manufacturer, or othen\-ise, doe~ not necessaril}
constitute or imply its endor~emcnt, recommendation, or fa"oring h}' the l 'nited
States GOlernment or the l' nhersity of California. The" iew'" and opinions of
authors expressed herein do not nece"arily state or reflect those of the l"nited
States Government thereof, and shall not he used for advertising or product en-
dorsement purposes.
Part IV
Nuclear Studies, Environmental Studies, Separations,

and Other Technological Aspects
HEAVY ION REACTIONS ON CURIUM TARGETS
Darleane C. Hoffman
Berkeley, California
Abstract: The availability of relatively large quant1t1es of curium

isotopes has made them available as targets for both the preparation
of new elements (californium from curium-242 and nobelium from
curium-246) and for heavy ion reactions to make new neutron-rich
isotopes for study. In addition, curium-248 has been used as a target
in a wide variety of attempts to make superheavy elements. The
availability of such target materials is a tribute to Professor Glenn
Seaborg's vision in establishing the Transplutonium Production Program
in the early 1960's when he was Chairman of the U. S. Atomic Energy
Commission. Some recent results of heavy ion experiments with
curium-248 will be discussed briefly.
The availability of relatively large quant1t1es of curium isotopes

has made it possible to use them as target materials, both for the
synthesis of new elements, for example, californium from
242Cm (a,n) 245Cf(44 m) in 1950 and nobelium from 246Cm (12C,
4n) 254No (1 m) in 1958, and for heavy-ion reactions to make new
neutron-rich isotopes and to study reaction mechanisms. More
recently, 248Cm has been widely used as a target for a variety of
attempts l ,2 to make superheavy elements, and in other heavy element
studies because of its high neutron-to-proton ratio. It is especially
convenient to use because of its long half-life (3.4 x 105 years),
and its availability in milligram amounts, nearly isotopically pure,
by milking from 252Cf. The availability of such target materials in
the U.S. is a tribute to Professor Glenn Seaborg's vision in
establishing the Transplutonium Production Program at the High Flux
Isotope Reactor (HFIR) at Oak Ridge National Laboratory in the early
1960's when he was Chairman of the U.S. Atomic Energy Commission. In
fact, as early as 1957 he had written a letter to then Chairman Lewis
Strauss pointing out that research on the new transuranium elements in
this country would be dependent on "substantial weighable quantities
(say milligrams) of berkelium, californium and einsteinium". He
further pointed out that this would require irradiation of substantial
quanitities of 239pu and re-irradiation of the products in a
proposed "very high flux reactor". And in fact, the HFIR began
241
242 D. C. HOFFMAN
operation in 1964, the Transplutonium Production Program was

established, and milligram quantities of 252Cf began to be produced
and became available to researchers.
Because its neutron-to-proton ratio (1.58) is nearly the highest
of any heavy element isotope feasible for use as a target, 248Cm has
been used in many attempts to make superheavy element (SHE) isotopes.
In a recent .attempt l , we bombarded 248Cm with 48Ca ions at
energies near the Coulomb barrier in order to try to produce SHE's
with low excitation energies so they would not be completely lost by
prompt fission. The resulting compound nucleus tS8ll6 is near
the island of stability which has been predicted to exist in the
region of 114 protons and 184 neutrons. However, no evidence for
SHE's with half-lives in the range from 1 microsecond to 10 years with
cross sections larger than 10- 34 to 10- 35 cm 2 was found. (See
Figure l.)
Yields of isotopes of elements with atomic numbers both larger and
smaller than that of the curium target were also measured 3 ,4 for
reactions of 248Cm with 40C a and 48Ca ions at energies from near
the Coulomb barriers to 60 to 80 MeV above the barriers. It is of
interest to compare reactions of these two projectiles to assess the
effect of the additional 8 neutrons in 48Ca. A comparison of the
mass-yield curves for these two systems for Bk, Cf, Es, and Fm is
shown in Figure 2 for energies about 5 to 10 MeV above the Coulomb
barrier. The maxima of the mass-yield distributions are only about 2
mass units larger for the 48Ca than for the 40C a reactions; thus
the 8-neutron difference in the projectiles is only partially
reflected in the heavy product yields. This is in contrast to our
results for 160 and 180 and 20Ne and 22Ne where the full two
mass unit increase was observed in the mass-yield distributions for
the heavier projectile of each pair. The maxima for these yield
curves for reactions of 248Cm with 48Ca (N/z = 1.4) occur at about
the same mass numbers as for reactions with 180 (N/z = 1.25) and
22Ne (N/z = 1.2), and the half-widths for all the distributions are
from 2 to 2.5~. The maximum cross sections for production of the Bk
and Cf isotopes are about the same for 40C a and 48Ca reactions,
but the maximum yields for Es and Fm are about 5 times larger for
40Ca than for 48Ca reactions although the yields for the most
neutron-rich isotopes are much higher for 48Ca reactions. A
comparison of the cross sections for actinide production from other
neutron-rich projectiles including l36Xe and 238U indicates that
cross sections for transfer of the same combinations of neutrons and
protons from projectile to heavy actinide targets are about the same
provided the reaction energy is not negative.
Excitation functions for these systems were also measured and are
shown for the production of Es and Fm isotopes from 40Ca and 48Ca
reactions in Figures 3 and 4, respectively. It is particularly
interesting to note that the yields are near their maxima at the
Coulomb barrier for the 40C a reactions, consistent with the
calculated 5 positive excitation energies for these reactions.
However, the observation that the yields decrease only slowly with
increasing projectile energy is somewhat surprising because the
HEAVY ION REACTIONS ON CURIUM TARGETS 243
fission barriers are only of the order of 5 to 6 MeV. Apparently only

a small fraction of the projectile kinetic energy appears as
excitation energy of the heavy product. Maxima in the mass-yield
distributions for Es and Fm from 48Ca shown in Figure 4 are observed
at about 20 MeV above the Coulomb barrier, consistent with
calculations showing that these reactions are endothermic by 10 to 15
MeV. Again, however, the cross sections decrease only slowly with
increasing projectile energies up to 80 MeV above the barrier.
Additional investigations are needed to try to ascertain how this
excess energy is dissipated. In any case, these observations are
encouraging for the production of new isotopes of the heaviest
elements using similar "transfer" reactions in which the heavy
product is formed with a low enough excitation energy that it is not
entirely lost by prompt fission or particle emission.
The yields of some isotopes of elements lighter than the target
were also measured and are shown in Figure 5 for 48Ca + 248Cm
reactions. The cross sections are remarkably high with maxima of the
order of 200 microbarns or more for elements down to Rn (Z = 86). The
half-widths of these isotopic distributions are 4.5 to 5 mass units,
considerably larger than those observed for the above target
distributions. Yields were measured for only a few isotopes of Th, U,
and Pu for the 40Ca reactions, but the yields were much lower than
for 48Ca. A comparison of the integrated elemental yields for
40Ca and 48Ca are shown in Figure 6. As can be seen, the yields
of the below target elements are lower by factors of 10 to 100 for the
40Ca reactions. This may be a result of the tendency toward N/z
equilibration in which protons would tend to flow from the proton-rich
40Ca to the neutron-rich (proton-deficient) 248Cm. The data for
the yields of Th, Ac, and Ra from the 48Ca reactions imply the
formation of the very neutron-rich Fe, Co, and Ni isotopes, 65Fe,
68Co , and 72Ni, as complementary fragments (assuming emission of
only one neutron from the light fragment) with similar cross sections
of the order of 200 micobarns.
In summary, a variety of different projectiles and projectile
energies have been used with 248Cm targets to megsure cross sections
and excitation functions for elements both heavier and lighter than
the target. Neutron-rich projectiles enhance the formation of
neutron-rich heavy products. Cross sections for above target elements
decrease rapidly with the number of nucleons transferred. Excitation
functions indicate that the excess kinetic energy of the projectile
does not go in to excitation energy of the target-like product and
that "cold" heavy products are produced. In general, the maxima of
the excitation functions are consistent with product excitation
energies calculated assuming binary transfer reactions. The yields of
below target elements for the 48Ca + 248Cm system imply formation
of very neutron-rich complementary fragments of Fe, Co, and Ni.
244 D. C. HOFFMAN
0G) GX0 ~ #l @®
\\ \® ~ / CV
~ ICD
I I I
5 \ \
! I
I-
\\ \ : I I I
~
--l 2 \\ \:/! I
5 10- 33 \\ I \I
'I
i I
\\ I /1
I I I
I-
U
W
(f)
5 \\\\ \\ / \\ '/
! /
'------\-;.-- -
,,------\ \ l I
'-. '/ I ,
(f)
(/)
o 2 ,\
\
\
'/
'/
0:: "
... _-\-
\~ .. I
I
U 10- 34 \
\ ,~ I
I
Z
o
I- 5
U
~
o
o 2
0::
0... 10- 35
151m 1h 1d 1y 100y
10- 9 10-7 10- 5 10-3 10-' 10' 10 3 10 5 107 109 10"

HALF LIFE (5)
Figure 1. Upper limits (at 95% confidence level) for t~8 production
cross sections of superheavy nuclei in the reaction of Ca with
248Cm in the energy range' 4.5 to 5.2 MeV/)1 as a function of the half-
life. The data result from experiments with recoil fragment
separators (curves 1,2), with fast on-line chemical separations
(3,4.5), and off-line chemistry (6,7,8). (T8ken from Ref. 1.)
221-234 MeV 40Ca

/' (open symbols~8
/
.~~ 247-263 MeV Co
I"~ "Ielooed .,mbol.)
I / j / \ \\\
f'
-
.a ,I I/ ~/,\\
Bk
\ :: t-----
Cf
i ---
iI--
:l..
-10 2
Z
o
/~ 1,.1 /
" \\\'\\\
i=
I / /~\
.
(.)
LLI
en
en
en 10 1
I / ,'/ ~ \~
o
a: / \ \
/
(.)
: ~\
r
250 252 254 256
PRODUCT MASS NUMBER
Figure 2. Comparison of heavy actinide yields from 40Ca and 48Ca

reactions with 248Cm . Projectile energies in the target are from
5 to 10% above the Coulomb barrier. (Taken from Ref. 3.)
246 D. C. HOFFMAN
10 2
248 Cm + 40 Ca o Es
o Fm
(x 10- 1)
1-4- 250 Es
10 1
252 Es
252 Fm
253 Es
.D
10 0
::l
z
0
~
~
U
W ~254mES
(f)
254 Fm
(f)
(f)
0
0:: 10- 1
U
220 240 260 280 300

ENERGY (MeV)
Figure 3. Excitation functions fzr some Es and Fm isotopes produced

in the bombardment of 248Cm with DCa. (Taken from Ref. 3.)
HEA VY ION REACTIONS ON CURIUM TARGETS 247
248Cm + 48Ca - Es , Fm <>Es

o Fm
- 10 1 252
..Cl
::i..
z 253
0 Es
~
U
W
en 10°
en
en
0
0::: 254
U 255
10 1 Fm
256
252
-2
10200
260 280 300 320
ENERGY (MeV)
Figure 4. Excitation functions for some Es and Fm isotopes produced

in the bombardment of 248Cm with 48Ca . (Taken from Ref. 3.)
248 D. C. HOFFMAN
1000
Rn
Ac
+ Th
r:r
Ra
100
:0
::t
z
o
I-
U 10
L.U
(/)
(/)
(/)
o0::
U
1
248 Cm + 48 Ca
(247-263 MeV)
0.1
200 210 220 230 240 250 260
MASS NUMBER
Figure 5. Mass-yield distribu~ions for some lighter than t2.rget

elements from the reaction of 8ea with 248em . (Data from Ref. 4.)
1026 /
.......... /
N
E
u
IX
'-';
/
1627 ! f-.-.
-
~ ~
::::: 1
I
a
u
OJ
" ,~
II)
II)
II)
1628
a
L..
w
246-259 MeV 40(Q (0)
247 - 263 MeV 48(0 (x)
10-30
90 95
ATOMIC NUMBER
. 40 48
Figure 6. Comparison of elemental Ylelds for Ca and Ca reactions
with 248Cm . (Data from Ref. 4.)
250 D.C. HOFFMAN
REFERENCES
1. P. Armbruster et al., Phys. Rev. Letters (submitted) 1984.

2. E. K. Hulet et al., Phys. Rev. Lett. 39, 385 (1977); J. V. I11ige
et al., Phys. Lett. 78B, 209 (1978); ~ J. Otto et al., J. Inorg.
Nucl. Chern. 40, 589 (1978); Yu. Ts. Oganessian et al., Nucl. Phys.
A291, 213 (1978).
3. D. C. Hoffman et al., Phys. Rev. C (submitted) 1984.
4. H. Gagge1er et al., in preparation, 1984.
5. D. C. Hoffman and M. M. Hoffman, Los Alamos National Laboratory
Report LA-UR-82-824, rev., March 1984.
6. D. Lee et al., Phys. Rev. C 25, 286 (1982).
7. D. Lee et al., Phys. Rev. C~, 2656 (1983).
This work is supported by the Director, Office of Energy Research,

Division of Nuclear Physics of the Office of High Energy and Nuclear
Physics of the U.S. Department of Energy under Contract
No. DE-AC03-76SF00098.
Synthesis of Transuranium Nuclides from Interaction of 160 with 238U
N.Shinohara, S.Ichikawa, S.Usuda, T.Suzuki, H.Okashita,

T.Sekine, K.Hata
Japan Atomic Energy Research Institute,
Tokai-mura, Naka-gun, Ibaraki-ken, 319-11 Japan
T.Horiguchi, Y.Yoshizawa
Hiroshima University,
1-1-89, Higashi-Senda-cho, Naka-ku, Hiroshima-ken, 730 Japan
S.Shibata
Institute of Nuclear Study, University of Tokyo,
3-2-1, ~1idori-cho, Tana-shi, Tokyo, 188 Japan
I.Fujiwara
Institute of Atomic Energy, Kyoto University,
Gokasho, Uji-shi, Kyoto-fu, 611 Japan
Many studies of actinides, especially of transuranium elements,

have been performed mainly owing to scientists' endeavors to discover
new elements and nuclides. (1) In spite of these efforts, the
mechanism of the formation of transuranium nuclides by heavy-ion
bombardment and the nuclear and chemical properties of the synthesized
actinide nuclides have not been clearly elucidated, and a great deal
remains to be examined in more detail. In this context, we have begun
the investigation of heavy-ion nuclear reactions (2): A svstem In
which a uranium target is irradiated by oxygen ions (160 +288U). was
chosen. For this reaction seventeen nuclides (250Fm, 244,245,246(f,
242cm. 238,23%p, 237, 23GU. 225, 22Q, 2c::i,228Th, 224,225Ac, and
223,224Ra ) were identified and the condition of formation for these
nuclides was clarified. This paper deals with a novel method of
mutual rapid separation of the synthesized transuranium elements by
ion exchange and a discussion of the mechanism which governs the
heavy-ion nuclear reactions.
Experimental
The uranium targets, 99.98 % 238U, were prepared by
electrodeposition from an isopropyl alcohol solution(3) onto an
aluminum backing of 7-)lm thickness. The targets varied in thickness
251
N. M. Edelstein et al. (eds.), Americium and Curium Chemistry and Technology, 251--260.
252 N. SHINOHARA ET AL.
from 0.3 to 2.0 mg/cm 2 of uranium. A target assembly consists of

aluminum foils for degrading the beam energy at the upstream side of
the target and an aluminum foil (7 pm thickness) for catching the
recoiling nuclei at the down stream side.
Irradiation by 160 ions was performed by the JAERI Tandem
accelerator. The beam energy was varied from 85 to 130 MeV and the
beam intensity was up to 150 pnA. Typical irradiation durations were
0.5 to 3 hours.
After irradiation, both the target and the aluminum catcher foil
or the catcher foil only were dissolved in aqua regia and the solution
was heated to near dryness. The sample was then redissolved in a
nitric acid and methyl alcohol mixture solution, and a rapid
anion-exchange procedure for separation of transuranium elements was
carried out using a high performance liquid chromatographic
technique. Figure 1 shows the typical elution curves for the
separation of transplutonium elements and rare-earths by anion
exchange using an acid-alcohol mixture as eluant. Chemical separation
of target-like nuclides was also carried out by ion exchange. After
separation, the fractions were mounted on tantalum discs and dried to
make the sources for radioactivity measurements. Time required for
the separation is about 20 minutes including the source preparation.
Alpha- and gamma-activities of the recoiling nuclei, which were
collected by the aluminum catcher foil, were measured with
Si-surface-barrier and Ge(Li) detectors immediately after
irradiation. The same measurements were performed for the chemically
separated samples. Measurements were continued for about two months
after irradiation.
Results and Discussion
Fe nni llIn
Fermium nuclides expected to be synthesized in 160 + 238U
reactions are 248Fm ( T1/2 = 36 sec.; E~6Dha = 7.87 MeV), 249pm
( Tl/2 = 2.6 min.; Ealpha = 7.53 MeV), and 2 Fm (Tl/2 = 30 min.;
Ealpha = 7.43 MeV). (4,5) After bombardment for 30 minutes, the
transplutonium fraction was separated from the irradiated sample by
the ion-exchange method and subjected to alpha spectrometry (Fig. 2).
The chemical behavior, the alpha energy, and the half-life observed
indicate formation of the 250Fm nuclides.
To study the conditions for the formation of 250Fm, the
dependence of the quantity of 250Fm produced on projectile energy was
investigated. The excitation function of 250Fm thus obtained is given
in Fig. 3. The 250Fm nuclides are synthesized' between about 84 ~leV
and 102 MeV of 160 ion energy on the target (lab. system) and the
formation cross section becomes maximum (about 2 x 10-30 cm2 ) when the
projectile energy is around 92 MeV.
Other fermium nuclides, 248, 249pm, could not be detected, but the
upper limit of the formation cross section of these nuclides was
determined to be 7 x 10-32 cm2 for 100-MeV 160 ions.
SYNTHESIS OF TRANSURANIUM NUCLIDES FROM INTERACTION OF 16 0 WITH 23 8U 253
1 M HN0 3 - 0.5 M HNOr 0.5 M

90% CH30H 80% CH30H HN03-
60% CH 30H
n Cs Ce
10
4 II
.~ P
Ru
Sr y
: CL activity n Th -
II
::CJI.l)
a
(\1
: S activity
,.':
,I
I I \ t\
I
II
I ,"
I
r,
"-' I I t
II I ' Pm I
: I I ' I
(I I I
II
I I
I
I
I
I
i"\
I I
I
Eu
r:;
I' I I , I
i I
I
I
I
-
,I I I
f\
':
,
I
I
,
'I I I , ICf I I
I I I I I fli II 'I
: I
,I,
: I I I
I I
I
I
I
I
I
I
I I
I I
I I I I I I I
•I"I I I I em 1 I
1 :
I I
j n~"~
I I", I I I
I I I :
I I!\ I I I
!7- v \ t
~:
I I
I \ I , I I
\ I I I
, \ I U I
: \.1
,
,
: :
I
1
I
I
I I
I I
i ~
I
1 j \
,
\
1
I
I
\
I
\ I \
\
\
, 1', \
'\
1 \
I \ -
\
\ '. ' . . ~_.J \
\ ,, Np \ ,
, '\
/'I, " ,
"
, I
I "
'_ ...
-
\
i \\ 1 \ \,
0 10 20
Effluent (ml)
Fig. 1 Elution curves for the separation of transplutonium
elements and rare-earths by anion-exchange using
acid-alcohol mixtures as eluants.
7S ~----------------------------~
238U + 160
E{ab = 88 MeV
<.J
~70
-:::.::.
~
-tI)
c:
2l
o
Us
O!l---~----I-Y'-...L...L..l~----L...,u..L...I..L....a,.&
4 5 6 7 8
Energy J MeV
Fig. 2 Alpha-spectrum of the transplutonium fraction after

the ion-exchange separation.
SYNTHESIS OF TRANSURANIUM NUCLIDES FROM INTERACTION OF 16 0 WITH 238 U 255
Californium and curium

By measuring alpha spectra of the aluminum catcher foils for long
periods after irradiation and examining chemical behavior and
half-lives, the formation of 246cf and 242cm was confirmed. The
excitation functions are also shown in Fig. 3.
The formation of other californium nuclides, short-lived
244,24Ocf, was also observed a short time after the bombardment. The
alpha spectrum of the californium fraction just after the separation
is given in Fig. 4.
Nepitmillm cmd urcmium
The formation of the target-like nuclides emitting gamma-rays was
investigated. After irradiation, the gamma-spectrum of the aluminum
catcher foil was measured with a Ge(Li) detector and the chemical
behavior of the ~amma--emi tter was studied. The formation of the
nuclides 238,23~p and 237, 2390 was confirmed. The formation cross
sections of these nuclides are also depicted in Fig. 3. Other
target-like nuclides, e.g., 240, 241 U, could not be recognized despite
prudent experiments.
17lOriwil, actinlllTil and radium
When the projectile ener~y increased to 110-130 MeV, formation of
the 2DOFm, 244-246cf and 24·2cm nuclIdes could not be observed and
instead production of thorium, actinium and radium nuclides was
detected. After measuring the alpha-activities and the half lives and
ex~mjnin~he chemical characteristics, various nuclides such as
22D,226,ar,228Th, 224,22DAc and 223,224Ra were identified. Figure 5
gives the formation cross sections of these nuclides as a function of
the number of neutrons and protons picked up from the target nucleus.
FonllGhon meclwnism of GchnicJes

