Académique Documents
Professionnel Documents
Culture Documents
;. ,_
v
SERIES
The
Radiochemistry Elements
of the Transcurium
COMM
Maasachueeth
Inetitute of Techuolo~
J. A. DeJUREN, Secre*y Westlnghouee Electric Corporation C. J. BORKOWSKI Oak Ridge National laboratory ROBERT G. COCERAN Texas Agricultural and Mechanical College SAMUEL California EPSTELN Inetltute of Technology J. W. IRVINE, JR. Mammchueette InBtitute of Technology E. D. KLEMA Northwestern W. WAYNE Univerai@ University
MEINICE of Michtgao
ROBERT L. PLATZMAN Laboratoire de Cbimie Physique D. M. VAN PATTER Bhrtal Research Foundation
Development
LIAISON
PAUL C. AEBERSOLD Atomtc Ene~ Commission J. HOWARD MoMILLEN National Scienoe Foundation
MEMBERS
CHARLES K. REED
SUBCOMMlllEE
W. WAYNE Untvereity MEINKE, of Mlchlgan Chairman
ON RADIOCHEMISTRY
HAROLD KIRBY Mound Labomtory GEORGE LEDDICOTTE
Oak Ridge National LalMmtory JULIAN NIZLSEN Hanfonl Laboratories ELLIS P. STEINBERG Argonne National Laboratory PETER C. STEVENSON of California (Livermore)
Los Alamos
ARTHUR W. FAIRHALL I@vez73ity of Washington JEROME HUDIS Brookhaven National Laboratory EARL HYDE Univerai@ of California
University
(Berkeley)
CONSULTANTS
NATHAN H&LOU Naval Radiological Defenee Laboratory JAMES DeVOE University of MicMgan
CHEMISTRY
G. H. HIGGINS
October
25, 1960
LIBRARES PROPERTY
of Sciences
Printed in USA. Price $0.50. Available from the Office of Technical Services, Department of Commerce, Washington 25, D. C.
FOREWORD
The Subcommittee on Radlochemlstry Is one of a number of subcommittees working under the Committee on Nuclear Science wlthln the National Academy of Sciences - National Research council . Its members represent government, industrial, and university laboratories In the areas of nuclear chemistry end analytical chemistg
The Subcommittee has concerned Itself with those areas of nuclear science which Involve the chemist, such as the collection and distribution of radlochemlcal procedures, the establishment of specifications for radlochemlcal.ly pure reagents, availability of cyclotron time for service irradlatlons, the place of radiochemistry h the undergraduate college program, etc .
This series of monographs has grown out of the need for up-to-date compilations of radlochemical Information and procedures. The Subcommittee has endeavored to present a series which will be of maximum use to the working sclentlst and which contains the latest available Information. Each monograph collects In one volume the pertinent information required for radlochemical work with an individual element or a group of closely related elements.
An expert In the radlochemlstry of the particular has written the monograph, following a standard format by the Subcommittee. The Atomic Energy Commlsslon has the printing of the series.
The Subcommittee Is confident these publications useful not only to the radlochemlst but also to the worker In other fields such as physics, biochemistry who wishes to use radlochemlcal techniques to solve problem.
iii
INTRODUCTION
This volume which deals with the radiochemistry of the transcurlum elements Is one of a series of monographs on radlochemistry of the elements. There is Included a review of the nuclear and chemical fe,atures of particular interest to the a discussion of problems of dissolution of a radiochemlst, sample and counting techniques, and finally, a collection of radlochemlcal procedures for the element as found In the literature. The series of monographs will cover all elements for which radiochemical procedures are pertinent. Plans Include revlslon of the monograph periodically as.new techniques and procedures warrant. The reader Is therefore encouraged to call to the attention of the author any published or unpublished material on the radiochemistry of the transcurlum elements which might be included in a revised version of the monograph.
iv
CONTENTS
I. II.
General Comments Reviews . . . of . . . 2 . . 1
General
the
Transcurium
III.
Table
of Isotopes
of the , . . Element
5
Elements
of Features
Most
of Transcurium
to Radiochemists
Coprecipit.ation Precipitation
B.
Complex Chelate
Ions
6 . 6 8
c. D.
Separations actinide
e and lanthanide
2.
Separations elements
v.
of Samples Related
Elements
~.
Counting Source
. .
20 23
VII.
Specific
The Radiochemistry
of the Transcurium
G. EL HIGGINS
Elements
Lawrence
Radiation
Laboratory
University Livermore,
of California California
I.