From the view of synthesizing actinides, the reactions are
classified roughly into two processes: Ci) complete fusion process and
(ii) nucleon transfer process, dependent on the angular momentum
carried into the system. (6) An example of the first mechanism is the
reaction, 238U(12c,4n)246(f(7), and of the latter is 27Al (160, 15N)28Si
(S2) .
Ci) compLete fusion process (CF); this implies that two nuclei
are fused in the bombardment to form one compound nucleus. Most of
the compound nuclei decay by fission but a very small fraction of the
nuclei undergoes nucleon evaporation reactions. The excitation
functions of 238U (160,4n )250Fm, 238U (160.CX4-6n )244- 246cf and
238U(160,2(y'4n) 242cm reactions can be calculated by ALICE code assuming
the particle evaporation from ths: compound nucleus. (.2) The observed
formation cross sections of 2~OFm have a nearly same feature as the
calculated values by the ALICE code. The 250fm could be formed by
evaporation of four neutrons, following the formation of the compound
nucleus 254Fm.
(ii) nucleon. transfer process; nucleon transfer process can be
classified into the following three mechanisms: quasi-elastic transfer
(QET), deep-inelastic transfer (DIT), and massive transfer (MT). QET
256 N. SHlNOHARA ET AL.
-24
10 r-
N
E -27
u 10
242
Cm
,..._0-- - - .....0
,...-' 0 "
o // '0
/
./0 0 "
/
/
0'
I
I 246 Cf
I
I
/
I
,o
I
I
I
f
I
1032 , I I I
80 90 100 110
16 0 ION ENERGY (LAB SYSTEM) MeV
Fig. 3 Excitation functions of actinides synthesized in the
16
o + 238 U reactlon.
.
The fission data quoted are
from V.E.Vio1a,Jr. et a1. [Phys. Rev. ,1962,128,767].
Ul
-<
Z
...,
:t
to1
Ul
C;;
o
"71
:?o -
238U + 160 ...,
;0
;l>
Z
Ul
C
;0
E1ab == 101 MeV ;l>
245 Cf Z
C
s:::
lJ) z
c
-+-' n
t""
8to1
C Ul
."
;0
246 Cf
:J o
o IO- s:::
Z
...,
tTl
;0
U ;l>
n...,
244Cf (3
z
o
."
o'"
::;::
:=i
:t
N
.I i i i i i Ij iii i I I I fFl ~F~~rnH~f I ~~~ I i I I " , , ! •• i l i i i f Ii . ,I W
-,
o700 ~., I •• i I I I I ( r Jl l l i l i l i l i ' I ' •
~fiitti rrr~~~'~'~~~~JJJr~~~~~~~~~-IJ 00
p~rt»HI
800 C
Charlnel
Fig. 4 Alpha-spectrum of the californium fraction after the ion-exchange separation.
N
V.
-->
10- 28 - - -.......- -~-

.......
Elab=113 MeV Elab=120 MeV

Elab=126
Me~
• -2p,-xn
CTh)
o -3p,-xn
(Ac)
!J. -4p,-xn
C\J (Ra)
E
U
.10- 30
z
o
f-
U
W
(f)
10- 31
(f)
(f)
o
0::::
U
10- 32
-12 -11 -iO -9 -8 -7 -12 -11 -10 -9 -8 -7 -12 -11 -10 -9 -8 -7
-xn
Fig. 5 Formation cross sections of the thorium, actinium

and radium nuclides synthesized in the 16 0 + 238 u
reaction. The abscissa indicates the number of the
picked up neutrons and the ordinate shows the measured
cross sections.
SYNTHESIS OF TRANSURANIUM NUCLIDES FROM INTERACTION OF 16 0 WITH 238 U 259
takes place at the outermost shell of nuclei and DIT is the reaction
in which the area of collision is larger than in the case of QET. MT
means that the ta~get nuc~eus.and a pa~t of the.~rojectile are fused
together. The obtalned excltatlon functlons of 24bCf and 242cm differ
apparently from the calculated ones by the ALICE code. The nuclides
of 244,245,246cf and 242cm would be formed by the transfer reaction,
probably QET or DIT, instead of the presumed particle evaporation
reactions.
In the synthesized target-like nuclides, the 238Np could be
formed by neutron-proton exchange reaction between target and
projectile nucleus, and the 239Np or 239u by a one proton or one
neutron transfer reaction from the projectile to the target. The
nuclide 237U could be formed by a one neutron pick-up reaction, in
which the projectile picks one neutron up from the target nucleus.
The nuclides of thorium, actinium and radium seem to be formed by
picking up 2 to 4 protons and 8 to 11 neutrons from the 238U target
(Fig. 5); He. Li. or Be fragments of various masses could be
transfered to the projectile. This reaction corresponds to either a
multinucleon pick-up reaction or Mr, and the Qgg systematics (lQ) may
be used to describe the reaction mechanism.
Conclusion
At least seventeen actinide nuclides were synthesized by 160 +
238U reactions and their formation conditions were investigated. We
can classify those nuclides into four categories: the first is the
reaction product 250Fm formed by the complete fusion process; the
second, the products 244-246cf and 242cm formed by quasi-elastic
transfer or de~~inelastic transfer processes; the third, target-like
nuclides 238.~p and 237. 239u formed by one-nucleon transfer
processes; and the last, products such as 225.226.227,228rh,
224.225Ac and 223,224Ra formed by multinucleon pick-up or massive
transfer processes. Because most of the radioactivity measurements
were limited to alpha-spectrometry only, other nuclides may have been
synthesized, which were not detected, and other mechanisms than those
mentioned above could have occurred.
The authors are most greatful to the operating staff of the JAERI
Tandem Accelerator for making this research possible by their
considerable help in many ways.
References
1) Ghiorso,A.:"Actinides in Perspective", Proceedings of the Actinides
1981 Conference, edited by Edelstein, N.M., Pergamon Press, 1982,
23-56.
2) Shinohara,N. et al.: "JAERI TANDEM Annual Report 1982", JAERI-M 83-
095 ,1983, 53-55.
3) Kono,N. et al.: private communication ,1982.
4) Lederer, C.M. and Shirley, V.S., Eds. : Table of Isotopes, 7th Ed.,
J.Wiley & Sons, New York ,1978.
5) Akap'ev,G.N. et al.: Atomnaya Energiya 1936,gj ,243.
6) Zucker,A. and Toth,K.S.: "Nuclear Chemistry·, edited by Yaffe, L.
Academic Press ,1968, 409-452.
7) Gerlet,Y.B. et al.:-Zh.. Eksperim.i. Teor. Fiz. 1957, 33, 339.
8) Newman,E. et al.: Phys. Rev. 1963, 119, 1720.
9) Blann,M.: Report COO-3494-29, 1976.
10)Artukh.A.G. et al.: Nuci. Phys. 1973, A211, 299.
A STUDY OF THE PRODUCTION OF TRANSURANIUM ELEMENTS AND ITS APPLICATION
TO THE SOLUTION CHEMISTRY IN TOHOKU UNIVERSITY
I. Satoh, T. Mitsugashira, M. Hara, M. Kishimoto, and S. Suzuki

The Research Institute for Iron, Steel and Other Metals,
Tohoku University
Japan
ABSTRACT. About 2.8 g of U02 were irradiated with neutrons(about 1.6x

10 20 nvt) at the Japan Material Testing Reactor(JMTR). After 140 days
cooling, the irradiated sample was processed chemically. The isotopiC
ratios of U and Pu were determined by a-ray spectrometry and mass spec-
trometry. A small amount of 241Am«100 ~g) was also irradiated in JMTR.
Am and Cm were purified mainly by ion-exchange chromatography. We have
tried to estimate the irradiation conditions in JMTR. The thermal neu-
tron flux($) and the epithermal ratio (the ratio of the epithermal to
the pure thermal neutron density)(f) were chosen as adjustable variables
for the calculation of the isotopic ratios of U, Pu, Am, and Cm. Then,
the most reasonable values of $ and f were obtained which explained the
values of the isotopic ratios obtained experimentally. Short-lived Bk
tracers, 2 43-246Bk, were produced by the 241Am + a and 243Am + a reac-
tions using the A.V.F. cyclotron at the Cyclotron and Radioisotope
Center, Tohoku University. A compressed aluminium powder disk, in which
Am· was suspended, was used as the target. Bk tracers were isolated from
Am and fission products by HDEHP or TTA extraction of Bk(IV). Stability
constants(a1 and a2) of the chloro and bromo complexes of trivalent Sm,
Eu, Gd, Tb, Ac, Am, Cm, Bk, and Cf were determined by a solvent extrac-
tion method using HDEHP with an ionic strength and acidity of 3.0 M and
0.15 M, respectively. Stability constants could be roughly estimated by
assuming inner sphere complex formation.
INTRODUCTION
We have two methods to produce the transuranium elements. One is by the

multiple neutron capture reaction in a nuclear reactor and the other is
by nuclear reactions in an accelerator. For the application of the
multiple neutron capture reaction, it is very effective to use a high
flux reactor. In 1970, the Japan Atomic Energy Research Institute began
irradiation service in the JMTR at the Oarai Reseach Establishment. We
constructed the chemical processing equipment(~) in the 6th hot-cell of
the Hot Laboratory of the Oarai Laboratory for Irradiation Experiment of
the Research Institute for Iron. Steel and Other Metals, Tohoku Univer-
261
262 I. SA TOH ET AL.
sity. First, the irradiated U02 was processed chemically, and then the
irradiated Am02 was processed.
The cyclotron at the Cyclotron and Radioisotope Center, Tohoku
University accelerates proton to 40 MeV and 4He to 50 MeV. The Bk
tracers were produced by bombardment of the Am02 target with 4He.
The stability constants of the chloro and bromo complexes of sev-
eral actinoid and lanthanoid elements, which were available or produced
by the nuclear reactions, were determined.
MATERIALS AND METHODS
Neutron irradiated uranium
Uranium dioxide pellets, which contained about 2.8 g of natural uranium

dioxide, were irradiated during three irradiation cycles of the JMTR at
the N-10 irradiation hole in the Be reflector zone. The irradiated U was
processed chemically about 140 days after the irradiation to reduce the
radioactivity of fission products. The flow sheet of the separation
scheme is shown in Figure 1. The pellets were dissolved in a 6 M HN03
solution and the Pu was adjusted to the tetravalent state by the addi-
3 M HN(}J (Washing)
0.01 M HN03 (Stri pping)
Figure 1. Separation scheme of neutron irradiated U02

THE PRODUCTION OF TRANS URANIUM ELEMENTS 263
tion of an equal volume of diluted NaN02 solution. Then, U(VI), and

Pu(IV) were extracted into a 30 vol% TBP/xylene solution. The separation
of U and Pu was carried out with the same system after the Pu was
reduced to the trivalent state and remained in the aqueous phase.
The chemical yields of U, Pu, and some fission products were deter-
mined by a- and y-ray spectrometry to examine the separation method. A
Si surface-barrier detector and a Ge(Li) detector were applied to the
the measurement of a-ray and y-ray spectra, respectively. A 4096-channel
PHA was used for the accumulation of the spectra.
A mass spectrometer(Atlas CH-4) was used for the determination of
the isotopic composition of U and Pu. An aliquot of the purified solu-
ions of U and Pu, which contained about 10 ~g of U and 1 ~g of Pu, was
placed onto rhenium ribbon filaments and evaporated to dryness. Ioniza-
tion cases of the double-filament type were used throughout the scanning
of mass spectra. For the detection of weak ion beams, a secondary elec-
tron multiplier tube was used.
Neutron irradiated americium
241Am02 was irradiated in the reflector area of the JMTR intermittently

for 384 day.(~) The authors obtained a part of it from the Japan Atomic
Energy Research Institute. The flow sheet of the separation procedure
for the transuranium elements is shown in Figure 2. The chemical separa-
tions were carried out by remote control via ion-exchange methods in the
6th hot-cell. After the dissolution of the irradiated sample, the trans-
uranium elements were separated from most of fission products and clad-
ding materials on anion exchange resin using a 9.9 M LiCl-0.1 M HCl solu-
tion. Then the actinoids were eluted with 6 M HCl at 87 OC. The column
was 80 rom in length and 8 rom in diameter; the flow rate was 0.25-0.35
ml/cm 2 /min.
The transuranium elements, in the HCl solution containing a small
amunt of LiCl, were coprecipitated with Fe(OH)3. The iron and actinoids
were separated by the anion exchange method. Subsequently, the trans-
uranium elements were separated by the following two methods.
Method 1: cation exchange separation with 2-hydroxyisobutyric acid
(2-HIB) was performed. An HCl solution of transuranium elements was
dried and several drops of 0.4 M 2-HIB(pH 4) were added. This solution
was placed and adsorbed on the top of the resin (maintained at 87 OC by
the vapor of trichloroethylene) and eluted slowly. Suitable aliquots of
the effluent were taken in polyethylene test tubes. Each fraction was
analysed radiochemically. The exchange resin column was 117 rom in length
and 4 rom in diameter; the flow rate was 0.3-0.6 ml/cm 2 /min.
Method 2: anion exchange separation with a HN03-methanol solution
was performed. The anion-exchange resin column was 70 rom in length and
4 rom in diameter; the flow rate was 0.25-0.35 ml/cm 2 /min. One ml of a
1.0 M HN03-90 %methanol solution of the transuranium elements, in which
152Eu and 137Cs were added, was absorbed on the resin and eluted with a
solution of 0.5 M HN03-methanol. The concentration of methanol was decr-
eased from 90 to 0 % in steps according to the elution of the elements.
After the chemical separation, isotopic ratios of Cm and Am were
determined by analysing their a- and y-ray spectra obtained by the use
264 I. SATOH ET AL.
( DiSsolutiOn)
and dry up
9.9 M LiCI- 0.1 M HCI
6 M HCI
.---_---'L---_ _.L---, Sb, Co, Ru
'-;:::==::r:==~r::;-""'" (Adsorbed)
FE'
(Adsorbed)
( Dry up )
Figure 2. Separation scheme of neutron irradiated Am02

Ln: Lanthanoid elements, An: Actinoid elements
of Si- and Ge(Li)-detectors, respectively. The 242mAm was quantified by

analysing the growth curve of 238NP, the a-decay product of 242mAm. The
measured isotopic ratios were compared with the values calculated from
the irradiation history in JMTR to consider the irradiation of 241Am.
Production of Bk tracers
The 2 43-246Bk, which were produced by the 241Am + a or 243Am + a reac-

tion, were isolated rapidly from the Am target by the solvent extraction
method shown in Figure 3. Bk was oxidized to the tetravalent state and
extracted into a TTA/xylene solution(l) or HDEHP/heptane solution.(~)
The y-ray spectra of the Bk fraction were measured using an intrinsic Ge
detector and a 4096-channel PHA.
Stability constants
The stability constants of the chloro and bromo complexes of trivalent

Sm, Eu, Gd, Tb, Ac, Am, Cm, Bk, and Cf were investigated. The tracers of
these elements were obtained as follows: 152Eu, 153Gd, 160Tb, and 252Cf
TT A-extraction HDEHP-extraction
Target Target
"'9.
. Wash by
J. Arn- roctlon~10M HN03.1M NaBrOl
£.g
arg. 3min.
Wash by
r
Am-fraction~ 2M H2SOr..O·2MNCllCn07
1 0 '9 Smin. Back-extrn by
Back-extrn by 10MHNOl.1M H202 3min
r
q (Bk(lV)- Bk(m))
10M HN03
aq. 10min.
Bk-fraction Bk-fraction
Figure 3. separation scheme of Bk
were obtained from the Radiochemical Centre, Amersham, and 241Am from
Oak Ridge National Laboratory. 225Ac was isolated from 229Th which was
obtained from 233u. Cm and Bk tracers were prepared as described above.
145Sm was produced by means of the Nd + a reaction and was purified by
successive extractions with HDEHP. These tracers were prepared in 3.0 M
HC104 solutions and stored in Pyrex vessels.
A 6 ml sample solution was prepared by mixing appropriate amounts
of stock solution, 3.0 M LiCl or LiBr solution, and 3.0 M LiC104 solu-
tions in a separatory funnel. The sample solution was equilibrated with
an equal volume of an HDEHP/octane solution pre-equilibrated with a
solution of the same composition as the sample solution. To determine
the relation between the distribution ratio and ligand concentration,
the acidity was fixed at 0.15 M and the concentration of HDEHP was con-
trolled so that the distribution ratio in the absence of the ligand was
to be 1.5-1.8. Extraction equilibrium was reached by shaking for 20 min
at about 20 0C. From each phase, a 2 ml portion was placed in a poly-
ethylene test tube and the radioactivity was counted. For bromide solu-
tions, values were corrected for self-absorption of y-rays using absorp-
tion data preliminarily determined.

Neutron irradiated uranium
144 Ce , 106 Ru , 134,137Cs, and 95Z r _95Nb were observed in the y-ray spec-
trum of irradiated U. All these nuclides were effectively removed from

the Pu-U fraction. The chemical yield of Pu in the Pu-U fraction was
greater than 90 %. The isotopic composition of U and Pu were determined
by a-ray spectrometry and mass spectrometry, and are shown in TABLE I.
TABLE I. The isotopic ratios of U and Pu
Isotopic ratio Measured Calcula ted *

(xl00) (xl00)
----- ..... -------.--,-----~-- .. -,.. ---
235U/ 238U 0.657 :!:. 0.010 0.657
23 6U/235U 1.86 -+ 0.23 1.650
240pu/ 239pu 2.846 -+ 0.045 2.873
241pu/ 24O pu 3.29 -+ 0.20 3.270
. .,.------ ----- --~~---
~=3.17xl013 n/cm 2 /sec and f=0.06

*
The yields and the isotopic ratios of actinoids were calculated
with a computer program(2) adjusting two parameters, ~ and f. We also
took into account the fluctuation of the neutron flux during the irradi-
ation assuming that the flux is proportional to the reactor power. As is
shown in TABLE I, the calculated isotopic ratios agreed well with the
measured values. Thus we could conclude that f=0.06 and ~=3.17xl013
n/cm 2 /sec at the N-l0 irradiation hole when the reactor power is 30 MWt.
As we did not consider the absorption of neutrons by the target, the
actual f and ~ will be 1.7-2.0 times greater than the fitted values. The
maximum power of JMTR is 50 MWt, so we can say that the neutron flux of
JMTR is high enough to apply JMTR to the production of transuranium ele-
ments through the irradiation of 241Am and 243Am.
Neutron irradiated americium
The a- and y-ray spectra of the irradiated sample showed that it con-
tained the transuranium elements 238pu, 241-243Am, and 242-244Cm, the
fission products 13 4 ,137Cs, 144Ce, 106Ru, and 125Sb, and the cladding
materials 110mAg and 60Co. Via the anion exchange separation procedure
with a LiCl solution, Cs, Ce, Sb, Co, and most of Ag and Ru were sepa-
rated from the transuranium elements.
In the case of the cation exchange separation procedure with 2-HIB,
the retention time of transuranium elements depends greatly on the pH
value of the 2-HIB. The most appropriate pH value was found to be 4.0.
Figure 4 shows the elution curve of the transuranium elements Np, Pu,
Am, and Cm using 0.4 M 2-HIB of pH 3.98. Although Cm cannot be perfectly
separated from Am, the separation factor of Cm/Am was found to be about
1.4. A similar value has been reported.(~)
The result of the anion exchange separation with the HN03-methanol
solution is shown in Figure 5. The two peaks are attributed to Cm and
Am. Cs was not adsorbed and eluted in the first peak; Eu eluted before
em and Am. The 239Np(tl/2=2.35 d), which is the daughter of 243Am, was
eluted while 243Am remained on the resin but its elution behavior was
not clearly known. In comparison with the cation exchange method with
30 Np
25 Pu em
~
"-..20
>-
>
U 15
0
Cb
~ 10
0
"i
a:
5
00 5 10 15 20 25 30
Effluent / ml
Figure 4. Elution curves for Np, Pu, Am, and Cm
10 7
~~
~
~
~
~
Cm Am ~
~ ii .l
rta! LO
0 LO R~ N
a> co
10 6 I I I ..,
I
""
~ ~~
~~
:x:
~
~
~ :x:
~
~
LOLO LO LO
00 0 0
rr r f+
-
>-
>
U 104
~
Ce
1031 I I I
0 50 100 150
Effl~t/ml
Figure 5. Elution curve of HN03-CH30H system

2-HIB, the anion exchange method with HN03-methanol is superior because

of the large separation factor of Cm/Am reported to be about 3.(7) The
anion exchange method has the additional merits that the separation can
be carried out at room temperature and salt-free samples can be prepared
easily for the a-ray measurements. But on the other hand, the latter is
inferior to the former with respect to the low flow rate of eluent and
the longer time needed for the separation. This disadvantage can be
overcome by use of high pressure liquid chromatography.
The isotopic ratios of Cm and Am were determined by the a-ray and
y-ray spectrometry and the results are shown in TABLE II. The quantity
of 242mAm was determined by analysing the growth of 23 8 Np which was the
daughter of 242mAm.(~) The yields of the nuclides of Cm and Am at the
time of separation were computed by a computer program.(5) For the cal-
culation, ~ and f were chosen as adjustable variables. Values of ~=(2.15
~ 0.20)x10 14 n/cm2/sec and f=0.084 ~ 0.026 were found to reproduce the
isotopic ratios measured within an error of 20.(8,9) The isotopic
ratios, which were calculated using the values of ~=2.1x1014 n/cm2/sec
and f=0.09, are shown in TABLE II.
TABLE II. Isotopic ratio of Cm and Am at the

time of separation
Isotopic ratio Measured Calcula ted *

242mAm/241 Am 0.0116 ~ 0.0017 0.0112
243Am/241Am 0.245 ~ 0.026 0.240
243Cm/242Cm 16.7~ 2.5 16.5
244Cm/242Cm 17.6~2.7 19.65
* ~=2.1x1014 n/cm2/sec and f=0.09
Production of Bk tracers
The two extraction methods give good results with respect to the removal
of Am and Al for the recovery of Bk. However, some fission products as
well as 141,143Ce could not be removed. 105Ru, 99Mo, and 99mTc were the
main impurities in the Bk fraction obtained by the HDEHP extraction. On
the other hand, 97Zr , 97Nb, and 99mTc were the main impurities in the TTA
extraction. In spite of the contamination of the fission products, the
KX-rays of Cm were isolated well enough from the y-rays of the fission
products that measurement of 243,244Bk was not disturbed when a Ge de-
tector was applied to the measurement of the spectrum. Therefore, when
244Bk(t1/2=4.35 h) and 243Bk(t1/2=4.5 h) are used as radiochemical
tracers, the HDEHP extraction method is more suitable than the TTA
extraction because the former is more rapid.
A thick target yield was calculated assuming a homogenous mixture
of 0.385 wt% of Am in Al. The result is shown in TABLE III. For 243Bk
and 244Bk, the emission rate of y-rays had never been determined. So, we
temporarily assumed that the disintegration rates of 243Bk and 244Bk
were equal to the emission rate of Cm KX-rays. For the preparation
of Bk tracers, a 241Am target seems to be more suitable than 2 43Am
target because the former gives a hi~her yield of 243Bk and 244Bk. The
radioactivity of the main product, 2 5Bk, using the latter target is not
high enough for application to radiochemical experiments.
TABLE III. Thick target yield of Bk
Nuclear Energy of a Yield

reaction (MeV) (KBq/IlAh)
241Am(a,n)244Bk 28.2 0.53

241Am(a,n)244Bk 44.7 2.1
241Am(a,2n)243Bk 28.2 0.55
241 Am(a, 2n) 243Bk 44.7 2.7
243Am(a,n)246Bk 48.2 0.07
243Am(a,2n)245Bk 48.2 0.15
243Am(a,3n)244Bk 48.2 2.0
243Am(a,4n)243Bk 48.2 0.3
Stability constants
The distribution ratios were calculated from the solvent extraction data
by an equation:
(1)
where [M]org and [M]aq mean the metal concentrations in the organic and
aqueous phases, respectively. In the presence of a complexing anion, L-
(L=Cl or Br), in the aqueous phase, the complex formation reaction of a
tripositive cation proceeds as follows,
M3+ + xL- ===== MLx3- x ,(x=1, 2, ••• ) (2)
and the stability constant is given as 8x =[MLx3- x ]/[M3+][L-]X. Therefore,

the distribution ratio can be expressed as follows:
D = [M]org/{[M3+] + [ML2+] + [ML2+] + ••• }
= Do /{1 + 81[L-] + 82[L-]2 + ••• }.
The following equation can be derived:
(4 )
where Do is the distribution ratio in the absence of the ligand.

The relation between D and [L-] are shown in Figure 6 and Figure 7.
The values of 81 and 82, shown in TABLE IV, were obtained via equation 4
by least-mean-square fitting(10) to the values of (D o /D)-1 vs [L-] cal-
culated from the data in Figure 6 and Figure 7. --
For the actinoids(III), 81 of the chloro complexes are 0.4-0.6 and
obviously larger than 81 of the bromo complexes. For the lanthanoids-
270 1. SA1'OH E1' AL.
Sm-
-Eu
10° 10-1
Gd ....
10-1 10 0
-Tb
10""' 10
Figure 6. Dependence of D of some lanthanoids on chloride ion(O) and

bromide ion ( ')
(III), S1 of the chloro complexes are also 0.4-0.6 and slightly larger
than 81 of the bromo complexes. But for 82, no significant difference
between chloro and bromo complexes were observed.
Yamada and Tanaka(11) proposed that the complex formation reaction
proceeds by the Eigen mechanism(l£) and the apparent formation constant
K is expressed as follows:
where Kos is an outer sphere formation constant and Kis is a transforma-

tion constant of an inner sphere complex. Fuoss(~) proposed an equation
which has been applied frequently to the calculation of Kos:
Kos = (NV/1000)exp(-u/kT), (6)

THE PRODUCTION OF TRANSURANIUM ELEMENTS 271
-Ac
+-Cm
-Cf
Figure 7. Dependence of D of some actinoids on chloride ion(O) and

bromide ion(')
where V is the exclusive volume of a cation and u is the electrostatic

energy; N, k, and T mean Avogadoro constant, Boltzmann constant, and
absolute temperature, respectively.
This equation gives calculated formation constants for the bromo
complexes of actinoids(III) and lanthanoids(III) of 0.34-0.35 in good
agreement with the experimental values of 8,. On the other hand for the
chloro complexes of actinoids(III), the experimental values of 8, are
obviously higher than the values calculated, i.e. Kos=0.35-0.36. Accor-
ding to equation 5, this implies that an inner sphere mechanism can not
be neglected for the formation of actinoid(III) chloro complexes.
272 I. SATOH ET AL.
TABLE IV. Stability constants of chloro and bromo

complexes
Anion Metal 131 132 Kos

Sm 0.41 :t. 0.04 0.25 :t. 0.03 0.36
Eu 0.52 :t. 0.02 0.22 :t. 0.02 0.35
Gd 0.56 :t. 0.02 0.21 :t. 0.02 0.35
Tb 0.45 :t. 0.02 0.26 :t. 0.02 0.35
Cl- Ac 0.44 :t. 0.02 0.31 :t. 0.02 0.38
Am 0.55 :t. 0.03 0.22 :t. 0.02 0.36
Cm 0.56 :t. 0.03 0.20 :t. 0.02 0.36
Bk 0.59 :t. 0.02 0.25 :t. 0.02 0.36
Cf 0.61 :t. 0.04 0.25 :t. 0.03 0.36
Sm 0.33 :t. 0.04 0.24 :t. 0.03 0.34

Eu 0.38 :t. 0.02 0.23 :t. 0.01 0.34
Gd 0.37 :t. 0.02 0.26 :t. 0.02 0.34
Tb 0.41 :t. 0.03 0.22 :t. 0.01 0.34
Br- Ac 0.42 :t. 0.02 0.29 :t. 0.01 0.37
Am 0.30 :t. 0.03 0.28 :t. 0.02 0.35
Cm 0.39 :t. 0.02 0.22 :t. 0.02 0.35
Bk 0.15 :t. 0.04 0.29 :t. 0.03 0.35
Cf 0.30 :t. 0.04 0.30 :t. 0.03 0.34
SmEu Gd Tb
58 60 62 64 66 68
I • • • •
0.80 ).
(.... -. . - -. --.
~
.
U
- 0.75
o Actinoids
• Lanthanoids
0.70 I I I I
-
90 92 94 96 98 100
Ac AmCmBk Cf
Figure 8. Variation of fc with atomic number

THE PRODUCTION OF TRANSURANIUM ELEMENTS 273
In order to examine the difference in the complexing ability bet-

ween actinoids(III) ,and lanthanoids(III), we calculated the fraction ·of
complex, i.e. fc:f1+f2' (fx is a mole fraction of the species of MLx 3- x
in the aqueous phase) for a [Cl-]:2.85 M. The results are shown in
Figure 8; fc shows a minimum at Cm, which may be due to the half-filled
shell effect of the 5f electrons, while for lanthanoids(III), fc incr-
eases continuously with atomic number. However, the large difference in
the complex formation between the actinoids(III) and lanthanoids(III),
which should be observed in the anionic complex formation and provides
the experimental basis for the group separation, can not be observed in
81 and 82 values experimentally determined in the aqueous system of
ionic stength 3.0 M and [Cl-] ~ 2.85 M.
ACKNOWLEDGMENTS
We wish to thank Dr. K. Ueno of the Japan Atomic Energy Research Insti-
tute for providing the irradiated 241Am. A part of the expenses for
this investigation has been defrayed by a Grant-in-aid for Scientific
Research No.505002 from the Ministry of Education, Science and Culture,
Japan.
LITERATURES CITED
1. Suzuki, S.; Mitsugashira, T.; Hara, M.; Sato, A.; Kawasuji, I.;
Shiokawa, Y.; Kishimoto, M.; Yamamura, Y.; Sci. Rep. RITU, 1979,
A-28 , 64.
2. Ueno, K.; Watanabe, K.; Sagawa, C.; Ishimori, T.; J. Nucl. Sci.
Technol., 1975, 12, 356.
3. Moore, F. L.; Anal. Chem., 1966, 38, 1872.
4. Peppard, D. F.; Moline, S. W.; Mason, G. W.; J. Inorg. Nucl. Chem.,
1957,4, 344.
5. Hara, M.; Mitsugashira, T.; Sato, A.; Suzuki, S.; Sci. Rep. RITU,
1979, A-28 , 41.
6. Choppin, G. R.; Harvey, B. G.; Thompson, S. G.; J. Inorg. Nucl.
Chem., 1956, 2, 66.
7. Guseva, L. I.; Lebedev, I. A.; Myasoedov, B. F.; Tikhomirova, G. S.;
8. Kawasuji, I.; Fukasawa, T.; Suzuki, S.; Radiochem. Radioanal. Lett.,
9. Suzuki, S.; Sato, A.; Hara, M.; Mitsugashira, T.; Kawasuji, 1.';
Kikuchi, H.; Fukasawa, T.; Sci. Rep. RITU, 1979, A-28, 73.
10. Fukasawa, T.; Kawasuji, I.; Mitsugashira, T.; Sato, A.; Suzuki, S.;
BulL Chem. Soc. Jpn., 1981, 55, 726.
11. Yamada, S.; Tanaka, M.; J. Inorg. NucL Chem., 1975,49,55.
12. Eigen, M.; Wilkins, R.; Mv. Chem. Ser., 1965, 49, 55.
13. Fuoss, R. M.; J. Am. Chem. Soc., 1958, 80, 5059.
GEOCHEMICAL STUDIES ON AMERICIUM AND PLUTONIUM IN SOIL
Masayoshi YAMAMOTO, Kazuhisa KOMURA*and Masanobu SAKANOUE*
School of Pharmacy, Hokuriku University, Kanagawa-machi,

Kanazawa-shi, Ishikawa 920-11, Japan
*Low-Level Radioactivity Laboratory, Kanazawa University,
Tatsunokuchi-machi,Nomi-gun, Ishikawa 923-12, Japan
ABSTRACT. Fallout Am-241 and Pu isotopes in soils from various

locations of Japan including Nagasaki and Hiroshima where the atomic
bombs had exploded in 1945 have been measured for studying their con-
tamination levels, distributions, and behaviors in soils.
From these results, it was estimated that the average deposited
amount of Pu-239,240 in soil was 1.5-1.7 mCi/km 2 , and the Am-24l/
Pu-239,240 activity ratio in soil was about 0.3 at present and its
ratio would have a peak of 0.41 in the year of 2033, at which time the
activity of Am-241 would become 0.62-0.70 mCi/km 2 . The studies on the
Nagasaki soils showed that the soils at around Nishiyama area in
Nagasaki City were highly contaminated with Pu-239,240 brought from
the Nagasaki atomic bomb. The contribution of atomic bomb Pu-239,240
to the total Pu-239,240 for the Nishiyama soils was 95-97% from the
activity ratios of Pu-24l/Pu-239,240 and Am-241/Pu-239,240 by comparing
them with those of global fallout. The leaching studies of Am-24l
and Pu-239,240 using the Nishiyama soil highly contaminated with
Pu-239,240 suggested that plausible environmental leaching conditions
might mobilize the Am much more easily than the Pu present in soil.
1. INTRODUCTION
Global contamination of the environment with americium (Am-241) and

various plutonium isotopes (Pu-238,-239,-240 and -241) have been
caused by atmospheric nuclear weapons testing [lJ. Most of Am-241
(an alpha-decay isotope with a 433-yr half-life) detectable in the
environmental samples is not a direct result of the atomic bomb, but
is formed in the environment by the decay of the beta emitter Pu-241,
which has a half-life of 14.4-yr.
The investigation of these transuranium elements in the environ-
ment are of importance not only from the geochemical point of view but
also from the standpoint of heaJth physics. In the terrestrial envi-
ronment, soil is the principal reservoir for these artificial radio-
nuclides and acts as the source of the transport system.
275
276 M. YAMAMOTO ET AL.
This paper presents the estimations of fallout levels and dis-

tributions of Am-241 and Pu-239,240 in surface soils of various areas
of Japan and the variation of Am-241/Pu-239,240 activity ratio with
time in soil. Furthermore, the study includes measurements of the
Am-241 and Pu isotopes present in the soils of Nagasaki and Hiroshima
where the atomic bombs had exploded in 1945. The depth profiles and
leaching characteristics of Am-241 and Pu-239,240 in soil are also
given together with other fallout radionuclide, cesium (Cs-137).
2. SAMPLES AND ANALYTICAL METHODS
Air-dried soil samples sieved through a 2-mm screen were used in this
studies, unless otherwise noted.
After gamma-spectrometric measurement of Cs-137, a 20-50g aliquot
was subjected to analysis for plutonium isotopes (Pu-238 and Pu-239,
240) and americium (Am-241). The sequential separation of plutonium
and americium was done according to the method described by Thein et
al. [2] or Yamato [3], Pu-242 and Am-243 being used as yield monitors.
The alpha activity of each electroplated sample was measured using an
alpha-ray spectrometer with a Si(Au) surface barrier detector.
To determine Pu-241, the amount of Am-241 ingrowth from electro-
plated Pu-241 stored for 2-3 years was measured either by comparing
the new alpha spectrum with the old one or by applying the radio-
chemical separation of Am-241 from the plate.
The determination of the Pu-240/Pu-239 isotopic ratio in some soil
samples was performed using our new method based on the measurement of
LX-/alpha-ray activity ratio using a Ge-LEPS (low-energy photon spec-
trometer) and a Si(Au) surface barrier detector [4].
3.1. The levels and distributions of Am-241 and Pu-239,240 in surface

soils of various areas of Japan
The soil samples were collected from the surface to a depth of 12-20
em at rice-fields of 15 national and/or prefectural agricultural
experimental stations in Japan during 1963-1966 (mostly in 1963) and
during 1972-1976 (mostly in 1976) [5].
As shown in Fig.l and Table I, considerable differences are found
for the integrated amounts of deposited Am-241, Pu-239,240 and Cs-137.
Higher values were obtained for the soil samples from Akita, Niigata,
Ishikawa and Tottori Prefectures located along the Japan Sea coast,
while the lowest values for the soil from Osaka. Generally, the Japan
Sea coast region has 2.5 to 3 times higher values than the Pacific
coast region. The average deposition of Pu-239,240 in Japan was
estimated to be 1.5-1.7 mCi/km 2 (2.8-2.9 mCi/km 2 for the Japan Sea
coast of Honshu and 1.0-1.2 mCi/km 2 for the Pacific coast).
The activity ratio, Am-24l/Pu-239,240, in the "1963" soil samples
ranged from 0.30 to 0.43 with a mean value of 0.34 ± 0.04, which
GEOCHEMICAL STUDIES ON AMERICIUM AND PLUTONIUM IN SOIL 277
(mCl/kJn 2 )
:lF~
°1963 1972
" "
1966 1976
Figure 1. Levels and distributions of Am-241 and Pu-239,240 of

integrated fallout in soils collected from Japanese rice-fields.
The Am-241 data are as of the dates of analysis from the end of 1981
to the beginning of 1982. The propagated counting error of one sigma
are given by the symbol "T" as the highest value on the top of each
bar. (11:Akita,12:Niigata(Joetsu),13:Ishikawa,14:Tottori)
was slightly higher than the mean value of 0.28 ± 0.04 (each value
ranged from 0.22 to 0.34) obtained for the "1976" soil samples.
These values are consistent with the reported data for global fallout
in the soil and the coastal sediment samples [6). A slight decrease
of Am-241/Pu-239,240 ratio may be explained by the contribution of
recent fallout causing low Am-241/Pu-239,240 ratio.
3.2. The time variation of the Am-241/Pu-239,240 activity ratio
The activity of Am-241 in the environment is quite dependent on the

N
--.I
00
TABLE I. Regional average depositions of Pu-239,240, Am-24l and Cs-137 in soils collected
from Japanese rice-fields, and their activity ratios
Concentration (P::i/kg) Deposition (nCijkm2) Activity ratio

Year of
Region Am-241 Pu*
sampling Pu* Am-241 Cs-137# Pu* Am-241 Cs-137 ~ Cs-137
"1963" Japan Sea coast 22.9/3.8 ** 7.6/1.2 1.91/.52 2.9/.8 0.98/.30 242/58 0.33/.02 0.012/.001
Pacific coast 9.2/3.8 3.0/1.2 0.68/.30 1.2/.6 0.38/.19 85/46 0.34/.03 0.014/.002
All area 13.0/7.1 4.4/2.3 1.02/.65 1.7/.9 0.55/.33 128/84 0.34/.04 0.013/.002
Japan Sea coast
Pac~hc coast
2.5 2.5 2.8 2.6 2.6 2.9
"1976" Japan Sea coast 21.2/6.7 5.9/1.7 1.23/3.9 2.8/.9 0.92/.33 163/52 0.28/.04 0.017/.001
Pacific coast 7.6/4.3 2.0/.9 0.44/.25 1. 0/.4 0.27/.10 55/30 0.29/.03 0.017/.002
All area 11.3/7.7 3.2/2.1 0.65/.45 1.5/.9 0.43/.27 85/57 0.28/.04 0.017/.002
Japan Sea coast
Pac~f~c coast
2.8 2.9 2.8 2.9 3.3 3.0
*) Pu: 239,24° Pu . #) P::i/g.

**) The number after slash denotes standard deviation of one sigma: 22.9/3.8 = 22.9 ± 3.8.
The 137Cs data were corrected for decay to the dates of sampling, while the 241Am data are as of the dates of
f::
-<
p
of analysis from the end of 1981 to the beginning of 1982. s:::
p
s:::
o
Cl
t"
..,
P
r
100J
.--;~;;,;~-~
o 0
Jm-241
10
1962 1965 1970 1975 198:>
Figure 2. The time variation of Pu isotopes, Am-241 and Cs-137 in

sediments periodically collected from the central area of Niu Bay,
Fukui Pref.,Japan. The concentrations of Pu isotopes and Cs-137 were
corrected for decay to the dates of sampling, while that of Am-241 is
as of the dates of analysis,May 1981.
elapsed time since most of Am-241 is due to the decay of deposited

Pu-241. To estimate the present or near future level of Am-241, it
is fundamental to know the time variation of the activity ratios of
both Am-241/Pu-239,240 and Pu-241/Pu-239,240 in the past. Therefore,
this work was undertaken to study the activity ratios of Am-241/Pu-239,
240 and Pu-241/Pu-239,240 in the coastal sediment samples collected
during 1964-1978 from Niu Bay, Fukui Pref., and the activity ratio of
Am-241/Pu-239,240 in soil samples collected during 1957-1980 from
Niigata and Akita Prefectures located along the Japan Sea coast [5].
Figure 2 shows the time variation of the concentrations of several
plutonium isotopes, Am-241 and Cs-137 in the sediments from the central
area (maximum depth: 13-15 m) of Niu Bay [7]. From these data, the
Am-241/Pu-239,240 activity ratios at the dates of analysis (May 1981)
were found to show the similar value (mean ratio of 0.30 ± 0.03) re-
gardless to the different dates of their sampling. This fact indicates
that the Arn-241 in the different samples has grown in from its
precursor Pu-241 from nearly the same date for all samples.
The Pu-241/Pu-239,240 activity ratios (R) at the date of the
sampling are shown in Fig.3 for each sample along with their Arn-241/
Pu-239,240 activity ratios (R') corrected to the growth of Arn-241 from
Pu-241 during the period from the sampling to the analysis. The
variations of these two activity ratios with time (t) can be expressed
by the following equations considering decay and growth, respectively:
-k 3 (t-t O)
(R) O· e (1)
(R' ) (2 )
t
where, 0.693 -1
k l = the decay constant of Pu-241 ( y )
14.4
0.693 -1
k2= the decay constant of Arn-241 ( ~ y )
The subscripts t and 0 refer to the ratios at time t and to' respec-
tively. The parameters (R)O' k3 and to were calculated to be 14 ± 2,
0.693/(13.2 ± 0.5) y-l and 1960 ± 1, respectively, by means of
non-linear optimization techniques based on the activity ratios of
Pu-241/Pu-239,240 and Arn-241/Pu-239,240 for the Niu Bay sediment
samples. The solid lines in Fig.3 show the regression curves calcu-
lated for this sediment. The estimated Arn-241/Pu-239,240 ratios for
the soil samples collected periodically during 1963-1980, as shown in
Fig.3, lay on this regression curve. These regression curves are close
to those reported by Bennett [8], as shown by dashed curves after the
year of 1963.
It is estimated from these regression curves that the activity
ratio of Arn-241/Pu-239,240 in soil in 1984 is about 0.3, and will
reach a maximum in the year of 2033 when its activity ratio becomes
0.41, assuming no further atmospheric nuclear testing. The maximum
accumulation of Arn-241 can be predicted to be 0.62-0.70 mCi/krn 2 by
using the average deposition of Pu-239,240 (1.5-1.7 mCi/krn 2 ) in Japan.
3.3. Studies for the soils from Nagasaki and Hiroshima
Based on the above-mentioned experimental results, similar studies

were extended to the soils from Nagasaki and Hiroshima. As is well
known, plutonium was used for the atomic bomb dropped on Nagasaki,
while U-235-enriched uranium was used for the atomic bomb dropped on
Hiroshima.
~
20 Pu-2411Pu-239,240
~
0
a:
~ 10 ,,
;: 8
~
u
""
Am-2411Pu-239,240
0.3
0.2
~ 0.1
~ ,-,
> ~/" '-
::; 0.[5
• : Nlu Boy(sed1Jrents)
"" 1''''''-'
. : Joetsu(rlce-fleld sells)
t
:' 0: Aklta(rlce-fleld sells)
Ci): LI terature Cilta
,I A1IJDStterlc trmsoort Krey et a!. (1970)
1T[l(E1 by Berrett
,/
O. 01 W...I-L...L..J...J-l...L...L...I-L...L..J...J-l...L...L-L...L....L...L...JL....L....L..L-L...L....L...L...JL....L....L..L-L..J
1951 1955 19f{) 19)0 1975 198] 1985
Figure 3. The variation with time of the Pu-241/Pu-239,240 and