GENERAL The
transcurium
97; californium
(Fro), number
(Cf),
100;
number
98; einsteinium
(Md),
(EH ), number
101;
99;
mendelevium
number
and nobelium
number
102. elements are all synthetic; or charged Their that is, particle discovery they are all usually reactions on isotopes
:. produced of ele -
These
by multiple
neutron capture
ments of lower
by Thompson.,l they shell of the etist the Ce+3 compose is being
atomic number.
With the the inclusion half
and production
is described
103
of the as
element the
second
completed. or rare
similar No),
in aqueous equivalent
solutions. to those
to Ce w The
chemical rest,
of any
one
of these to speak
elements of many
are
quite
similar
of the
of their can
chemical usually
radiochemical
procedures
The
isolation
fraction.
the lanthanides.
have
characteristic with
a decay some
energies
isotopes fission
may
be confused .
spontaneous
half-lives without
Because entirely
of these
being
separated for
of the procedures
do not provide
complete
element, natural
Bk,
is five
atomic
numbers
beyond
The
mass
numbers is
so even
element
from
these
quantities.
C unningham2
reported
as well
as the
absorption colored
about
Neither peaks
ion is at 7800
strongly and
8300A.
These
studies
are of Bk
were
performed possible
been
no chemical
even
at tracer
possible
are
so short. except
about
elements
is derived lanthanides
and comparisons
the chemistry
of the
11.
REVIEWS
OF
THE
CHEMISTRY
OF
THE
TRANSCURHJM
reviews
of the books
of the transcurium
elements
can be
found
in the following
G. Publishing
T.
Seaborg,
Um Elements,
II Ad&~On.We~leY
, 1958. [Ref. 4. ]
I!chemistry [Ref. G. R. 5. ] Choppin, and G. T. Seaborg, of the Actinide Elements,
J. K.
Methuen S. J. Am.
T. Seaborg,
1957.
and Co. G.
, London, B. G.
Thompson, Sot.
Harvey,
Chem.
[Ref.6. Educ.
Muga, Proc. ---.-,
] 1959). [Ref. 2. ]
and Peaceful
B. B. S. G.
Research
Cunningham, Thompson
36 (January,
!lMethoda U. N. ,-----
and M.
Elements, Geneva,
Uses
Atomic
III.
TABLE
OF
ISOTOPES 1/2
OF
THE
TRANSCURIUM Mode
ELEMENTS of Decay
99+ L70; a,
99 +~a; a,
O. 15% 6X 10-37,
99 +~.; a, O. 11~
16 h 314d 3.13h
$-, ~-,
30~
a 2.2x10-370;
SF,
6X10 -6~O.
Pa EC,
h
7070; a, 307
2X 10-4%
.5X10 4X 10-4~0
15%
-270
98cf249 cF50
cf251 cf252
360 y
10.9 CIS 800 2.2y y y
a; SF-O.
a
a,
9770;
SF,
3~0
111.
TABLE
OF
ISOTOPES
OF
THE
TRANSCURIUM Mode
ELEMENTS of Decav
(Contd. )
Nuclide ~f253
M_
17 d { / 56d
7,3m
a,
EC
a 25 m 2h 8h 1.5d =140d 20.03 480 37 h 24 d Ehort d d EC, EC, EC EC, a a; SF, a; no ~~-, P1399+70; EC =0. 17, 8X10-670 99 +7,; a, 0.53~0
99+~o; a,
0.3~o O. ls~o
E~249
~B250 EB251 E~252
99 +~,;
a,
~ooFm
248
a,
EC
a =170
EC -9970;
a;
EC,
a;
SF,
X10-2~0
Fm25 Frn256
a; SF
< 4. 5X 10-3~
SF = 100~o
Md256 =30 m
a+?
EC
102N253
=10s
a+?
HI.
TABLE
OF
ISOTOPES
OF
THE
TRANSCURIUM
ELEMENTS
(Contd,
Nuclide N0254
k 1
Mode
of Decay
38
a+?
~~3
0.25
a+?
above
are
h = hour~,
a . a particle fission
p- = negatron
emission,
= spontaneous
decay.
complete
description
of most
of these
nuclides
can be found
in
in Reviews a particle
of Modern energies,
585-904. are
and genetic
relationship
IV.
REVIEW
MOST
OF FEATURES
OF TRANSCURIUM
ELEMENT
CHEMISTRY
INTERESTING
TO RADIOCHEMISTS
IV. A.
Chemistry such Ce marked or all La) form similarity is ordinarily insoluble acids to the used lanas a from
of the
precipitation
They Less
fluorides
oxalates ( *O.
strong
phosphates ofides in
in slightly basic
solutions. readily
oxides (40%)
carbonates, complet-
but they
carbonate
or many
of the
acids
as
several acid
other
at lower or
the precipitation Sc +3 , Y +3 ,
=3M HC1
HN03
thanides
and actinides,
thorium,
earths.
group tated
is
left
in solution oxides
when from
the
of these
elements
are
precipiSr ++
as hydrated
carbonate with
solutions.