Am-241/Pu-239,240 activity ratios in soils or sediments. The
regression lines for the Niu Bay sediment data are given in solid
lines. Also are given in dashed lines the variation with time of
these two ratios estimated by Bennett based on the atmospheric
transport model.
The sampling points for the Nagasaki soils are shown in Fig.4
together with the accumulations of Pu-239,240 and Cs-137 per unit area.
As seen in this figure, extremely high Pu-239,240 accumulation was
found in the soils of the Nishiyama area, which is located 2-4 km from
the epicenter. The accumulation level of Pu-239,240 ranging from 14.1
to 45.1 mCi/km 2 found in the Nishiyama area is higher on an average by
a factor of about fifteen than the values of 1.0-3.7 mCi/km 2 in other
areas. Whereas, the accumulation level of Cs-137 in the Nishiyama
area (98.7-145 mCi/km 2 ) is not so largely different from the levels in
the soils collected from other areas (59.8-135 mCi/km 2 ), indicating
that most of Cs-137 is derived from global fallout and the contribution
of the atomic bomb in 1945 is relatively small.
In order to clarify the contribution of the atomic bomb, it seems
much better to use the activity ratios instead of comparing only the
accumulation levels of the fallout radionuclides. Because the
lro -'9 -i. -~ 2'""i • Cs-I37 50

lLj() Q Q CI Cl CJ Pu-239,2L()
120
_100
11"- 00
u
§ ro
"-
~
~ Lj() 2.0 ~
~ I~ ~ :~ In
I
.~ 2
CI)
u 20 1.0
0 o
2.7 3.5 3.8 4.5 4 10 6 10 8 32 6 261qn
[ E I [§LJ DLJ CLJ [ill ~
Distance and Direction from the Epicenter
Figure 4. Sampling points for the Nagasaki soils and the integrated
deposits of Pu-239,240 and Cs-137 in soils (0-10 cm depth). The
Cs-137 values are corrected for decay to the dates of sampling (1976).
accumulation of fallout nuclides in a given area is influenced by many

causes such as the difference of soil nature, configuration of the
ground surface, local meterology such as the precipitation and so on.
Fig.5 shows the activity ratios of Pu-238/Pu-239,240, Pu-239,240/
Cs-137 and Am-241/Pu-239,240. As shown in this figure, the activity
ratios of Pu-238/Pu-239,240 (0.050-0.062), Pu-239,240/Cs-137
-tf-i)i ---- ------ --------------------------
E~m~-~i~ i-;-;'~fo~~~i-~
;;:;~~~~
0.4 00000 Pu-239,2I()/CS-I37
.3 O.ce
....
E 0.1:6
>0
.; 0.04
!i 0.02
.3
~ 0.3 0.41
l: 0.2
>
.... 0.1
~ 0 IIIII
2.7 28 353.845 4 10 6 10 8 32 6 26jqn
I E I ~[J[]m~ f!I
D1stance and D1rect1on from the Ep1center
Figure 5. Activity ratios of Pu-238/Pu-239,240, Pu-239,240/Cs-137

and Am-241/Pu-239,240 in soils from Nishiyama and other area in
Nagasaki. The propagated counting error of one sigma is given by the
symbollT" as the highest value on the top of each bar. The Cs-137
values were corrected for decay to the dates of sampling (1976), while
the Am-241 values are as of the dates of analysis from the end of 1982
to the beginning of 1983.
(0.15-0.31) and Am-241/Pu-239,240 (0.04-0.05) of the Nishiyama soils

are distinctly different from the corresponding global fallout values
of 0.03-0.04 [1], about 0.02 [5] and about 0.3 [5] ,respectively. The
Pu-240/Pu-239 atom ratios (0.02-0.04), shown in Table II, deviate
significantly from the commonly accepted value of 0.18 for global
fallout. These results indicate that fairly large amount of weapons-
grade Pu having a low Pu-240/Pu-239 atom ratio due to the Nagasaki
atomic bomb still remain in the soils at Nishiyama area. The
contribution of atomic bomb Pu-239,240 to the total Pu-239,240 activity
for the Nishiyama soil has recently been estimated to be 95-97% by the
measurements of Pu-241/Pu-239,240 and Am-241/Pu-239,240 activity
tv
00
...
TABLE II. Atom ratio Pu-240/Pu-239 and activity ratios of some nuclide pairs
in soils collected from Nagasaki and Hiroshima
Activi ty ratio Atan ratio

Location SarrpUng Pu-239,240
SantJle ooncentration
(Depth) date Pu-238 Am-241 Pu-239.240 Pu-240
(pCi/g) Pu-239,240 Pu-239,240 Cs-137 P'ti=239
E-2.8* July 1979 1.380/.030 0.055/.005 0.041/.003*1 0.23/.01 0.031/.012
(0-5 an)
"Nishiyama"
district E-3.5 June 1976 0.337/.009 0.052/.003 0.048/.003*2 0.15/.01 0.034/.010
(Nagasaki) (0-10 an)
E-4.5 June 1976 0.462/.009 0.050/.003 0.051/.003*2 0.19/.01 0.020/.009
(0-10 an)
*3
~-10 July 1983 0.050/.002 0.033/.003 0.090/.010 0.015/.001 0.179/.023
"Black rain"
area (0-5 an)
(Hiroshima) NWN-12 July 1983 0.061/.004 0.036/.002 0.13/.01*3 0.020/.001 0.173/.023
(0-5 an)
*) Direction and distance fran epicenter.

'!he nurrber after slash denotes the propagated oounting error of one sigma: 1.380/.030 '" 1.380 ± 0.030.
'!he 239,240Pu/137csratios were decay oorrected to the dates of sanpling, while the 241Am/239,24°Pu ratios
are as of the dates of analysis: *1) January 1981, *2) March 1983, *3) August 1983. a::
-<
;J>
~
;J>
~
..,o
o
..,m
;J>
!'"'
ratios [10].
By contrast, the soils from Hiroshima did not show, in the
activity ratios among the plutonium isotopes, Am-241 and Cs-137, any
significant differences from global fallout. Therefore, the contri-
bution of the transuranic elements derived from the Hiroshima atomic
bomb was found to be negligibly small as compared with those from
global fallout.
3.4. Depth profiles of Am-24l as compared with those of

Pu-239,240 and Cs-137
The in-situ gamma-spectrometric measurements of environmental radio-