Holdback step.
enhances
the separation
achieved
precipitation carry
appreciably
on acid
phosphate,
hydroxides.
IV. B.
Ions
and Chelate
Formations power for of different anions anions, is fluoride and carbonate formation +3 ions are for and and > > is so
of the completing > per chlorate for dinegative in ion on cation Complex lactate, known
mononegative The
anions.
measures with
required substances,
rapid
organic
tartrate, are
a-hydrox+s
EDTA,
TTA,
acetate, For as
thiocyanate
to form
moderately
complexes, Cf is listed
instance, 10 - 19.09+C.2
constant
of the EDTA
complex
IV. C.,
Behavior rapid extraction of Bk -1-4 separation away from for Bk 3, the transcurium Cm+3, from HN03 and elements Cf+3 into . The that in-
volves
the
extraction
solutions than 10
is more
6 times
6 (Section
VU of this
report)
is based
on this
extraction. Cf, lanthanides 2 -ethylhexyl solutions. cf. 1 10 Es, Fm, and Cm can be separated into from each other and from phosphoric aqueous the acid, HC1 of
with
appropriate
phosphoric These
acidjor
phosphoric with
extractions
effective
concentrations
extractions discussed
of the by Best
lanthanides et al. , 13 12
into of
tri-n-butyl Bk with
phos this re -
is described Magnussen
by Hulet. et al. 14
have
reported O. lM
the extraction
coefficients
elements The
from data
ammonium
chloroacetate
solutions.
K=
HT activity The
is the
TTA
HT
by
fHT
0.24
(HT)0.48.
data
solvent
by Poskanzer obtained
who subtracted K.
O. 2 pH unit
pH5 ~ value
and recalculated
Table
I. tion
coefficients
elements TTA-toluene
for
extrac
O. lM ammonium K ==1.5X1O
solutions.
pH -7
for
507.
(Benzene)
Cf 3
E +3 Fm+3
under Lu is
nearly -3.0,
the
same
conditions, -actinide
i. e. ,
PH50
separations earth by
Group
separations
group,
a solution pH to 4.5
to pH 2,
organic
then This
not been
reported
IV. D. -.
Chemistry between the various transcurium elements With by their has the exrelative
similarity
interest No,
in and work
on their elements
positions devised
exchange
procedures they
been
which
use
of ion exchange
operation,
in general to compare
various
sources,
column This
eluate
volumes abbreviated
have
been
reduced is
to units
of Ilfree
volume,
FCV, for as
loading
any
by finding etc.
organic
The
FCV
is about
column
bore.
IV. D. 1
Separations
of the
actinides
and lanthanides.
The
chloride
cyanate
plexes eluted with
complexes
of the from
of the actinides
When cation
are
stronger
mixtures such
resins
12M HC1
2M NH4CNS, are
before the
obtained. AG with
6, 16
225
separations Figure
2 shows eluate.
elution
positions
using
1. 8M NH4CNS
complexes
in very are
strong such
agents species
13M H(ZL,
2M NH4CNS of the
Similar
species
lanthanides are
separations resin. 18
possible
complex-
ing agents
relative
elution 6..
positions
from have
13M HC1.
Slmllar
or better
Rh
Fm Cf, Es
Bk
Am Cm
Yb
1.0
0 o I 2 FREE
Fig. 1. Relative elution positions Dowex-50 AC with 20% ethyl alcohol elements appear as a group between
3 COLUMN
4 VOLUMES
of transplutonium actinides, Y, saturated (S= 12. 5~ ) with HC1. O. 3 and 3 free column volumee.
Yb, The
Lo
Es
Cf
Bk
Cm
Am
0.01
2 3 4 FREE
Fig. Z. Dowex-50
5 COLUMN
VOLUMES
actinides from
10
LANTHANIDES Cf Bk Es Fm
m m
1
4 FREE 6 COLUMN
1
0
10
VOLUMES
12
14
transplutonium
11
Cm
Am
Es
Bk Cf
4 FREE
6 COLUMN
10
VOLUMES
12
14
Fig. Dowex-
actinides
from
12
been shows
reported the
using
the elution
same
eluant
IRA-400. resin
19
Figure
relative
positions of about
using and
2M NH4CNS. elutions
Lithium equivalent
chloride to
solutions
give
adsorptions
13M HC1. actinides with are O. 1~ eluted to 6~ from HC1, but cation very resins little like
the actinidea
and lanthanides
is obtained, 7 (Section
separations
cations
Procedure
report)
a IIcleanupl!
column
operated at
Fe, 5.
and Al.