nuclides have been made extensively by using a potable Ge(Li) detector
to evaluate the exposure rates along with the contents of natural and
artificial radionuclides [11] [12]. These results showed that the
accumulation of fallout radionuclides was rather high in the natural
forest or the area just under the eaves of roofs where snow and
rainwater might potentially deposit fallout. In order to investigate
the depth profiles of Am-241, Pu-239,240 and Cs-137, soil core samples
were collected up to a depth of 20-30 em from such three locations,
Kohno (under the eaves of a temple), Oguroi and Kanagawa (from rela-
tively flat area in the forests).
The depth profiles of Am-241, Pu-239,240 and Cs-137 in the soils
from these locations are shown together with their activity ratios in
Fig.6. As seen from this figure, nearly all of the Am-241,Pu-239,240
and Cs-137 were found in the soil layer up to a depth of 20-21 em.
The concentrations of these nuclides decreased smoothly with increas-
ing depth. Over 80% of these nuclides, as seen in Table III, were
retained in the top 10 cm layer of all soils.
A comparison of the activity ratios of Pu-239,240/Cs-137 or
Am-241/Pu-239,240 among each depth fraction of core sample gives us
information about the relative mobility of these nuclides in soils.
As seen in the upper part of Fig.6, the Pu-239,240/Cs-137 activity
ratios have rather constant values for Kohno and Kanagawa samples,
indicating that the behavior of Pu-239,240 is similar to that ofCs-137
in the soil. On the other hand, this ratio has a tendency to increase
with depth for the Oguroi sample. This fact may be explained by the
different mobilities of these nuclides in the soil of this area, that
is, more rapid leaching of Pu-239,240. Alternatively, if the soil of
this area is low in K and clay minerals, enough plant (root) uptake of
Cs-137 retards downward migration.
The Am-241/Pu-239,240 activity ratios in the soil profiles were
found to be in the range of 0.25-0.40 for the Kohno sample and
0.27-0.38 for the Kanagawa sample. These values agree well with the
Am-24l/Pu-239,240 ratios obtained for the rice-field surface soil (see
Fig.3). For the Oguroi sample, the Am-24l/Pu-239,240 ratios increase
from 0.25 to 0.62 with depth, though the measurement error is rather
high in the deeper fractions. As pointed out by other investigator
[13], the greater downward movement of Am-241 relative to Pu-239,240
may cause the increase of the Am-241/Pu-239,240 ratios with depth.
'"
.......
~
"
....,., 0.1
~ ••• +
•••
....u
« •••• ++
0.01
aP-----------------o-----------------------
o 0
o o
,.,.... ---"0 ---- --- -- - - -- -- -0---- --- ----- --00 --- -
""! o 137CS
CI
:::;
U o 0
.:; , 0 e 0
<I)
c: 0.1 --e------- --- - --------- - _..0_ - - --- - e- ---- _<:t -
¢
...2
0
OJ ¢ e e
...c: o ¢ 0 e 21l,2~
o 0 •_. . _________ ~____
___ ~_________________ e _
c e
'"uc: 0.01
0
u • 0 • Oe
o Q• 241M! Cl Q; •
9+ *
t
0.001 0
Kohno Ogurol Kanagawa
~~~~I~I~! , ! ,
a 10 20 3J o 10
20 a 10 20
Depth of soil core sClTllle (em)
Figure 6. Depth profiles of Am-241, Pu-239,240 and Cs-137 in soils,

and their activity ratios. The soils from Kohno,Oguroi and Kanagawa
were collected on Sept. 1978, May 1980 and Oct. 1982, respectively.
The Cs-137 data were corrected for decay to the dates of sampling,
while the Am-241 data are as of the dates of analysis within three
months after the sampling.
However, since most of the environmental Am-241 is grown up in-situ

by the decay of short-lived Pu-241, one must consider the larger
amount of Am-241 derived from Pu-241 in the layer containing old
plutonium. Here, the determination of Pu-241 is desired to clarify
these circumstances.
C'l
rn
o
('l
::r:
rn
~
i'i
;l>
TABLE III. Depth distributions of Pu-239,240, Am-241 and Cs-137 in soils (% of total) r-
'"...,
c::
1:1
R
Kohno (Sept. 1978) Oguroi (May 1980) Kanagawa (Oct.1982) '"o
z
;l>
I£pth ~
DePth Pu* lID-241 Cs-137 Pu* IID-241 Cs-137 Depth Pu* Jm-241 Cs-137 en
(an) (an) (an) :;c
i'i
0-1.5 19.3 22.1 19.7 0-3 43.4 33.9 52.5 0-3 47.4 40.6 45.4
2
~
;l>
1.5-4.0 46.4 45.6 46.8 3-6 26.0 25.5 29.0 3-6 25.6 28.4 25.4 Z
4.0-6.5 24.7 26.3 24.3 6-9 17.6 22.4 13.0 6-9 12.2 16.3 15.4 ...r-1:1
6.5-10 4.8 2.8 9-12 5.7 6.1 2.8 9-12 9.6 10.1
...,c::
5.2 10.2 o
z
10-15 2.8 2.2 2.1 12-15 3.3 5.1 1.4 12-15 3.0 2.8 2.6 2
~
15-20 1. 2 1.0 1.3 15-18 2.1 4.2 0.8 15-18 2.2 1.8 1.0 Z
20-25 0.5 0.4 18-21 1. 9 2.8 0.5 '"op
25-30 0.3
(~~~~2)--;~~-----;~;-----~~~---------------;~~------~~~-----;~~---------------;~~-----~~;-----~~~
*) Pu: 239, 240 Pu •

The 137cs data were corrected for decay to the dates of sampling, while the 241Arn data
are as of the dates of analysis within three IlDnths after the sarrpling.
N
00
--.l
-: 1M -HN03
---:O.lM- HN03
20
4 6 8 10 12 14 16 18
Volurre throwh the soi I column(L)
Figure 7. Dynamic leaching of Am-24l and Pu-239,240 from the soils

collected at Nishiyama (circle symbol) in Nagasaki and oguroi (square
symbol) in Fukui using diluted nitric acid solution.
3.5. Leaching characteristics of Am-24l and Pu-239,240 in soil
To know whether there is any difference in the behavior of Pu and Am

in soil, both column and batch leaching experiments were performed
with diluted nitric acid solution using the Nishiyama soil highly
contaminated with Pu-239,240.
For the column experiment, about 100 g of field-moist Nishiyama
soil was packed into the cylindrical column, and the leaching solution
(lM- and 0.lM-HN03) was fed upward through the column at flow-rate of
200 ml per hour. The effluent was collected in 1000 ml fractions,
and analysed.
For the batch experiment, 10 g of the air-dried soil was suspended
in nitric acid solutions (1000 ml) of various concentrations ranging
from 1M to O.OOOIM. After filtering ( pore size of 0.4S-~ ), both
the leaching solution and the residual soil on the filter were analysed
for Am-24l and Pu-239,240.
The experimental results of the column leaching with lM-HN03 are
Figure 8. Batch leaching of Am-241 and Pu-239,240 from the Nishiyama

soil using nitric acid solutions ranging in concentration from 1M to
O.OOOlM. (Soil: 10 g, Extractant: 1000 ml, Shaking time: Two months,
Temp.: Room Temp.)
shown in Fig.7 together with those with 0.lM-HN03. The data are
plotted in terms of the cumulative percentage of leaching for Am-241
and Pu-239,240. In this figure, the results for the Oguroi soil con-
taminated only with global fallout are also shown for comparison.
The continued leaching with the 17 liters of lM-HN03 solution showed
the high solubility of Am-241 (about 90% of the total) and the low
solubility of Pu-239,240 (about 10% of the total). These results are
similar to the results for the Oguroi soil. Even in the case of the
leaching with 0.lM-HN03' approximately 50% of the total Am-241 was
removed, while the Pu-239,240 was only slightly leached (less than 2%
of the total).
The batch leaching experiments with lM-HN03 removed nearly 85%
of the total Am-241 as shown in Fig.8, and the leaching percentage of
Am-241 was reduced with decreasing concentration of nitric acid.
Below 0.001M-HN03, Am-24l was not significantly leached. On the other
hand, only an about 10% of the total Pu-239,240 was removed with
100
ffi
~ 60
......
§
~
~
Lj()
20 , I
/ ¢' Pu-239,2L()
1~-4 1~-3 1~-2 I~-I I~-O

Ini t1al concentratim of f-Kl:3 (M)
Figure 9. Batch leaching of Am and Pu from the soil prepared by

adsorbing Am-241 and Pu-242 tracers from the solution of pH about 7
followed by air-drying, and the soil containing refractory Pu-239,240
oxide prepared by ignition at 1000°C, using nitric acid solutions
ranging in concentration from 1M to O.OOOlM. (Soil: 0.5 g, Extractant:
50 ml, Shaking time: Two months, Temp.: Room Temp.)
lM-HN03, and below 0.lM-HN03 Pu-239,240 was not leached.

A similar batch leaching experiment was performed using the
following mixed soil samples which contained Am-241, Pu-242 and
Pu-239,240 : a soil sample prepared by adsorbing Am-241 and Pu-242
tracers from the solution of pH about 7 followed by air-drying, and
another one containing refractory Pu-239,240 oxide prepared by ignition
at 1000°C.
The results obtained are shown in Fig.9. The results of Am-241
leaching are very close to the results for the Nishiyama soil shown in
Fig.8, indicating that the Am-241 in the Nishiyama soil is likely to
be present in the form similar to the Am-241 prepared here, probably
adsorbed onto soil as the hydrolyzed or colloidal species. As for
plutonium, high solubility of Pu-242 (about 80% of the Total) was
observed in the leaching experiment with lM-HN03 and its solubility
was reduced rapidly with decreasing concentration of nitric acid.

Whereas, no significant leaching of Pu-239,240 was observed even at
the high concentration of IM-HN03_ These two data are somewhat dif-
ferent from the result for the Pu-239,240 in the Nishiyama soil. The
situation for Pu may be more complicated as compared with that for
Am because Pu is liable to hydrolyze and polymerize. Comparison of
these results with the data for the Nishiyama soil suggests that the
Pu in the Nishiyama soil is likely to be present not as the refractory
plutonium oxide ignited at high temparature, but rather as the hydro-
lyzed forms of Pu which are difficult to be desorbed with weak acidic
solution.
From these experimental results, it seems most reasonable to
conclude that the Am and Pu in the Nishiyama soil are present in dif-
ferent forms, and the Am is more leachable than the Pu. Although the
Am and Pu in the Nishiyama soil were unlikely to be dissolved under
conditions studied at the low concentration of nitric acid solution,
plausible environmental leaching conditions might be expected to
mobilize the Am much more easily than the Pu present in the soil.
These findings may be useful for the radioactive waste disposal
problems.
ACKNOWLEDGMENTS. A part of this work was supported by a Grant-in-Aid

for Scientific Research from the Ministry of Education, Science and
Culture,Japan. We would like to express our thanks to Prof.K.Kodaira,
Ashikaga Institute of Technology, Prof.S.Okajima, Atomic Disease
Institute,Nagasaki University, and Dr.T.Nakanishi,Faculty of Science,
Kanazawa University, for supplying the valuable samples of the
Japanese rice-field surface soils and the Nagasaki soils.
REFERENCES
[1] PERKINS,P.W., THOMAS,C.W., 'Worldwide fallout', in Transuranic

Elements in the Environment (W.C.Hanson,Ed.), pp.53-81. USDOE
Technical Information Center, Oak Ridge,Tenn.,1980.
[2] THEIN,M.,BALLESTRA,S.,YAMATO,M.,FUKAI,R., 'Delivery of transuranic
elements by rain to the Mediterranean Sea', Geochim. Cosmochim.
Acta 44(8), 1091(1980).
[3] YAMATO,A., , An anion exchange method for the determination of
Am-241 and plutonium in environmental and biological samples',
~. Radioanal. Chern. 75,265(1982).
[4] KOMURA,K.,YAMAMOTO,M.,SAKANOUE,M., 'Determination of Pu-240/Pu-239
ratio in environmental samples based on the measurement of LX/
alpha-ray activity ratio', Health Phys. 46(6) ,1213(1984).
[5] YAMAMOTO,M.,KOMURA,K.,SAKANOUE,M., 'Am-241 and plutonium in
Japanese rice-field surface soil', J. Radiat. Res. 24,237(1983).
[6] YAMAMOTO,M. , KOMURA,K. ,SAKANOUE,M., 'Distribution and character-

istics of Pu and Am in soil', in Environmental Migration of
Long-lived Radionuclides, pp.481-489,STI/PUB/59(Vienna,IAEA),1982.
[7] YAMAMOTO,M.,IGARASHI,S.,YOSHIOKA,M.,KITAGAWA,T.,SAKANOUE,M.,
'Transuranic elements in Niu Bay sediments', Health Phys. 46(2),
455(1984).
[8] BENNETT,B.G., 'Environmental aspects of americium', Thesis New
York Univ. ,1979.
[9] YAMAMOTO,M.,KOMURA,K.,HOSHI,M.,SAWADA,S.,OKAJIMA,S.,SAKANOUE,M.,
'Pu isotopes, Am-241 and Cs-137 in soils from the atomic bombed
areas in Nagasaki and Hiroshima', J. Radiat. Res. in press.
[10] YAMAMOTO,M.,KOMURA,K.,SAKANOUE,M.,-'Discrimination of the
plutonium due to atomic explosion in 1945 from global fallout
plutonium in Nagasaki soil', ~. Radiat. Res. 24,250(1983).
[11] SAKANOUE,M.,KOMURA,K., 'Application of in-situ gamma-spectrometry
to the estimation of radiation dose and environmental radioactive
nuclides', Report of Kyoto Univ. Reactor Lab.,KURRI-TR-155,
20(1977). -- - - - -
[12] SAKANOUE,M.,MARUO,Y.,KOMURA,K., 'In-Situ low-level gamma-ray
spectrometry and X-ray fluoresence analysis', in Methods of Low
Level Counting and Spectrometry, IAEA,vienna STI/PUB/592,-- ---
pp. 105-124 (1981-)-.-
[13] ESSINGTON,E.H.,FOWLER,E.B.,GILBERT,R.O.,EBERHARDT,L.L., 'Plutonium,
americium and uranium concentrations in Nevada Test Site soil
profiles', in Transuranium Nuclides in the Environment, IAEA,
vienna,pp.157-173(1976).
PRODUCTION AND RECOVERY OF AMERICIUM-24l
James D. Navratil
Rockwell International
Rocky Flats Plant
P. O. Box 464
Golden, Colorado 80402-0464
ABSTRACT. Nuclear reactors produce mixtures of 24lAm and 242Am.

However, beta decay of 24lpu produces radioactively-pure 24lAm •
Separation and purification processes for 24lAm include ion exchange,
precipitation, and both liquid-liquid and molten-salt extraction.
This paper reviews the principal production and recovery processes.
1. INTRODUCTION
Americium has isotopes with mass numbers between 232 and 247.1 Only
three isotopes have half-lives greater than a few hours: 243Am (7400
yr), 24lAm (432 yr) and 242Am (152 yr). 24lAm decays to 237Np , emit-
ting alpha and gamma radiation. Because of its essentially monoener-
getic alpha and gamma radiations, 24lAm is particularly suited for
use as an excitation source and in a multitude of industrial and
scientific thickness and density measurements. The list of applica-
tions for 24lAm is one of the largest for any actinide isotope.
Nuclear reactors produce mixtures of 24lAm and 242Am. However,
24lAm is a by-product of plutonium scrap recovery operations as it is
produced from the beta decay of the 24lpu present in small quantities
in the 239pu stream. High purity americium oxide has been produced
at the U.S. Department of Energy's Rocky Flats Plant (RFP) since 1962.
The diverse operations at RFP for separating and purifying amer-
icium have included aqueous precipitation, ion exchange and both
conventional liquid-liquid as well as molten salt extraction pro-
cesses. An overview of these production and recovery processes is
presented.
2. PRODUCTION
Americium, atomic number 95, was the fourth transuranium element to

be discovered. l 24lAm was identified by Seaborg, James, Morgan and
Ghiorso late in 1944 at the wartime Metallurgical Laboratory (now
Argonne National Laboratory) of the University of Chicago as a result
293
294 J. D. NAVRATIL
of successive neutron capture reactions by plutonium isotopes in a

nuclear reactor.
Present-day nuclear reactors yield mixtures of americium
isotopes, whereas isotopically pure 24lAm is produced by the beta
decay of the 24lpu present in small quantities in the 239pu stream.
Kilogram amounts of 24lAm are separated and purified by appropriate
chemical processes from plutonium and other impurity elements.
24lAm was first offered for sale in March 1962 at $1500 per gram
by the U.S. Atomic Energy Commission (AEC). The first allotment of
200 grams, offered through the US AEC Isotope Pool at Oak Ridge
National Laboratory (ORNL), came from RFP. In the past, RFP as the
sole source of 24lAm has been supplemented from nuclear fuel repro-
cessing facilities at US DOE Hanford and Savannah River facilities,
and more recently from the Los Alamos National Laboratories plutonium
scrap recovery facility.
3. EARLY AQUEOUS PROCESSES
Production scale plutonium processing commenced at RFP in 1952 and

was based on processes developed at Los Alamos. 2 Originally the only
means of separating the americium from the main plutonium stream was
by precipitation of plutonium with hydrogen peroxide. Americium
contained in the plutonium peroxide filtrate was precipitated with
ammonia or sodium hydroxide and stored until 1959 when it was recov-
ered by a thiocyanate ion exchange process. 3 The thiocyanate process
produced high purity Am02 low in chromium, iron, lead, nickel, plu-
tonium and rare earths. This very inefficient process caused exces-
sive corrosion to process equipment and glove-boxes and generated
considerable aqueous waste. To eliminate the necessity of recovering
americium from plutonium peroxide filtrates, a molten salt extraction
(MSE) process was developed in 1967 to extract americium directly
from aged plutonium metal. 4 ,5 The MSE residue salts (NaCl, KCl and
MgC12) were originally processed through six operations: dissolution
in dilute acid or water, precipitation of the americium and plutonium
with sodium hydroxide, separation of the americium from the plutonium
by anion exchange, purification of the americium through the thio-
cyanate process, oxalate precipitation of the americium and calci-
nation of the americium oxalate to americium oxide.
Through optimization of the MSE process, a sixfold increase in
the MgC12 content of the residue salt resulted. As a consequence,
filtration times for the hydroxide precipitate increased by a factor
of 25. However, by 1975, sodium hydroxide had been replaced by a
cation exchange process and a double oxalate precipitation had
replaced the thiocyanate process. 6
The MSE residues did not contain aluminum, calcium, lead, rare
earths, zinc or other interfering impurities. But the process
changes resulted in Am02 with a purity comparable to that obtained
using the thiocyanate process. This purity met the specifications
(above 95 wt.% Am02 and below 1 wt.% individual contaminant elements)
established by the US DOE Isotope Pool at ORNL.
PRODUCTION AND RECOVERY OF AMERICIUM-241 295
4. MOLTEN SALT EXTRACTION PROCESS
MSE has been used successfully at RFP to remove americium from

plutonium metal since 1967. 4 ,5 The current process places 2 kg
batches of molten plutonium metal in contact with a molten salt
mixture containing 35 mol % NaCl, 35 mol % KCl and 30 mol % MgC12
under an argon atmosphere. The alkali metal salts act as a diluent
and MgC12 reacts with americium according to the reaction
Am + 3/2MgC12 750 °C~ AmC13 + 3/2Mg (1)
A small amount of plutonium is also lost to the salt as PuC13. To
minimize both the plutonium losses and the quantity of salt used, and
to achieve the proper level of americium removal, a two-step counter-
current extraction scheme is used (Fig. 1). The residue salts,
processed by a variety of aqueous methods, are currently the only
recoverable source of americium at RFP.
5. ROCKY FLATS PLANT AMERICIUM RECOVERY PROCESS
The present method of processing MSE residue salt at RFP is outlined

in Figure 2. MSE residues are first dissolved in dilute hydrochloric
acid, and the resulting solution is filtered. After allowing for
acidity adjustments, the filtrate is passed through Dowex 50-x8
cation exchange resin to convert from a chloride to nitrate system
and remove gross amounts of monovalent impurities. 6 The trivalent
actinides are sorbed along with trivalent and divalent impurities.
The loaded resin bed is washed with dilute nitric acid; subsequently
the actinides are eluted with 7M HN03. This eluate is passed through
an Amberlite IRA-938 resin column where plutonium loads on the resin
and americium follows the effluent. Americium in the effluent is
precipitated as the oxalate and calcined to Am02 at 600 °C.
RFP has found the present cation exchange process very efficient
for removing chlorides and relatively insensitive to fluctuations in
process parameters. However, large volumes of acid are required to
elute the plutonium. Use of a macroreticular resin ~Dowex MSC-l)
would decrease the magnitude of this latter problem. Ion selec-
tivity is another problem which results in residual cations such as
calcium, lead, magnesium and potassium being separated from the
plutonium in the anion exchange step but are carried to a limited
extent into the americium oxalate precipitation step.
To replace cation exchange, a carbonate precipitation process is
presently being tested at RFP.8 The actinides are first precipitated
as carbonates 9 and then redissolved in 7M HN03 before being sent to
an anion exchange step. However, the narrow pH range (5 - 6)
required is difficult to control, and calcium and lead contamination
in the americium product create a further problem.
6. NEW SOLVENT EXTRACTION PROCESS
A variety of experimental MSE residues and alloys contain aluminum,

296 J. D. NAVRATIL
Fresh Salt
KCI 89 g
NaCI 69g
MgCI2 97 g
l
Impure Pu Metal f----.
Pu 2000 g Purified Pu Metal
Am 3g r--+ Stage 1
750°C
Stage 2
750°C
--.. Pu 1940 g
Pu02 Variable ~
Am 0.3 g
I
Spent Salt
KCI 89 g
NaCI 69 g
To Aqueous Processing
MgCI 2 97 g
Pu 60 g
Am 2.7 g
Figure 1. RFP MSE process (the asterisk indicates that the salt-to-
metal ratio is variable, depending on the americum content
of plutonium).
r---------
I Proposed :
.. 1 Carbonate L ------,
II L.!,:!c~~a~o~ J I
I
I
Figure 2. RFP americium recovery process.

7M HN0 3 0_35M HN0 3

MSE Wash Eluent
Residues
I
~ ~
Ilissolution- Feed Anion Plutonium
Filtration 1-+ Adjustment r-. Exchange f-+ Eluate
1 ~
Effluent
7M HN0 3
& Wash
H2O 7M HN03
Eluent Wash
Oxalate
t t
Eluate Extraction Effluent
Precipitation- ~ ~ ~
to Waste
Product Chromotography
Calcination Treatment
~
7M HN03 Wash to
Feed Makeup Dr
Waste Treatment
Figure 3. CMP process.
calcium, zinc and other minor impurities such as lead. Because the
present RFP americium recovery process does not effectively separate
these elements, it was necessary to develop a new carbamoylmethyl-
phosphonate (CMF) solvent extraction process.10,11 In this process,
anion exchange and extraction chromatography techniques are combined
(Fig. 3) in the first large-scale application of a bifunctional
solvent extractant in an extraction chromatography mode. The key to
the process is the selective extraction of americium by dihexyl-N,
N-diethylcarbamolymethylphosphonate which is sorbed on an inert solid
support of Amberlite XAD-4 (a non-ionic polystyrene divinylbenzene
resin), manufactured by the Rohm and Haas Co.
Plutonium is removed from the 7M HN03 feed solution containing
actinide and impurity elements by sorption on an anion exchange
process. To selectively sorb the americium, the anion column
effluent and wash solutions pass through the supported CMP extract-
ant. The extractant is then washed with 7M HN03 to remove residual
impurities. Following its elution with water, americium is finally
precipitated from solution as the oxalate and calcined to Am02.
298 J. D. NAVRATIL
That americium can be effectively separated and purified from

impurities such as aluminum, copper, chlorine, fluorine, iron, lead,
magnesium, plutonium, potassium, sodium and zinc was demonstrated by
CMP pilot plant operations at RFP.12 The oxide produced (100 g)
contained 96.5 wt % Am02 with 0.085 wt % Pu and less than 0.15 wt %
of any other individual impurity element. Throughout the trial
period, no significant hydrolysis or radiolysis effects on the separ-
ation materials were observed. Because of the excellent americium
recovery, low waste volumes and the ability to use existing ion
exchange equipment, RFP found this process to be very attractive.
Moreover, by sorbing the relatively expensive solvent extractant on
a support, significantly less solvent inventory is required compared
to liquid-liquid extraction. Furthermore, a small back-up column of
Amberlite XAD-4 support prevents loss of extractant to the aqueous
stream.l 3
Production testing of the CMP process is presently underway at
RFP. The results will determine the length of time the extractant
support will maintain its capacity for americium, the necessary
frequency of hydrolysis product removal by washing with NaOH and the
overall deterioration and degradation of the support.
7. CONCLUSIONS
RFP has played an important role in developing new 241Am separation

and purification processes. These processes, which include both
molten salt and organic solvent extraction, precipitation and ion
exchange, have provided high purity americium oxide to the US DOE
Isotope Pool. The production of americium as a by-product of plu-
tonium scrap recovery operations will continue to require improved
recovery methods, however.
8. ACKNOWLEDGMENTS
This paper was prepared under contract with the US Department of

Energy.
9. REFERENCES
1. W. W. Schulz, The Chemistry of Americium, Rep. TID-2697l, Energy

Research and Development Administration, Washington, DC, 1976.
2. E. L. Christensen, L. W. Gray, J. D. Navratil and W. W. Schulz,

'Present Status and Future Directions of Plutonium Process
Chemistry'. In W. T. Carnall and G. R. Choppin (eds.), Plutonium
Chemistry, American Chemical Society, Washington, DC, 1983, p. 349.
3. V. A. Ryan and J. W. Pringle, 'Preparation of Pure Americium',

USAEC Rep. RFP-130, 1960 (Dow Chemical Company, Golden, CO).
4. J. B. Knighton, R. C. Auge, J. W. Berry and R. C. Franchini,

'Molten Salt Extraction of Americium from Molten Plutonium Metal',
U.S. ERDA Rep. RFP-2365, March 1976 (Dow Chemical Company, Golden,
CO).
5. J. B. Knighton, P. G. Hagan, J. D. Navratil and G. H. Thompson,

'Status of Americium-24l Recovery at Rocky Flats Plant'. In J.D.
Navratil and W. W. Schulz (eds.), Transplutonium Elements -
Production and Recovery, American Chemical Society, Washington, DC,
1981, p. 53.
6. S. G. Proctor, 'Cation Exchange Process for Molten Salt

Extraction Residues', U.S. ERDA Rep. RFP-2347, March 1975 (Dow
Chemical Company, Golden, CO).
7. R. A. Silva and J. D. Navratil, Solvent Extr. Ion Exch., 1

(1983) 824.
8. P. G. Hagan and F. J. Miner, U.S. Patent 3,996,331, 1976.
9. P. G. Hagan, J. D. Navratil and R. S. Chichorz, J. Inorg. Nucl.

Chem., 43 (1981) 1054.
10. J. D. Navratil, L. L. Martella and G. H. Thompson, 'Americium

Recovery and Purification at Rocky Flats'. In J. D. Navratil and W.
W. Schulz (eds.), Actinide Separations, American Chemical Society,
Washington, DC, 1980, p. 455.
11. J. D. Navratil, L. L. Martella and G. H. Thompson, Proc. Int.

Solvent Extraction Conf., Vol. 3, Univ. of Liege, Liege, 1980, Paper
106.
12. W. I. Yamada, L. L. Martella and J. D. Navratil, J. Less-Common
Met., 86 (1982) 211.
13. J. D. Navratil, J. Nucl. Sci. Technol., 18 (1981) 561.

PRODUCTION OF AMERICIUM ISOTOPES IN FRANCE
G. KOEHLY, J. BOURGES, C. MADIC, T.H. NGUYEN, M. LECOMTE

Departement de Genie Radioactif, Service des Etudes de
Procedes, Section des Transuraniens, Centre d'Etudes
Nucleaires de Fontenay-aux- Roses, B. P. n° 6 92260 Fontenay-
aux-Roses, France
ABSTRACT
The program of productions of amerlClUm 241 and 243 isotopes is

based respectively on the retreatment of aged plutonium alloys or
plutonium dioxide and on the treatment of plutonium targets irradiated
either in CELESTIN reactors for Pu-Al alloys or OSIRIS reactor for
pluton ium 242 d iox ide. All the operations, including amer ic ium final
purifications, are carried out in hot cells equipped with remote
manipulators. The chemical processes are based on the use of
extraction chromatography with hydrophobic Si02 impregnated with
extracting agents. Plutonium targets and aged plutonium alloys are
dissolved in nitric acid using conventional techniques while Plutonium
dioxide dissolutions are performed routine at 300 grams scale with
electrogenerated silver II in 4 ~ HN03 at room temperature. The
separation between plutonium and americium is performed by extraction
of Pu(IV) either on TBP/Si02 or TOAHN03/Si02 column. Americium
recovery from waste streams rid of plutonium is realized by
chromatographic extraction of Am(III) using mainly TBP and
episodically DHDECMP as extractant. The final purification of both
ameriCium isotopes uses the selective extraction of Am(VI) on
HDDiBMP/Si02 column at 60 grams scale. Using the overall process a
total amount of 1000 grams of ameriCium 241 and 100 grams of
americium 243 has been produced nowadays and the Am02 final product
indicates a purity better than 98.5 %.
Introduction
The French Atomic Energy Commission is engaged in two programs of

producing americium 241 and 243 mainly to satisfy domestic and foreign
requirements of these isotopes and to contribute to the solution of
the elimination americium 241 from industrial nuclear wastes.
Americium 243 - Curium 244 mixtures were .originally produced by
irradiation of plutonium 239/Al targets in the Celestin reactors at
the Marcoule Plant 111 and are currently being produced by irradiation
of 242Pu02 targets in the Osiris reactor at Saclay.
301
302 G. KOEHL Y ET AL.
Americium 241 is typically recovered from two sources of supply

recycling of aged plutonium alloys or dioxide,
processing of large volumes of alpha active wastes. 121
All the chemical processes for the production and the
purification of these isotopes are carried out in hot cells using
nitric acid media and are performed by means of the liquid-liquid
chromatography (L.L.C.) technique 131 14/.
The total amounts of americium and curium isotopes produced since
the beginning of the program are respectively :
Americium 243 100 grams
Americium 241 one kilogram
Curium 244 100 grams
This paper describes the experience gained over ten years and
focuses mainly on some original processes developed at the pilot plant
scale.
EXPERIMENTAL
Americium 243 and Americium 241 sources

The main characteristics of the targets irradiated to produce
americium 243 are given Table I.
TABLE I
Characteristics of irradiated targets
239Pu/Al targets 242Pu02 targets

Fuel element
Total mass 5445 g 375 g with 360 g Ni
Mass of plutonium 400 g 12.6 g
Dimensions 1067 x 79.7 x 67.1 mm o 22 mm, L 90 mm
No. of elements 11 plates 3 orthocylindrical
containers
Irradiation, Cooling
Reactor Celestin (Marcoule) Osiris (Saclay)
Integrated flux' 11.28 n·kb-1 1.9 n·kb-1
Cooling time 3 years 2 months
Composition after cooling

Actinide mass :
Plutonium 242 44 to 50 g 10.280 g
Americium 243 8 to 10 g 1.600 g
Curium 244 7·5 to 9 g 0.780 g
Fission products
Total mass 340 g 0.560 g
Rare earths 240 ~
~ ,y Activity 3.7x1OCi 150 Ci
PRODUCTION OF AMERICIUM ISOTOPES IN FRANCE 303
A 242Pu02 target element consists of an annular nickel container,

the annular region of which has been filled with 5 g of plutonium
dioxide of isotopic composition exceeding 92 % 242Pu. Irradiated PulAl
targets are generally processed after three years cooling while PU02
targets are processed after one or two months cooling.
Two main sources provided the americium 241 :

Processing of aged stocks of plutonium metal alloys or
plutonium dioxide rich in plutonium 241 on the scale of
300 g of fissile material.
Recovery of ameriCium from alpha aqueous liquid wastes
resulting from the reprocessing of scrap from fabrication of
(U, Pu)02 fuels.
The annual volume of these liquid wastes are estimated to be

several tens of m3 of highly varied chemical composition. The
compositions of two americium 241 liquid wastes are given Table II.
TABLE II
Characteristics of alpha wastes solutions
Component VALDUC criticality station HASURCA
HN03 (N) 7.85 1• 1

Uranium 2 12
Neptunium 0.18
Plutonium 0.50 0.07
Americium 2.36 0.108
Iron gil 9.2 11. 1
Cadmium 35.4
Nickel 4.5 1. 0 1
Chromium 4 1.5
Gadolinium 0.07
Cerium 144 ~ * 0.28
Ruthenium 106 mCil1 * 1.34
Cesium 137
* At very low concentration.* 9. 1
Hot Cells.
The equipment and operation of the Hot Cells have been described
in detail in a previous paper 131, so the working principles will only
be summarized here :
Nitric acid is used to minimize corrosion of stainless steel
equipment.
The dissolution of irradiated targets are performed and the high
beta-gamma activity cycle in the hot cell named Petrus,
surrounded by 80 cm of barytes concrete. The process for the
medium beta-gamma activity cycle is carried out in Candide, a hot
cell shielded with 15 cm of lead.
304 G. KOEHL YET AL.
The recovery and purification of americium 241 from waste

solutions is carried out in hot cells shielded with 10 cm of
steel: Castor, Petronille and Irene.
Dissolvers
243Aro production
The irradiated targets are dissolved as indicated :
For Pu/Al: in Uranus 55 stainless steel dissolver of 50-liter
capacity using nitric acid with traces of mercuric
ions.
For PU02 in a tantalum dissolver of 4-liters capacity using
nitric acid and traces of HF.
To handle safely the various gaseous products that escape during

the dissolution, the Uranus dissolver is equipped with soda lime,
charcoal and iron filings absorbers, and the tantalum vessel with
charcoal and silver zeolite columns for iodine trapping.
241Aro production
Plutonium alloys were generally dissolved in a tantalum reactor
under reflux conditions with 14 M HN03, 0.05 M HF, while pure
plutonium dioxide and plutonium metal scrap, previously converted to
oxide by calcination in air at 500-600°c, were dissolved at room
temperature in an electrolytic dissolver by electrogenerated
silver(II) as described in the next paragraph.
Plutonium Oxide Dissolution with Electrogenerated Silver(II).
Recently, Bray and Ryan 151 elucidated the conditions needed to

perform a Pu02 dissolution with electrogenerated strong oxidizing
agents such as Ce 4+, C03+, Ag2+, in nitric acid solutions free from
fluoride ions. For our own purpose, the principle of a Pu02
dissolution with Ag2+ was found sufficiently attractive that an
extensive parametric study of this technique was undertaken. That
study demonstrated that it was possible to define the experimental
conditions to perform a quantitative plutonium dioxide dissolution
with a current efficiency, equal to unity 16/. An experimental reactor
that allows the dissolution of 300 g. of pure aged plutonium dioxide
per day has been tested and determined to be useful to the americium
production program.
The plutonium dioxide dissolution with Ag(II) at the 300-gram

scale is typically performed under in the following chemical
conditions :
Nitric acid 4M
Temperature 30 ~ 10°C
Silver concentration 0.05 ~
Current density 35 mA.cm- 2
The dissolver used for this technique is a 3.5-liter-capacity
glass electrolyzer composed of two separated compartments :
An anodic compartment equipped with a platinum grid having a

surface area of 850 cm 2 .
A cathodic compartment consisting of a 0.2-liter-capacity

aluminum silicate diaphragm in which is immersed a tantalum rod
6 mm in diameter.
The heat generated by the electrolysis is removed by a coolant
flowing through a glass coil. The plutonium dioxide powder and the
anolyte solution are vigorously stirred by a teflon propeller driven
by an electric motor. The electrolytic dissolver is also equipped with
a temperature sensor to control the cooling unit dissolver and with a
liquid draw-off line.
Chromatographic equipment
The chromatographic equipment includes: a plexiglass column

packed with a stationary phase impregnated with a suitable extractant,
positive-displacement proportioning pumps of Prominent Label, storage
tanks for various solutions and a detector for in-line analysis at the
column outlet.
As a rule, the L. L. C. columns are discarded after use. The dry
packed columns are placed in the hot cell where they are pre-
equilibrated with solutions that displace the air and produce the
chemical conditions for extraction. When a column has been used to the
point of a 50 % decrease in exchange capacity, it is dried with
compressed air, cut into sections and removed as solid waste.
Our studies have been directed toward the application to L. L. C.
of pure compounds for which extraction properties are well known as a
result of prior use in liquid-liquid extraction processes.
The preparation and characteristics of the stationary phase was
reported in references 131 and 14/, so, the characteristics of typical
columns used for actinide extraction will only be summarized in
Table III
306 G. KOEHLY ET AL.
TABLE III
Characteristics of liquid-liquid chromatographic (L.L.C.) columns

used in extraction of uranium, plutonium, and americium.
Stationary phase Extracted compound Exchange Exchange

(%) capacity capacity (g)
by weight mole.kg- 1 for actinides
(2.8 kg column)
U02(N03)2(TBP)2 0.507 337

TBP (27 %) Pu( N03)4(TBP)2 0.507 339
Am( N03)3(TBP)3 0.338 222
TOA (25 %) Pu(N03)6(TOAH)2(TOAHN03)2 0.177 119
Pu( N03)4(POX 11)2 0.433 290

POX 11 (30 %)
Am( N03)3(POX 11)4 0.216 145
DHDECMP (30 %) Am(N03)3 (DHDECMP)3 0.275 185
HD(DiBM)P (30 %) Am°2(D(DiBM)P2(HD(DiBM)P)2 0.214 144
TBP = Tributylphosphate
TOA Trioctylamine
POX 11 = Di-n-hexyloctoxymethylphosphine oxide
DHDECMP = Di-hexyl di-ethyl carbamoyl methylene phosphonate
DH(DiBM)P = Bis-2.6-dimethyl-4-heptyl phosphoric acid
'1;j
Nitric eluate tram TBP column :<l
50 < Americ ium < 60 9 o
t:l
Feed
?3
..,
AmVI 2 5 9.l-1
5
0.3 M HN03 2.10- 2 M H3 PO. z
10-2 M [Ag] 0.1 M K2 52 08
o'll
;..
a::
m
:<l
Washing Elution ()
0.3 M HN03 0.5 M N2 H. N·O)
;:::
10-2 M HJ PO.
a::
1 N H N 03 en
HN03 1 0-3 [ A9] ..,o
a.1M K?S,O o'1;j
D m
i '"Z
B
M 'll
5.5 M K2 COJ Oxidizing solution :<l
;»
1.4 M HNO) 2.10-2 M H3 PO. P
0.25 M K2S20a R
10- 3 M Ag "V 1(}2M [A9] 0.25M K2 5 1 0 S m
Ln ill, CmlIl4 I
3
H20
1 N HCl
Carbonate effluents ' - - -......- .........., Heating to 50° 1-1_ _. . . . .
AmV_AmVI
Fi ltration Ag Cl
Ln III + Am '" 50 - 100 mg.l- 1
3 - 5 l NH40H
Oxalate
Figure I - Americium purification process combining precipitation of potassium americyl carbonate

and Am(VI) l.L.C. extraction w
o
....,
w
o
00
I Dissolution t.M HNO) 0.1 M HAN I 0.5 M H2 SO, J

I I J I 0.1 M HN03 0.1 M HNOJ
1 1 Pu N L LC with TBP
1 Pu Pu to
Filtration o xa late
or TOAHNOJ E l u ate prec i p itatior
[Al (NO]h-.(OH).l
t
FR@d adj ustment J
8 M Li N03 JI 17M Li NO]
I DTPA 0.1 M pH 1.7
t ~ .-
Co@xtradion Lnm, Cmm,Amm Ln m Eff lu ent
to waste
LLC with T8P treatment
Cm, AAl, Lnrn
~ TBP chromatography I J Fe, Co,Ni J

reconditioning c yde J -, to waste
Cm ,Am, Ln
Oxidizing J Cm ill /Lnrn LLC Cm to
solution Cmill + Lnrn o x alate
with TBP p red pitutio~
~ 1
+
K3 Am02(C~
precipitation
Am 0/+ Am 0 2 2+ LLC Am to
o x a l ah
~ with
o;.:
HD(DiBM)P prKipitation o
tTl
::c
t'"
><:
tTl
""i
Figure 2 - Conceptual PLOWSHEET for chemical treatment of Pu-Al and Pu<>2 targets ;.-
"
Am(VI) Extraction Chromatography Process
This process is based on a combination of two processes : the

precipitation of potassium americyl carbonate, first described at the
mul tigram scale by Burney 17/, and the Am( VI) extraction chromato-
graphy by HD(DiBM)P solvent discovered by Peppard /8/ and applied
first in L.L.C. to americium 243 at the multigram scale /1/.
The steps of the process, which is illustrated schematically in
Figure 1 and routinely carried out at the 50-gram scale are the
followings :
Precipitation of potassium americyl carbonate in 3.5 ~ K2C03
solutions at 80 ~ 10°C by addition of K2S208 /5/.
Dissolution of the water-washed precipitate with an oxidizing
acid solution containing K2S208 and Ag(II) ions acting as a
catalyst in the oxidation of Am(V) to Am(VI) by S2082- ions.
Total conversion of Am(V) to Am(VI) by warming the resultant
solution to 50°C and checking the oxidation quantitativity by
spectrophotometric measurement.
Rapid Am(VI) extraction on a HD(DiBM)P column previously treated
by an oxidizing solution containing S208 2 - and Ag(II) ions until
a persistent dark color of Ag(II) ions is observed in the
effluent.
Slow elution of Am(VI) from the column by a reducing solution
0.5~, N2H4N03, 1 tl, HN03 (after oxidizing washes eliminate the
impurities).
Under ideal conditions, the americium is recovered in 2.5 to
3 liters of eluate.
Analytical control~
In addition to the routine controls, Q and y counting and spec-

trometry are used as well as in-line gamma detectors /3/ monitoring
the operation of the chromatographic columns. The quality of the final
products (Am02 or Cm02) is determined by mass spectrography and
calorimetry.
The oxidation of americium to Am( VI) is controlled by a Hewlett
Packard 8450 A spectrophotometer.
Processing of irradiated targets
The production of ameriCium 243 and curium 244 was initiated

around 1970 by the irradiation of Pu/Al targets. The chemical
processing of the industr ial targets /3/ has generated a stock of
400 grams of plutonium 242 of average isotopic purity around 90 %
which now supplies a high isotopic purity americium 243 by irradiation
of 242Pu02 targets.
The conceptual flowsheet for the chemical processing of both
types of targets (Figure 2) is the same.
310 G. KOEHL YET AL.
After nitric acid dissolution of the targets (see Tables I and

II), the first step of the process is the recovery and purification of
plutonium 242 which is accomplished by extraction chromatography using
TOAHN03 or TBP columns. To prevent clogging of the columns by solids
(essentially fission product precipitates) the feed solution is
filtered through a small pre-column containing a silica bed.
After the column is washed with nitric aqid solution, the elution
of plutonium 242 is performed with sulfonitric acid for TOAHN03 or
hydroxylammonium nitrate (HAN) reducing solution for a TBP column. The
plutonium eluate undergoes the classical procedure of PuC IV) oxalate
precipitation to obtain plutonium dioxide after calcination of the
oxalate. The second step of the process concerns the separation of
americium-curium from lanthanides, which is performed on a TBP column
in high nitrate medium using DTPA. The L.L.C. TBP process III 131 141
implies three successive stages :
Coextraction of lanthanides and americium-curium trivalent
elements on a TBP column from a feed solution previously adjusted
to 0 ~ 0.05 free acid and to 1.8 ~ in AI(N03)3 by use of aluminum
nitrate solution deficient in nitrate ion (AI(N03)3-x (OH)x.)
Elimination of certain fission products: (e.g. Ru, Cs) by
scrubbing the column with 8 ~ LiN03 salting-out solution.
Sequential elution of curium and americium by 7 ~ LiN03, 0.1 ~
DTPA, pH 1.2, permitting the collection of curium, americium,
europium and cerium. (in order of appearance).
As the intergroup separation factor is not sufficiently high Ill,

complete decontamination of the mixture of americium and curium from
lanthanides necessitates several cycles using 7 ~ LiN03 , 0.1 ~ DTPA,
pH = 1.2 elution solution. A new TBP cycle can be carried out from a
previous eluate by neutralizing the complexing power of DTPA by
addition of 0.5 ~ AI(N03)3.
The separation of americium 243 from curium 244 constitutes the

third step of the process. This separation can be accomplished either
by the L.L.C. TBP process or by precipitation of potassium americyl
carbonate. However, as the final americium purification is performed
by Am(VI) extraction, the americium-curium separation is preferably
done by precipitation of K3Am02(C03)2 which supplies a suitable
product for the Am(VI) L.L.C. process. The L.L.C. TBP process is
mainly used to purify curium. The purity of the americium 243 ranges
from 97 to 98 %.
The processing of Pul Al target by means of the L. L. C. technique

does not involve major problems and is typically accomplished in a
three month campaign. The overall process starting from 88 liters of
dissolution solution generates around 250 liters of highly salted
liquid wastes. The overall actinide recovery is 96 %. The amount of
insolubles during dissolution is estimated to be less than 2 %. In
comparison, the Pu02 target processing, which was expected to be
easier to perform because of lower initial concentrations of
lanthanides, encountered two major difficulties :
'"0
;;0
o
t:1
C
()
...,
(3
Z
o'"!1
;..
;;::
Pu Extraction r.1
3 Pu ;;0
D i sso l uti on chromatography Eluate n
with T8P c;;::
r;;
...,o
o'"0
r.1
Ul
Z
H2 0 '"!1
;;0
Eluant ;..
Z
()
r.1
Efflu ent To AmMand K

Am carbonate
to waste OR Eluate precipitation
Am(ID) extracti on
t r e atmt'nt ..,.;E-------- chromatography
with DHDECMP O.SM
Eluant
Am to oxa late
precipitation
and calcination
Figure 3 - Conceptual flow diagram for recycling of aged plutonium alloys on plutonium dioxide
Potential releases of radioactive iodine outside the hot cell

during the dissolution step must be monitored.
The presence of high nickel concentration in solution (1.7 tD
ahead of the first cycle of americium and curium extraction
complicates the adjustment of the feed solution to 0.0 :t 0.2 H+
and 1·7!:1 A13+.
The main advantage of conducting the final americum 243 purifi-
cation by the Am02 2+ L.L.C. process is to obtain nearly complete
decontamination of americium from curium and trivalent lanthanides.
However, poor decontamination factors of americium from plutonium and
cerium (144Ce) are observed in this process, since both elements are
extracted on the HD(DiBM)P column (Pu02 2 + for Pu, Ce(IV) for Ce)
during the fixation step and are recovered with the americium during
the reducing elution (partially in the case of plutonium). Therefore,
traces of plutonium and cerium should be eliminated in prior steps
before using this process.
Recycling of aged plutonium alloys or plutonium dioxide
A total amount of 5 kilograms of plutonium alloy or metal scrap

or plutonium dioxide containing 5 % of americium by weight has been
recycled according to the flow diagram shown in Figure 3.
An example of the kinetics of the dissolution of 300 g of Pu02 is
presented in Figure 4. Quantitative dissolution of this PU02 is
obtained in about 210 minutes; this corresponds to an average current
efficiency of 56 %.
After dissolution : the resultant solution undergoes a filtration

and a chemical reduction by H202 to adjust the plutonium to the
tetravalent state. Aluminium nitrate is added to complex excess
fluoride when the dissolution is performed with HF. Pu(IV) is
extracted at the 300 g-scale on two TBP columns in series
(2.7 kilograms each). Americium passes through the columns during this
step. After washing the columns, the plutonium is eluted with a
reducing solution of 0.05!:1 HN03, 0.5!:1 HAN, and 0.1 !:1 N2H5N03 at
50°C. The plutonium eluate is acidified then heated slowly to 60°C in
order to destroy excess reducing agents and to oxidize plutonium(III)
to plutonium(IV). Plutonium is converted to the oxalate form by
precipitation at 60°C. The oxalate is converted to oxide by calci-
nation at 500-600°C for 4 hours. The plutonium losses are minimized by
systematically concentrating and recycling the effluents.
The raffinate containing the ameriCium is concentrated by a

factor of ten by evaporation of the effluents to provide a stock of
concentrated americium solution which is periodically treated by the
L.L.C. technique using either TBP or DHDECMP as described in the next
paragraph.
This recycling of aged plutonium has resulted in the production
of 250 grams of americium 241.
PRODUCTION or AMERICIUM ISOTOPES IN rRANCE 313
100,---------------------~--------------~~o-----o_,
Cl
lLi
>
-l
o
~ 75
Cl
f-
Z
lLi
U
a::
lLi
a..
50
25
o 30 60 90 120 150 1ao 210 240

ELECTROLYSIS TIME (mn)
Figure" - Pu02 dissolution with electrogenerated Silver II
Experimental conditions
PuOz 295.5 g 30 ± 0.1 A V = 5V T
Anolyte solution
4 M HN03 0.1 MAg Volume 3.5 liters
Catholyte solution
8 M HN03 Volume 0.2 liter

MASURCA VALDUC -..,.
An Others An Others
- - ---
U Cd U Fe
Np Fe Pu Ni
Pu Ni Am Cr
Am Cr FP
FP
Np, PU,Am
'---,_ _ _ _ _.,--'. Cd, Fe,Ni. Cr, FP
I
I Cd, Fe, Ni, FP.
U I
I
L.. _.!~~m__ _ Pu extraction
Fe,Ni, Cr, FP. with TBP
--------8
Effluents
to
wastes
Am to
tinal
o
~
purificat ion o
:Tl
=
r
-<
...,m
Figure 5 - Coneeptual now diagram for deeontamination of alpha liquid wastes ;..
!""
Recovery of americium 241 from alpha aqueous wastes
The objective of the waste treatment is first, the elimination of

alpha emitters from the waste and second, the recovery of
americium 241. The conceptual flow diagram for both types of liquid
waste (Table III) is presented in Figure 5. As the chemical process
flowsheet for Masurca wastes has been described earlier 13/, we shall
only discuss the major principles here in dwelling on the three
extractants tested in L. L. C. techn ique for Am (I I I) extraction : TBP,
POX 11 and DHDECMP, an extracting molecule developed in the V.S.A. 191
110/.
Because the uranium and plutonium present in such effluents
generally exhibit a higher affinity for these extractants than
amenclUm, their prior elimination is necessary. The V + Pu coex-
traction is performed with TBP either by liquid-liquid extraction in
mixer-settlers when the V + Pu concentration is high (V = 12 g.1-1 for
Masurca wastes) or by L. L. C. when the exchange capaci ty of the TBP
column is sufficient (as for Valduc criticality station wastes).
This operation does not require prior feed adjustment because the
acidity and nitrate ion concentration of the wastes are sufficiently
high. After elimination of V + Np + Pu from the liquid wastes (neptu-
nium present in Masurca wastes requires a special extraction cycle)
the Am( II I) extraction chromatography by the above three extractants
requires that the feed solution to be adjusted to the chemical
conditions given in Table IV.
TABLE IV
Usual chemical conditions for Am(III) extraction chromatography
Extractant Feed solution adjustment kD Am(I I I)

(ml.g- 1 )
TBP 1.8 M Al( N03)3 0.00 ~ 0.02 M H+ 200
POX 11 3.6 !:1 LiN03 0.1 M HN03 5x10 3
DHDECMP 5 !:1 HN03 25
However the above chemical conditions for efficient amerICIum

recovery were found inadequate for the treatment of Masurca and Valduc
liquid wastes containing high concentrations of hydrolyzable cations
such as fe(III) , Ni(II), Co(I1), and Cd(II). Nevertheless, comple-
mentary studies demonstrated :
L. L. C. with TBP could be performed if the neutralization of the
feed solution to a free acidity around zero is done in the
presence of DTPA or ammonium oxalate in equal concentration to
the hydrolyzable cations (fe, Ni, Co). The hydrolysis of cations
is indeed suppressed and the kD Am(III) value of 100 is preserved
in presence of high aluminum nitrate concentration.
316 G. KOEHL Y ET AL.
L.L.C. with POX 11 is efficient in the presence of large amounts

of iron(III) if EDTA has been added in equal concentration to the
Fe(III). This avoids the slow extraction of Fe(III) by POX 11 and
restores all the extractive properties of POX 11 for Am(lII) 13/.
L.L.C. with DHDECMP can be used to extract trivalent americium
from moderate volumes of 5 to 7 M HN03 in spite of the relatively
low maximum kD value of Am(III). If americium recovery from
larger volumes is required, it is necessary to increase the kD
Am(III) value by adding a salting-out agent such as LiN03 and by
simultaneously lowering the acidity of the feed solution 111/. In
related studies, investigations have shown that the exchange
kinetics is faster in L.L.E. than in L.L.C. For instance,
equilibrium is reached in two minutes in liquid-liquid extraction
in HN03 or LiN03 salted medium but may require ten minutes in
L.L.C. (DHDECMP 0.82 M/Si02) with the same media.
In spite of complicated feed solution adjustments, POX 11 and TBP

extractants used in the L.L.C. technique have worked out
satisfactorily for americium recovery from 4 m3 of Masurca wastes and
0.4 m3 of Valduc wastes. In a period of two years working at a normal
pace, six chemist-technicians have recovered 1.020 kg of
americium 241. Both processes have produced a total amount of 8 m3 of
highly salted waste solutions containing less than 1 mgll of
americium: the acceptable release limit for a subsequent waste
treatment. The L.L.C. with DHDECMP absorbed on Si02, tested
episodically on the first americium recovery cycle from Valduc wastes,
was found inadequate because of its relatively low extraction power
and its slow exchange kinetics. But DHDECMP in L.L.C. was much more
effective in americium recovery from reacidified carbonate effluents
resulting from the potassium americyl carbonate precipitation process.
Generally, a second cycle of Am(III) chroma-tographic extraction with
TBP was necessary to improve the amerlClum decontamination from
hydrolyzable cations such as Fe, Co, Ni, Cd, etc ... before proceeding
to the final americium purification by Am022+extraction.
The final americium purification, beginning with the process

combining K3Am02(C03)2 precipitation and Am(VI) L.L.C. extraction,
routinely performed at the 50-g scale as illustrated in Table V, has
required the attainment of the following experimental conditions :
The Am(III) chromatographic extraction preceeding the potassium
americyl carbonate precipitation must be efficient enough to
leave in the Am(III) eluate low concentrations of transition
elements able to form insoluble hydroxides or carbonates which
could hinder Am(III) solubilization in potassium carbonate
medium.
The correct Am022+ chromatographic extraction procedure requires
that the Am(V) present in K3Am02(C03)2 be quantitatively oxidized
to Am(VI) by an oxidizing acid dissolution and the subsequent
Am(VI) extraction be carried out rapidly to limit the radiolytic
reduction of Am(VI) to Am(Vi or to Am(III) in americium 241
concentrations such as 25 g.l- .
VOLUMES OF SOLUTIONS MASS OF 241 AMERICIUM
241Am Feed Wash Elu- Recondi-Fixa- Wash Recondi- Puri- Puri-

Expe- tion tioning tion tioning fied cation
riment feed loss loss loss weight yield
No (g) (l) (l) (l) (l) (g) (g) (g) (g) (%)
39.47 2.0 3.2 0.690 0.66 38.29 97

2 46.5 1.75 1.3 5.68 4 1.39 3.22 0.230 39.78 85
3 55 2.18 1.70 3.39 5 1.36 4.87 0.160 49,59 90
4 36.35 1.50 0.80 3.86 1.37 2.71 31.32 86
5 50 2.0 1.35 5.13 4.3 0.262 1,02 0.242 49.50 99
6 33.3 2.25 1.25 4.48 3.1 1.016 3.26 0.564 28.46 85
7 59.1 1.8 1.50 3.50 3 2.28 5.68 0.702 48.10 81
8 51.35 1.65 0.40 4.20 3 0.850 1.46 1.260 51.80 100
9 58.88 1.90 1.20 3.20 4.5 3.09 6.08 1.340 49.47 84

10 76.15 3.5 1.55 5.08 5.37 8.28 - 62.29 81
TABLE V
Am022+ extraction chromatography on HD(DiBM}P column

Characteristics of columns used :
- in runs 1 to 4 = 0,8 kg column
- in runs 5 to 9 = 2,9 kg column
Flow rates feed and wash 5 to 10 1,h- 1 Elution 0,5 1,h- 1
The average yield of the potassium americyl carbonate

precipitation process was found 99.5 % while the Am022+ L.L.C. yield
has fluctuated from 80 to 100 % in spite of the above experimental
precautions. The americium losses which occur mainly in the fixation
and wash steps, were linked to incomplete oxidation and to radiolytic
reduction of Am02 2+ to Am02+ and Am3+ as detected by in-line
spectrophotometric measurements.
In other studies, HD(DiBM)P adsorbed on Si02 at 30 % by weight
was found to retain a small fraction of the Am022+ randomly
fluctuating from 0.5 to 2 %as observed in a number of chromatographic
runs (Table V).
The subsequent steps of the americium 241 final purification

include :
Americium hydroxide precipitation by NH40H after elimination of
Ag+ by heating the eluate reducing solution at 60°C (see
figure 1).
The conventional Am(III) oxalate precipitation /12/.
The conversion of Am(III) oxalate to Am02 by calcination of the
oxalate in a furnace at 800°C for 4 hours.
The above final steps involve a minimal loss of amerlClUm of

0.1 %, attributed to a slight amerICIum carrying during AgCl
precipitation and a slight solubility of americium in ammoniacal
effluents (2 to 10 mg/liter).
The americium 241 purity, as determined by calorimetric

measurements on weighed samples of 70 to 100 mg, was found to average
better than 99 %.
CONCLUSIONS
Initially recovered from irradiated Pu-Al targets, americium 243

is now produced by processing irradiated 242Pu02 targets. The
chemical processing of both types of targets, performed mainly by
extraction chromatography, remains the same. However, PU02 target
dissolution provides moderate solution volumes with small quantities
of fission products and permits a reduction in the processing time and
a decrease in the size of the equipment. The typical isotopic purity
of americium 243 products has increased from 96 to 99.2 % by weight.
The pr incipal sources of supply of amer icium 241 have been and
remain alpha active and aged plutonium scrap. Most of the chemical
processes involve liquid-liquid chromatography operated on the scale
of 100 grams of actinides. The L.L.C. technique was found quite
appropriate for our requirements : most of our personnel work a normal
schedule and the equipment is simple and light and easy to manage
(easy to discard or to maintain). During the previous decade, several
extractants, such as TBP, POX 11, DHDECMP, and HD(DiBM)P, have been
tested for americium 241 recovery and purification at the 50 gram

scale. Conventional TBP and POX. 11 extractants were found effective
for Am(III) recovery (yield 99.3 %) but generate problems for liquid
waste management. The D~DECMP molecule, which theoretically allows
direct Am(III) extraction from high nitric acid effluents, did not
work out properly in the first cycle of americium recovery from highly
salted effluents. This extractant adsorbed on Si02 exhibits moderate
extraction power for Am(III) and slow adsorption/desorption kinetics.
The HD(DiBM)P has proved to be a reliable extractant in the final

americium purification when the quantitative oxidation of americium to
the hexavalent state was ensured.
The main progress in americium technology has been the
development of two original processes :
The Am(VI) chromatographic extraction with HD(DiBM)P at the 50-
gram scale assures the purity of the americium product.
The rapid and quantitative plutonium dioxide dissolution using
electrogenerated silver( II), now performed at the 300-gram scale
in Fontenay-aux-Roses, appears to be a promising technique for
industrial applications.
LITERATURE CITED
BOURGES, J.; MADIC, C.; KOEHLY, G.; A.C.S. Symposium Series
117, (1980) 83.
2 MADIC, C.; KERTESZ, C.; SONTAG, R.; KOEHLY, G.; Separation
Science and Technology 154 (1980) 745.
3 KOEHLY, G.; BOURGES, J.; MADIC, C.; SONTAG, R.; KERTESZ, C.;
A.C.S. Symposium Series 161, (1981) 19.
4 MADIC, C.; BOURGES, J.; KOEHLY, G.; IAEA TC 518 (1984) 14.
5 BRAY, L.A. ; RYAN, J.L. ; Actinide Recovery from Waste and
Low grade sources. Navratil, J.D. SCHULTZ, W.W. Eds.
Harwood Academic Publishers - New-York (1982), 129
6 Commissariat a l'Energie Atomique - Brevatome N° 84.4766
March, 27th, (1984) Patent.
7 BURNEY, G.A.; Nucl. Appl. (1968) 217.
8 MASON, G.W.; BOLLMEIER, A.F.; PEPPARD, D.F.; J. Inorg. Chern.

32 (1970) 1011.
9 Mc ISAAC, L.D. ; BAKER, J.D. ; KRUPA, J.F. ; MEIKRANTZ, D.H.

; SCHROEDER, N.C. "A.C.S. Symposium Series 117, (1980), 395.
10 KNIGHTON, J.B. ; HAGAN, P.G. ; : NAVRATIL, J.D. ; THOMPSON,

G.H. ; ACS Symposium Series 161, (1981), 53.
11 HORWITZ, E.P. ; KALINA, D.G. ; MUSCATELLO, A.C. Separation

Science and Technology 16, (1981), 403.
12 CLEVELAND, J.M. ; Plutonium handbook Edited by Wick, O.J.,

Vol. 1 (1967) Chapter 12.
AMERICIUM METAL PREPARATION ON THE MULTIGRAM SCALE*
J. G. Reavis, S. A. Apgar III, and L. J. Mullins

Materials Science and Technology Division,
Los Alamos National Laboratory,
Los Alamos, NM 87545
ABSTRACT. The Materials Science and Technology Division of Los Alamos

National Laboratory has responded to periodic requests for tens of
grams of americium metal. The apparatus used for americium prepara-
tion has grown progressively simpler as experience has been gained
with the preparation. The metal was prepared by heating a mixture of
americium oxide and excess lanthanum metal under an atmosphere of ar-
gon in a tantalum crucible. A simple entrainment baffle rested on the
mixture and the crucible was covered by a loose-fitting lid which pre-
cluded line-of-sight exit of a gas but allowed evacuation. The ameri-
cium metal produced by reduction of the oxide was distilled to the
cooler upper portion of the crucible wall in vacuo, the crucible was
cut into two pieces, and the top section was reheated to melt and cast
the americium into a ceramic crucible. A coating of yttrium oxide ap-
plied to the tantalum crucible before use improved the yield of cast
americium.
1. INTRODUCTION
Americium metal was apparently first prepared on the microgram scale

by Westrum and Eyring (1) in 1946, although this work was not repor-
ted in the open literature until 1951. There were several reports
(2, 3, 4, 5) of preparation and study of the metal on the micro-
gram and milligram scales during the ensuing years up to 1962. Re-
duction of AmF3 at elevated temperatures by barium or lithium vapor
in a vacuum system was the method most often used, but reduction of
the dioxide by lanthanum was also used (4) in these studies.
Preparation of americium metal on the multigram scale was first
reported by Johnson and Leary (6) at Los Alamos in 1964. Since that
time, multigram batches of americium metal have been prepared at Los
Alamos, Livermore (7), Karlsruhe (8), and Rocky Flats (9, 10). There
have also been reports of metal preparation on the I-g scale (11, 12).
*Work done in the Materials Science and Technology Division of the Los
Alamos National Laboratory under the auspices of the United States
Department of Energy.
321
N. M. Edelstein et al. (eds.), Americium and Curium Chemistry and Technology. 321-330.
322 J. G. REAVIS ET AL.
This report describes the evolution of the preparative techniques

used at Los Alamos.
2. CHOICE OF THE METAL PREPARATION PROCESS
The commonly used quantities for prediction of the course of reactions

at high temperatures between halides or oxides and active metals are
the free energies of formation of the reactants and products of reac-
tions. Free energies of formation of several oxides, chlorides, and
fluorides that may be considered in the preparation of americium metal
are listed in Table I. The values listed in Table I are in general
based on the compilation by Glassner (13), although extrapolations
were made for Am0 2 and AmF 4 by comparison with other actinides. One
would predict that the americium compounds listed here could be re-
duced by heating them with an excess of metals that would form com-
pounds having more negative free energies of formation (those found
TABLE I. FREE ENERGIES OF FORMATION OF SELECTED OXIDES,

CHLORIDES, AND FLUORIDES AT 1000 K
(Values stated in kcal per gram-atom of anion)
Oxide -M Chloride -M Fluoride -M
CaO 127 BaC1 2 84 CaF 2 125

Th0 2 123 LiCl 79 BaF2 123
La203 122 CaC1 2 78 LiF 122
Am 20 3 120 NaCl 76 LaF3 121
BaO 111 LaC1 3 67 NaF 112
U0 2 109 AmC1 3 66 MgF 2 III
Am02 95 PuC1 3 59 AmF3 110
H2O 46 HCl 24 HF 65
higher in Table I) than the free energy of formation of the americium

compound. Care must be used, however, in using this oversimplified
method of predicting suitability of a reductant. This is illustrated
by the experience with AmC1 3 . At first glance, one would predict suc-
cessful reduction of AmC1 3 by calcium, but this method failed (6). It
should be pointed out, however, that this method might have been suc-
cessful had it been known at that time that the melting point of
americium is 1173°C instead of the much lower value (994°C) that had
been reported (5). A metal regulus might have been successfully pro-
duced had higher temperatures been used. On the other hand, one would
predict from Table I that hydrogen would not reduce americium com-
pounds, but it has been demonstrated that under certain conditions
of high gas purity, rapid flow rates, and high temperatures, Am02 can
be reduced by hydrogen (8, 12).
In addition to the thermochemistry of the reactions, one must
also consider certain engineering details when selecting a method for
preparation of active metals such as americium. These details include
availability of pure reductants and suitable container materials,
separability of the products of the reaction, and radiation exposure
AMERICIUM METAL PREPARATION ON THE MULTIGRAM SCALE 323
of personnel performing the operation. After consideration of the

many factors involved, those who wished to prepare americium metal on
the multigram scale selected the methods listed in Table II. As was
mentioned in the preceding paragraph, all of the reactions are energet-
ically favored, with the exception of reaction No.3. A number of
factors combine to make this reaction proceed. The system is op-
erated with ultrapure flowing hydrogen containing concentrations of
oxygen and water in the parts-per-billion range (12). The free energy
of formation of PtsAm helps to drive the reaction, but the free ener-
gies of formation of the actinide-noble metal intermetallic compounds
TABLE II. METHODS USED FOR PREPARATION OF AMERICIUM METAL

AND THE ATTENDANT FREE ENERGY CHANGES
ill', kcal/
No. Reaction g-mole Am
1 Am0 2 + 4/3 La 7 2/3 La203 + Am -40

2 Am02 + Th 7 Th0 2 + Am -55
3 Am0 2 (Pt) + 2H2 7 2H 2 0 + PtsAm +100(a)
4 AmF 4 + 2Ca 7 2CaF 2 + Am -140
5 Pu + Am distillation
(a)This value of ill' was calculated for the reaction in
the absence of platinum.
are probably only -10 kcal/mole (14). Another significant effect may
be the introduction of a high activity coefficient of hydrogen in the
presence of platinum. Americium is distilled away from the mixed pro-
ducts of reactions 1-3. The feasibility of this procedure can be seen
by comparing vapor pressure curves shown in Fig. 1. The vapor pressure
of americium is greater than that of lanthanum by a factor of approxi-
mately 3 x 10 4 , and vapor pressures of platinum and thorium are much
lower than that of lanthanum. Figure 1 also gives an indication of
the feasibility of separation of americium from certain nonvolatile
impurities as well as an indication of the difficulty of separation
from certain more-volatile impurities such as calcium, samarium, and
magnesium.
Reaction No. 4 of Table II is energetic and is used only with the
sealed pressure vessel or "bomb" technique (9). The products of reac-
tion are mechanically separable and the americium appears in the at-
tractive form of a regulus having almost the minimum possible surface
area per gram of product. The use of the fluoride, however, has a
serious drawback. The alpha particles emitted by americium interact
with fluorine atoms and generate an intense field of neutrons. It is
much more difficult to shield personnel from these neutrons than from
the alpha activity or the 60-keV gamma radiation of 241Am. A few mil-
limeters of lead will almost totally attenuate the gamma radiation,
whereas several centimeters of hydrogenous material are required to
significantly attenuate neutrons.
The fifth process listed in Table II is an attractive method of
preparing americium metal, but it requires a special feed material that
has a limited availability. Hundreds of kilograms of 241Am are formed
Sm
/'
AI
:/ /
Pu
600 700 800 1000 1200 1400 1600 2000

TEMPERATURE (ae>
Figure 1. Vapor pressures of selected metals (and CaF 2 )
encountered in americium preparation as reactants, pro-
ducts, or impurities.
worldwide each year (15) by decay of 241pu, but the concentration is

very low, and direct separation by distillation of the americium is not
feasible. One product of a process called "molten salt extraction"
consists of a plutonium/americium alloy containing about 5% americium
(10, 16). As can be seen from Fig. 1, the vapor pressure of americium
is more than three orders of magnitude greater than that of plutonium,
allowing separation of the two by a double-distillation process.
Consideration of the various factors discussed above led the au-
thors to prefer lanthanum reduction of Am0 2 over the other methods of
metal production that are discussed. Factors that influenced this de-
cision were availability of equipment, facilities, and feedstocks.
Other investigators may select other methods because of their particu-
lar situations.
3. EXPERIMENTAL
3.1. Equipment
Americium metal has been prepared in our laboratories in batches of 10-

25 g in stainless steel gloveboxes routinely used for plutonium
processing. The design of these gloveboxes includes walls consisting
of a sandwich of 0.25 in. of lead between an inner wall of 0.19 in.
stainless steel and an outer skin of 0.0625 in. stainless steel.
Leaded glass, 0.2s-in. thick, was added to the standard 0.2s-in.-thick

safety glass windows. The gloves were 0.030-in.-thick leaded neoprene
with Hypalon coatings (Hypalon is a radiation-resistant modified poly-
ethylene manufactured by the Du Pont Company.) both inside and outside.
The atmosphere inside the glovebox was argon containing less than
500 ppm oxygen and water. The pumping system consisted of a two-stage
mechanical pump and an oil diffusion pump equipped with a water-cooled
baffle. The vacuum envelope of the furnace was a ss-mm~o.d. quartz
tube sealed to metal flanges at both ends by means of Vi ton O-rings.
Heating of the reactants and products was by coupling of a 10-kHz in-
duction field directly to the walls of the tantalum furnace.
3.2. Evolution of Furnace Design
The evolution of the design of the furnace for amer1c1um metal prepa-
ration at Los Alamos has been toward simplification. This evolution
is illustrated in Fig. 2. All parts of the furnace were fabricated
ft ENTRAINMENT
~-BAFFLES
',/ " /
/
//
"",'
/ /
"/""
,
"/"
/
"/
/
/ /
(a) (b) (e) (d)
Figure 2. Evolutionary stages of the tantalum furnace used

for americium metal preparation.
from tantalum. The techniques used were deep drawing, machining and
welding. All furnaces contained the reactants in a strongly-heated
reaction zone at the bottom, and all had top condenser sections which
were heated much less strongly by using nonuniform spacing of the in-
duction field coils (Fig. 3) whose field coupled directly to the tan-
talum furance walls. All furnaces had entrainment baffles of varying
degrees of simplicity. Designs (a) and (b) were used in the earliest
multigram preparations. Design (c), which was originated at Livermore
(7), was used at a later date. There were two major problems with
these designs. One problem was high expense of fabrication of a de-
vice that had a low rate of reuse (usually zero to three times). The
second problem was retention of 25-35% of the product metal because of
formation of a surface film that would not drain from the condenser
into the casting crucible. Later preparations were performed in de-
sign (d). In this design, the reactor/di·tillation pot and the distil-
late condenser are combined in the form of a single flat-bottom,
welded-construction tantalum crucible that is 25 mm in diameter by
175 mm deep with D.5-mm-thick walls (Fig. 3). A loose-fitting entrain-
ment baffle consists of two thin tantalum discs penetrated by small
random holes. The discs are held approximately 6 mm apart by tantalum
wire,and the assembly rests on the surface of the reacting mixture.
The crucible is covered by a loose-fitting tantalum lid and the top
(condenser) section is cooled by a water-cooled collar. The furnace
of design (d) was the only furnace that used water cooling. The con-
denser sections of the other furnaces cooled by radiation of heat to
the surroundings. In the furnace of design (d), a thin (D.25-mm-
thick) split cylinder of tantalum in direct contact with the quartz
vacuum envelope served as a heat reflector. The temperature of the
tantalum crucible was determined by sighting an optical pyrometer
through the O.l-in.-wide vertical slit in the heat reflector. Py-
rometry corrections were made for light absorption by the quartz tube
and the glovebox window. Metallic mirror formation on the inside of
the quartz tube during distillation sometimes gave rise to uncertain-
ties in temperature measurement. Whenever metallic mirror formation
became detectable, distillation was discontinued, the system was dis-
assembled, the quartz tube and tantalum reflector were repositioned
to allow observation through a clean quartz surface, and distillation
continued.
3.3. Operation of the System
The empty apparatus was degassed before use by heating to approximate-

ly 1500 0 C in vacuo until the pressure had fallen to the background of
about 10-5~o~An excess (about 75%) of finely divided lanthanum
chips was mixed with Am0 2 powder by combining and tumbling in a lead-
shielded steel container. The mixture was transferred to the tantalum
crucible by use of a long-stem stainless steel funnel (to avoid dust
transfer to the walls) and was tamped for intimate contact. These
operations were performed in the argon atmosphere containing less than
500 ppm oxygen and water. The loaded crucible was placed in the vacuum
system and alternately evacuated slowly to the background pressure and
backfilled with high-purity argon three times. The last filling of

argon was left in the furnace and the system was slowly heated. A
temperature spike of about 350°C was usually observed when the reac-
tion started at about 800°C. Heating was continued approximately 1
min, then discontinued. The system was then evacuated and heated at
a rate slow enough to maintain observed pressures only slightly above
the background pressure. The temperature was held at about 1400 0 C for
times sufficient for distillation of all the americium, assuming a
distillation rate of 3 g/h. This rate is an overall batch rate that
was determined empirically. The actual rate probably varied widely
during the course of distillation. After distillation, the system was
cooled, disassembled, and inspected by gamma scanning to verify that
the americium had indeed been transferred from the reaction zone to
the condenser zone. Figure 3 shows the spatial relationship between
the induction coil and the furnace, the temperature profile during
distillation, and the gamma activity profile at the end of distilla-
tion.
After verification that the americium had been transported to the
condenser section, the reactor and condenser sections of the apparatus
T ANT ALUM LID GAMMA ACTIVITY (mr)
CYLINDRICAL
WATER-COOLED-"
~ o 100 200 300
COLLAR II E
..s:::;: 150
o
55-mm-o.d.
QUARTZ TUBE
~~ f-
bto
w
25 mm-o.d. X
ffi 100
(3
175-mm-DEEP ::J
a:
TANTALUM CRUCIBLE~ u
:::;:
o
INDUCTION a:
FIELD COIL - ~ 50
u
z
..:
PERFORATED ~ f-
TANTALUM BAFFLE ~
en
is
Am~/La MIXTURE '-~!-~""!!"""".A.I
TANTALUM __----~~~L--------~II
REFLECTOR
Figure 3. Americium preparation furnace, the crucible

temperature profile during the distillation phase of the
preparation, and the gamma activity profile of the ameri-
cium at the end of distillation, all shown with the same
scale and juxtaposition.
were separated and the condenser section was heated in an argon atmos-
phere to melt the americium and cast it into a Y203 crucible. To
lessen thermal shock of the crucible by the molten metal, a surround-
ing tantalum susceptor was used to heat the crucible simultaneously.
In the use of furnace designs (b) and (c) (Fig. 2), the condenser sec-
tions were inverted for the casting operation. In the use of design
Cd), the bottom 50 mm of the crucible containing the La203, excess
lanthanum, and the entrainment baffle was cut off by use of tubing
cutters. This bottom section was discarded and the condenser section
was inverted and heated to 1200 0 C for 1.5 min under an atmosphere of
argon to cast the americium product.
The yield of the casting operation was increased by using coat-
ings to reduce the degree of wetting of the tantalum. Best results
were obtained by use of Y20 3 applied as a slurry to the inside and
outside of the upper section of the crucible after it has been heated
briefly to dull red heat in air. This heating seems to produce a sur-
face that can be more evenly coated with the Y20 3 slurry. The slurry
was applied at a crucible temperature slightly less than 100°C. The
coated crucible was first baked at a low temperature in air, then out-
gassed in vacuo at 1500 0 C just before use.
4. PRODUCT YIELD AND PURITY
The overall yields of amer~c~um in the early work (6) using designs
(a) and (b) (Fig. 2) averaged about 75% per batch. The average yield
using design (d) on the 25-g scale was 89%. It was feared that the
simplified design (d) would allow greater contamination of the pro-
duct by lanthanum, but the change was hardly significant. Americium
product from design (b) contained 2500 ppm lanthanum, whereas that
from design (d) contained 4000 ppm. The only other impurities in the
latter product that could be detected by spectroscopic analysis were
20 ppm magnesium and 20 ppm calcium. The yttrium concentration was
reported as less than 200 ppm. No analyses for oxygen or other
anionic impurities were made.
5. SUMMARY
It was demonstrated that amer~c~um metal of approximately 99.5% purity

can be produced on the 20- to 25-g scale by lanthanum reduction of the
oxide in a very simple apparatus. As was predicted from relative vapor
pressures, volatile metal impurities such as calcium and magnesium ac-
company the americium during distillation. The major impurity detected
was lanthanum at a concentration that would be predicted for the equi-
librium vapor composition above lanthanum metal containing 1% americium.
It is speculated that higher-purity americium might be produced if dis-
tillation were to be discontinued earlier, with no attempt at quanti-
tative recovery of the metal.
LITERATURE CITED
l. Westrum, E. F. ; Eyring, LeRoy, J. Am. Chem. Soc. , 1951, 73,

3396-3398.
2. Carniglia, S. C. ; Cunningham, B. B. , -
1502.
J. - - Chem. Soc. , 1955, 77,
Am.
3. Graf, P.; Cunningham, B. B.; Dauben, C. H.; Wallmann, J. C.;

Templeton, D. H.; Ruben, H., ~ Am. Chem. Soc., 1956, 78,2340.
4. McWhan, D. B.; Wallmann, J. C.; Cunningham, B. B.; Asprey, L. B.;

Ellinger, F. H.; Zachariasen, W. H., J. Inorg. Nucl. Chem., 1960,
15, i85-187.
5. McWhan, D. B.; Cunningham, B. B.; Wallmann J. C., J. Inorg. Nucl.

Chem., 1962, 24, 1025-1038.
6. Johnson, K. W. R.; Leary, J. A., 'Preparation of Americium Metal',

Los Alamos Scientific Laboratory report LA-2992, January 1964.
7. Wade, W. Z.; Wolf, T., J. Inorg. Nucl. Chem., 1967, 29, 2577-
2587.
8. Spirlet, J. C.; Muller, W., J. of the Less-Common Met. 1973,

31, 35-46.
9. Conner, W. V., ~. of the Less-Common Met. 1974, 34, 301-308.
10. Berry, J. W.; Knighton, J. B.; Nannie, C. A., 'Vacuum Distilla-

tion of Americium Metal', Rocky Flats report RFP-3211,
January 1982.
11. Adair, H. L., ~. Inorg. Nucl. Chem., 1970, 32, 1173-1181.
12. Erdmann, B.; Keller, C., Inorg. Nucl. Chem. Lett., 1971,2,675-
683.
13. Glassner, A., 'The Thermochemical Properties of the Oxides,

Fluorides and Chlorides to 2500 K', Argonne National Laboratory
report ANL-5750 (1957).
14. Peterson, D. E. in Plutonium Chemistry (W. T. Carnall and G. R.

Choppin, eds.), pp. 99-108, ACS Symposium Series 216, Am. Chem.
Soc., Washington, D. C. (1983).
15. Schulz, W. W., The Chemistry of Americium, p. 28, ERDA (now DOE)
Technical Information Publication TID-26971 (1976).
330 1. G. REAVIS ET AL.
16. Knighton, J. B.; Hagan, P. G.; Navratil, J. D.; Thompson, G. H.,

in Transplutonium Elements -- Production and Recovery (J. D.
Navratil and W. W. Schulz, eds.), pp. 53-64, ACS Symposium Series
161, Am. Chern .. Soc., Washington, D. C. (1981).
INDEX
Absorption 5 in the filtrate 27

spectrum 164 isotopes 293, 294
Acidic layer 21 oxalate 294
A-Cm 20 3 oxide 294
preparat~on of high purity 37
radiation-induced structural preparat10n on the multi-gram
change of 160 scale 321
Acoustic shielding 21 production of 297
Actinide behavior, model in France 301
trivalent 153 purification processes 297
Actinide concept 6, 43 reference solution of, by
Actinide contraction 223 coulometry 87
Actinide metals, heavy 213 separation from plutonium 294
late 135 separation processes 297
Actinide oxides 147 sesquioxide 148
Actinides 26, 251 soluble tetravalent 29
Actinide sesquioxides 153 specific heat of 39
Actinide transition series 3 superconductivity 48
Actinium, oxalates of 167 synthesis of 19
Actinium (Ac) 255 titration 115
224 Ac 255 trivalent elements 310
225 Ac 255 Americium(II) 201
Americium(III) 28, 193, 199
Alice 255 compounds 199
Alpha activity, intense 22 oxidation with silver-catalysed
Alpha-alpha correlations 24 ammonium persulfate 90
Alpha decay series 22 Americium(III)-chloride 183
Alpha particle, long range determination of the vapor
activity 21 pressured 183
Alpha particles 5, 19, 21, 24 Americium(IV) 194
Alpha recoil techniques 22 in Ce02 and ThO 195, 197
Alpha spectrometry 252, 261 /Th02 196, 197
Americium 3-6, 8, 11, 12, 16, 25, Americium(V)
40, 43, 53, 81, 82, 87, 167, radiolytic reduction 89
199, 213, 295, 297, 301 solution, preparation of 91
40th anniversary of the discovery stability of, in nitrate media
3 89
discovery of 15 Americium(VI) 28
distilled 321 chromatographic extraction 319
isotopic ratios of 261 process 309
halides 31 radio lytic reduction 89
hexavalent 28, 30 solution, preparation of 91
history 25 stability of, in nitrate media 89
331
332 INDEX
Americium-241 21, 31, 301, 302 Beta decay 26

activity ratio 277 Beta-gamma activity, intense
applications for 293 21
fallout of isotopes in soils 275 Bi (V)
behaviors 275 concentration of 92
contamination levels 275 in the nitric acid solution
distribution 275 mixed with NaBi0 3 92
production of 293, 304
in the solution free from
purity 318
the undissolved oxidant 92
recovery of 293
from alpha aqueous wastes 315 209 Bi by 58 Fe 24
separated and purified 294 Big kicks 22
Americium-243 301,309 Birch equations 220
pentavalent 30 Blaise, J. 123
production 304 Breakthrough 24
separation from curium-244 310 Bromo complexes
AmAs0 4 173 stability constants (6 1 and
AmI 2 207 62) of the 261
a-Am2(Mo04)3 170 Bulk modulus 220
P-Am2(Mo04)3 170
Am(N03)3·6H20 168
Californium 215
. suscept1. b 1. I 1ty
243 AmO 2, magnet1c . Californium-244 255
of 199 Californium-245 255
+ carbonate complex 36
Am02- Californium-246 255
Am022+ chromatographic extraction 40 Ca and 48 Ca
procedure 316
Am022+ L.L.C. process 312 integrated elemental yields
AmOHC0 3 225 for 293
isostructural with NdOHC03-type A Carbamoylmethylphosphonate
231 (CMP) solvent extraction pro-
Am(Re04)3 170 cess 297
AmV0 4 173 Carbonate precipitation pro-
AmX3 (X=CI,Br,I) 193 cess 295
Amperometry 82 Cation exchange 295
Anion exchange 294, 295, 297 process 294
Apgar, S. A. III 321 C-Cm 20 3
Armbruster, Peter 24 radiation-induced structural
Asprey, L. B. 15 change of 168
Atomic coordinates CCP structure
in curium (III)-molybdate 171 trigonally distorted 220
in curium (III)-tungstate 171 CELESTIA reactors 301
Atomic sphere approximation- Cerium 222
LMTO (ASA-LMTO) method 217 ce0 2 196
Atomic volumes 213
Certified solutions 87
Band intensities 194 Chalcogenides 160
Batch leaching 289 Characteristic physical iden-
Beginning steps 24 tities 21
Berkeley 60-inch Cyclotron Charge up 21
3, 6, 8, 14 Chloro complexes, stability
Berkelium 215 constants (6 1 and 62 ) of the 261
INDEX 333
Chromatographic equipment 305 methods for the determination 53

Clinton Laboratories Tennessee monofluoroacetate 177
3,4,5,9 optical spectra of 293
Clinton pile 21 oxalate decahydrate 180
Clinton reactor 11, 12 oxide, purified 164
Coextraction of lanthanides oxyfluoride 178
310 pentavalent 159
Collection time 21 preparation 159
Column leaching 288 of high purity 37
Comparison of properties 159
crystal structures 135 purification of 36, 160
heats of vaporization 135 recovery of 160
phase transitions 288 reference of, by coulometry 87
vapor pressures 135 relative isotope shift of 134
Compensating errors 22 sesquioxide 149
Complete fusion 255 silicides 164
Complexation 53 silide residues 164
Complexometry with EDTA 115 synthesis of 19
Compressibility 213 tetravalent 159
Condensor microphones, sensi- trivalent elements 207, 310
tive 21 Curium(I)
Conduction electron electronic structure of 124
hybridise with 213 energy levels 123
Conical-slit method ground configurations of 123
energy-dispersive 217 identified configurations in 125
Configuration Curium(II)
itinerant 213 electronic structure of 124
localized 213 energy levels 123
Conventional chemical identifi- ground configurations of 125
cation 24 ground state of 127
Conway, J. G. 123 identified configurations in 123
Coprecipitation method with Curium(III) 194
BiP0 4 and ThF4 90 absorption spectrum of 163
in cubic compounds 202
Coulometry 82
in D20 194
constant-current 81
in SrCl2 203
Crystal, detection 24
oxyhalides of 177
Crystal entropy 141
ternary oxides· of 169
Crystal structures Curium(III)-arsenate 173
low-symmetry 213 Curium(III)-chloride 183
Cubic close packed structure 217 Curium(III)-chromate(V) 175
Curium 3-6, 8, 11, 12, 16, 40, 43, Curium(III)-chromate (VI) 176
53, 65, 208, 215, 252 Curium(III)-formate 167, 168
dioxide 150 Curium(III)-fluoride 181
discovery of 14, 24 Curium(III)-hydroxide 181
emission spectrum 123 Curium(III)-iron(III)-oxide 177
investigation of the properties Curium(III)-molybdate 170
of 38 Curium(III)-oxalate 178
ionized, neutral and singly 123 pyrolysis of Mg quantities of
isolation of 36 163
isotopic ratios of 261
334 INDEX
Curium(III)-oxalate-decahydrate
°
CmP0 4 160
167 CmP0 4 'H 159
Curium(III)-oxide 167 Cm( Reo4 Y3 159, 170
Curium(III)-oxybromide 180 Cm(Re04)1'xH20 159
Curium(III)-oxychloride 178 CmSc0 3 159, 175
Curium(III)-oxyfluoride 177 CmTa0 4 160
Curium(III)-perrhenate, anhydrous CmV0 3 159, 176
169 CmV0 4 159, 173
Curium(III)-phosphate hydrate 172 crnX0 3 169
Curium(III)-scandium oxide 175 crnXo 169
Curium(III)-trifluoroacetate 181 Cm(XB) 169
Curium(III)-tungstate 170 cmO'5~a80'502 160
Curium(III)-vanadate 173 Cm 20 1 150,170,175
Curium(III)-vanadate(III) 176 lattice constants of 159
Curium(III)/LuP04 206 Cm2(MoO~)3 170
Curium(III)/ThSi0 4 205 Cm 2 (W0 4 J 3 172
Curium(IV) 183, 199 Cm 2 (XO ,,) 3 169
Curium(IV)-oxide 167 Cm2(C204)3'lOH20 159,187
Curium(V) 183 (Cm 2 / 1 1/3)Mo0 4 170
compounds of 183 Cm/LaCl 3 202
Curium(VI) 70 Curium oxygen system 160
Curium-242 21,252,302,309 phase diagram of 160
Curium-244 81, 87, 159, 302, 309 phase transformation of 160
mixtures 301 Curyl configuration 187
recovery of, from silicide residues Cyclotron at Washington University
162 60-inch 4
reference solution of 87 Cunningham, B. 26
Curium-248 201, 248 Davis, Watson 15
CrnAl0 3 173 Decker equation of state 220
CrnAs04 159, 173 Decomposition apparatus 103
CrnBr3 159 Deep-inelastic transfer 255
CmCl3 159, 160, 183 Dehydration 169
vapor phase hydrolysis of 159, 177 Delute aqueous carbonate
CmCr0 3 159 solutions 235
CmCr04 159, 175 Depth profiles 276
CmF 3 1~9, 181 Dihexyl-N, N-diethylcarbamo-
lattice constants of 159 lyrnethylphosphonate 297
procedure for the preparation 181 Dilithium-trioxo-curiate (IV),
CmF 4 159,160,183 Li 2Cm0 3 183, 185
CrnFe01 159
Dioxide 302
Cm(HCOO)3 159, 187
Dioxo ions 31
CmI 3 159 Dipotassium americium hexafluo-
Cm(Mo0 4 )3 159 ride 30
Cm(N03)3 172 Discharge 22
CrnNb0 4 160
Discoveries of new elements
Cm0 2 160, 164, 169, 183, 185 24
CmOBr 159
new methods 22
CmOC 1 159 , 160, 177, 178 Disproportionation of Am (V)
CmOF 159
28
Cm(N03)3'XHO 168 Dissolution 294
INDEX 335
Dissolve plutonium turnings First major isolation 25

27 Fission 22
Distinctive ranges 21 Fission rate, enhanced spon-
Double glove box 37 taneous 21
Double-hexagonal close-parked Fission, spontaneous 24
(dhcp) 215 Fission events, spontaneous 22
Dry chemistry work 166 Flat absorbes 21
Fluoride ion 29
Efficiency, high 19 Fluxes of neutrons, increasing
Electrical resistivities 38 21
Electrochemical methods 58 f-orbital delocalization 48
Electrode reactions 114 Fourier Transform 86, 87
Electrolysis 21 Fried-Davidson apparatus 164,
Electron paramagnetic resonan- 166, 169, 170, 173, 175, 176,
ce (epr) 194, 195 178
Element-101 24 quartz reaction tube for 182
Frisch-grid ion chambers 22
Element- 258 104 24 Frisch-grid method 19
258 Funny incident 21
Element- 105, electron-cap-
ture decay 24 Fullbright, Harry 4
Element-106 24
y-ray spectrometry 115, 263
Element- 262 107 24 Gd I
Element- 266 109 24 identified configurations in
one single atom 24 126
Element syntheses 24 Gd I I
Energy (ies) 5, 19 identified configurations in
stored in graphite 26 126
cohesive 213 Genetic method 24
Epithermal ratio (f) 261 2n geometry 19
European Institute for Trans- Ghiorso, A. 4, 9. 43
uranium Elements research Ghiorso Uncertainty Principle
programme 35 22
Excitation function(s) 242, Gofman, John W. 5
252 52 GPa 213
Extraction chromatography 36, Gram-scale separation 25
297, 301 Graphite-moderated reactor 25
GSI 24
Fast electron collection 19 g-values 123
Fast Fourier Transform 86, 87
f delocalization 45 Haire 45
5f electrons 135, 213 Half-life 38
delocalization of 213 Hanford Engineer works, Was-
localization of, in americium hington 3, 9, 12
39 Hara, M. 89, 261
role of, in the chemical bond Hazards 21
35 Heavy-ion 251
Fermi 25 experiments 241
Fermium nuclear reactions 251
divalency of 45 Helium gas jet 24
heat of sublimation of 45 Highest oxidation states 54
336 INDEX
High Flux Isotope Reactor Kennedy, Jae 6

(HFIR) 241 Key components
High intensity deuteron 21 preparation of 167
Highly radio-active targets Kishimoto, M. 261
24 Kleinschmidt 45
High pressure transitions
systematics of 213 LaCl 3 193
High temperature experiments
166 Lanthanum 27
Hiroshima 275 Lanthanum reduction of amer-
Hiroshima atomic bomb 285 icium oxide 37
Hot Cells 303 Laser excitation 194
Hubener 45 Lattice constants, change of
Hulet, E. K. 132 178
in CmOCI 179
Implant 24 Lattice constants, relative
Impurity content change of
differences in 220 in GmOGI 179
Inner sphere complex 261 Lawrence Livermore National
Instrumentation 19 Laboratory 215
Interplanar distances 217 Lawrencium
Intramolecular electron trans- heat of sublimation 45
fer in the phosphato complex- oxidation state 45
es 103 Leaching characteristics 276
Ion exchange 36, 251, 293, 297 Liquid-liquid as well as mol-
Ionization chambers, gaseous ton salt extraction 293
19 Liquid-liquid chromatography
Iridium spirnl crucibles 302
apparat(l.~ Lor ... cork with 165 Li2Arn03 185
Iridium spiral furnace 166,
Li 2Cm0 3 183, 185
174, 175
Irradiated targets, processing Los Alamos National Laborato-
of 309 ry 14, 25, 21 5, 321
Irradiation 159 Low geometries 19
Isolation methods 54 Low-geometry counter 164
Isotopes 22, 159 Low symmetry crystal struc-
new 22 tures 213
Isotope shifts 123
Magnetic measurements 193
Jaffey, Arthur H. 4 Magnetic order 215
James, Ralph 8, 22
Magnetic properties 193
Japan Material Testing Reactor
Magnetic susceptibility 194
(JMTR) 261
Japan, various locations of of 243 Arn02 199
275
Maly 45
Jones, George Herbert, Labora-
Mahogany-colored 30
tory 4
Manhattan Project 44
Manning, W. M. 15
K3Arn0 2 (C0 3 )2 precipitation 316 Marcoule Plant 301
Keller, 0. L., Jr 43 Massive transfer 255
INDEX 337
Mass spectrometry 116, 261 Nobelium

Mass-yield distributions 242 heat of sublimation of 45
Measured position 24 Nuclear reactors 293, 294
Mendelevium Nuclear waste isolation 153
divalency of 45 Nucleon evaporation reactions
heat of sublimation of 45 255
Metallic bonding, contribution Nucleon transfer 255
to 213
Metallurgical Laboratory in 16 0 251
Chicago 3, 8, 12, 13, 15, 25
Metals, redetermination of Odd-even staggering 132
the vapour pressures of 39 Organic solvent extraction
Mica, split sheets of 21 297
Microchemical preparation Orthorhombic system 235
techniques 166 Orbitals
Microcomputer 81, 86, 87 hybridised 213
Micro DTA apparatus 167 OSIRIS reactor 301
Micro platinum boat 180 Outer sphere formation
Mitsugashira, T. 261 constant 270
Molar-extinction coefficients Oxalate 27
Oxalate precipitation 294
115
Oxidation 28
Molten salt extraction 294,
Oxidation states 53
297
process 295 Ozone 30
Monovalent 31 Paramagnetism, temperature
Morgan, Tom 8, 16 independent 200
Mullins, L. J. 321 Periodic table 44
Multi-channel pulse height Peroxydisulfate 28
analyzers 22 Phase hydrolysis apparatus
Murnaghan equations 220 180
Mutual rapid separation 251 Phase transition 215
second order 220
Na 3Cm0 4 185, 187 Physical methods 19
Platinum plate 21
Na 3Am0 4 187
Platinum spiral crucibles
Na 7Am 6F31 160 apparatus for work with 165
Plutonium 31, 167, 294, 295,
Na 3Pu0 4 187
297
Na 3U0 4 187 alloys 301, 312
aged 302
Na3Np04 187 activity ratios 277, 280
Nagasaki 275 atom ratio 283
Napkin rings 159 element-239 21
targets 43
~ -Nd 2 (MoO 4) 3
170 element-240 21
Neptunium (Np) 255 hydroxide 164
oxide 26 element-241 21, 26
Neptllnillm-238 25') element-242 21
Neptunium-239 255 242pU0 2 target e I ement 301 ,
New Chemistry 4
Nishiyama area 283 303
338 INDEX
Plutonium (cont.) Radium 255

extraction of 4 Radium-223 255
fallout of isotopes in soils Radium-224 255
275 Range curve 21
contamination levels 275 Range measurements 19
distributions 275 Rare-earth metals, early 135
behaviors 275 Rate constants
isotopic ratios of 261 cathodic 195
processing 294 for the reduction of 241 Am (V)
purification of 4 and 241 AM(VI) 99
scrap recovery facility 294 Reaction products 24
scrap recovery operations Reaction tube 182
293, 297 of Fried-Davidson-apparatus
spiral furnace 174, 175 182
Plutonium oxide 21 of vapor phase hydrolysis
dissolution 304 apparatus 182
Plutonium dioxide 312 Reactor neutrons 21
Plutonium dioxide dissolution Reavis, J. G. 321
using electrogenerated sil- Recoils 24
ver (II) 319 Recoil technique 24
Plutonium peroxide 294 Recycling 40, 312
precipitation of 27 Redox method 115
PuAs0 4 173 Reference samples 81
Pu (Re0 4)3 170 Regular intervals 22
Relative volumes 217
Polynomial approximation 86 Relativistic effects 45
Polynomial filting 87 Remote counting stations 24
Potassium bicarbonate 30 Rocky Flats Plant 293
Precipitation 36, 55, 293, Roof 45
294, 297 Ruby fluorescence method 217
of plutonium peroxide 27
Pressure 213
effect of 215 Safety precautions in work
with Cm 160
Prictides 160
Promethium (III)-hydroxide Satoh, 1. 261
172
Seaborg, Glenn 25, 26, 43, 241
Seaborg group 22
Pulse coulometry 115
Self-irradiation 180
Separation 293, 294
Quartz fiber torsion balance
Am from Cm 310
156 Am from Pu 294
Quasi-elastic transfer 255
methods 54
Quiz kids national radio pro-
Short fission half-life 21
gram 15
Sikkeland 45
Silicides 160
Radiation Laboratory of the Silver (II), electrogenerated
University of California 304
Berkeley 4 Single crystals, growth of 41
Radiations 19
Radio-active, weighings of 166 Si0 2 301
Radio-activity, experiments 22 Sodium bicarbonate 30
Radiopolarographic behavior 105 Sodium bismuth trioxide
INDEX 339
solubility of 90 Unique genetic chain 24

Solid-slate detectors 24 Uranium 21, 25, 31, 255
Solubility product constant ~-type structure 220
225 element-237 255
Solvent extraction 56 element-238 251
Sorption 57 element-239 255
Specific chemical separations isotopic ratio of 261
22 oxides of mixed 40
Spectrometry Uranyl-type, linear dioxo 31
gamma-ray 115, 263 U. S. Department of Energy's
mass 116 Rocky Flats Plant 293
Spectrophotometry UV photoemission spectroscopy,
direct absorption 116 resolution 39
Spin polarisation energy 222
Spiral furnaces 166 Velocity separator SHIP 24
St. Louis cyclotron 8 Virgin curium oxide 154
Super conductor 48 Volume collapse 217
Superheavy elements 241 Volume decrease 213
Survey meters 21
Suzuki, S. 89, 261 Wahl, Art 6
Ward 45
Tan precipitate 30 Washington University cyclo-
Target 241 tron 21
TBP/Si0 2 301 Worden, E. F. 123
Thermal neutron flux (¢) 261
Thiocyanate ~on exchange pro- X-ray capillary 174
cess 294 X-ray diffraction 26, 213
Thorides 26 X-ray powder diffraction pat-
Thorium 255 tern of AmOHC0 3 228
reduction of curium oxide 37 X-ray powder diffraction pat-
Thorium-225 255 tern of Nd2(C03)3.2H20 226
Thorium-226 255
Thorium-227 255 X-ray powder diffraction pat-
Thorium-228 255 tern of NdOHC0 3 -Type A 226
Time variation 277 X-ray spectroscopy 39
Titrimetric methods 115 X-ray work 167
TOAHN0 3 /Si0 2 301
Transfer coefficients 105 Zachariasen, W. H. 26
Transfer reactions 243 Zero field splitting for Gd 3 +
Transition pressures 222 3+
and Cm 203
Transplutonium 135 Zvara 45
elements 24
oxides 147
Production Program 241
Transuranium 251
in the environment 275
production of 261
synthesis of 251
Trisodium-tetraoxo-curiate
(V) 183, 185

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1985 Book AmericiumAndCuriumChemistryAnd

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Americium and Curium Chemistry and Technology

TOPICS IN {-ELEMENT CHEMISTRY

JERRY L. ATWOOD, University of Alabama, U.S.A.

Editorial Advisory Board

W. J. EVANS, University of California, Irvine, U. S. A.

D. Reidel Publishing Company

Dordrecht / Boston / Lancaster

Main entry under title:

(Topics in f-element chemistry)

ISBN-13: 978-94-010-8904-3 e-ISBN-13: 978-94-009-5444-1

Published by D. Reidel Publishing Company

Sold and distributed in the U.S.A. and Canada

In all other countries, sold and distributed

All Rights Reserved

Glenn T. Seaborg / The 40th Anniversary of the Discovery of

B.F. Myasoedov and N.Yu. Kremliakova / Studies of Americium

Earl F. Worden, John G. Conway, and Jean Blaise / Electronic

Norman Edelstein / The Electronic and Magnetic Properties of

Darleane C. Hoffman / Heavy Ion Reactions on Curium Targets 241

The papers included in this volume were presented at the symposium on

Historical Aspects and General Papers

Dr. Glenn T. Seaborg

ABSTRACT: The recogn1t10n, in July 1944, that the unknown elements

The discovery of two very interesting synthetic elements--the

A number of factors contributed to the special status that this

procedures. Chemical fractions were isolated, and their radiations

Figure 1. Original mica absorption d239 showing presence of 242 96

carrying the non-oxidizable element 95 as its insoluble fluoride on

first of these was removed on November 10 and returned to Chicago on

239 240 pu 241

242 95 (3- 242 96

The same isotope 242 96 had been produced 1n helium-ion-bombarded

Aiding us in coming to this conclusion was the information we

Figure 3. Summary alpha particle absorption curves presented at

A good summary of our understanding at that time can also be seen

(n,y) 95 242 • The ratio of the yields in the Hanford as compared

the production of 242 96 by the reactions 241 95 (n,Y)

_s- ) 242 96 • Soon thereafter W. M. Manning and L. B.

Asprey measured the half-life of 242 95 as about 16 hours.

The significance of this lies in the fact

that we were able to obtain declassification (permission to publish)

haven't disclosed any planets beyond Pluto. So we'll have to go

This work is supported by the Director, Office of Energy Research

1. Seaborg, G. T., James, R. A. and Morgan, L. 0., 'The New Element

fI\ leA ABSORBER

G. MUt\iehbeY"9 ~i 0(. t'lS2.

The big breakthrough came when we introduced the recoil technique

*This work was supported by the Director, Office of Energy Research,

R.A. Penneman (Consultant)

ABSTRACT. For this 40th Anniversary Discovery Celebration,

The discovery of americium was made in 1944, as just re-

first measurements of the energy stored in graphite as a

to make in the early work. Other major contributions were

First of all, the building had to be outfitted for the

Los Alamos work began to focus on the new americium

1. The discovery of hexavalent americium,

2. Its similarity to hexavalent uranium in their

3. The oxidation of Am(III) to Am(VI) by peroxydi-

4. The measurement of the reversible couple,

22. Asprey, L.B. and Penneman, R.A., em~ ~b~m~ §Q£~,

.78~----~-- ~- J_ _ _ _ _ _~------U