Columns
operated is boiled
in Fig.
Trichloroethylene
A
\
ELUANT+
5.
Column
apparatus
for
eluis con-
at 87C.
ducted around
jacket con-
bed,
and the
1
TRICHLOROETHYLENE -F
densed
vapor
returned
to the flask.
into
a condenser
flask, are
proprac-
at 87 C.
Higher of vapor
because with
solutions
resin
bed;
however,
temperatures
to
can be used.
13
IV. D. 2. separations relatively from its The elements Lating glycolic, cessfully tors the if
Separations
from other is
each are
other. obtained
While with
of the transcurium concentrated neighbor. most from convenient each acid other anions lactic, 21 . HC1
no element
separated
cleanly
used
method from
for
separation resin
them
cation
organic
Several and
anions
those have
tartaric, as eluants.
obutyric is
While
advantage
the general
same
Figure
6 is a typical
with at room
elution
curve
of the same
Similar
-linked)
from
Zeo-Carb
the
positions
from to
cation
Cm=
1.00. 16
Data and
have
Choppin
Milsted
and Beadle.
the elution
position
depends
the resin
of the
solution
of weak Figure
acid
concentration.
7 shows sobutyric
of ammonium obutyric
a-hydroxyi acid
The
of a change assuming
of a-hydroxyis Kd will
concentration
be unchanged
when is
concentration
constant
of the acid
spacing than
between
of the Bk for
Md pH
and
Fm,
less
and confor 23
of eluant. separations
spacing
has
attained
in columns
utilizing
continuously
variable
eluants,
14
I.0
Cm
>
1: ;
a
u
> L
0.1
a J u c
0.01 o
2
10
12
14
Fig. 6. Relative elution PO .sitione of curium and the trans from Dowex-50 1270 cross -linked resin with pH 4.2 a~onium butyrate at 87 C.
15
Table
II. resin
Elution with
positions
of actinides
and acid.
lanthanides
from
cation
exchange
a-hydrox~Bobutyric
Element
Dowex-50 25C
4L70at
Zeo-Carb 77C
225
at
Dowex-50 12~0 at 87 C
Md Fm Es Cf Bk Cm Am Lu Yb Tm Er Ho Y Dy Tb Gd Eu Sm Pm Nd La Ce
0.050 0.069 0.13 0,20 0.45 1.00 1.4 0.015 0.020 0.026 0.037 0.055 0.06 0.078 0.14 0.28 0.39 0.71 1.2 2.1 r.
-0, 039 0.069 0.076 0.14 0.22 0.34 0.7 1.1 2.3
--.---.
-3.4
3,5
there
are .
no reports
that
this
has
been
accomplished
with
the transcurium
flow
rate peake .
at which Figure
a column 8 shows
is
operated for
affects
the apparent
width
elution
Dowex-50
127 resin, is O. 4~
to settle acid
when The
the eluate
curve
greater
at the 5 or
when
coarser
half-width ratea.
of about
and slow-
16
100
50
10
4.4
4.8
17
...
o
FLOW
I
2
RATE
I
3
I
4
(ml/min/cm20F
COLUMN
AREA)
Fig. 8. Full width at half maximum (half-width) of the elution peak of curium from Dowex-50 12L70cross -linked resin with O. 4~ ammonium lactate at 87 C on one particular column. Similar curves would be obtained with other eluants and other columns, but the resin particle size, temperature of operation, length-to-diameter ratio of the resin bed, technique, and the presence or absence of carriers or mass impurities all affect the absolute value of half-width at any flow rate. v. DISSOLUTION UDLING The emission. siderable These OF TI-IX transcurium Spontaneous numbers make SAMP-LES TRANSCURIUM elements fission are is also may AND SPECIAL ELEMENTS all unstable with respect mode to a particle con. PROBLEMS RELATED TO
so that
be emitted
samples quantities
facts
of microgram
elements must
difficult
be carried
on in gloved
instances
18
-control
handling product 8
equipment contamination.
is
required For
even
after
the samples
are 252
of fission 42 X 10
instance, about
1 microgram
of Cf
a tolerance eq,uipped
working to handle
dose the as
Laboratories a-particle
and neutron
survey
meters
transcurium The
elements
produced isotopes
in at least are
three
different by heavy-ion
kinds
of target.
bombardments
by reactions L + ~8Cf
>40n
in which
atoms
collected The
on !Irecoil
catchersil
separate are
from
material.
techniques
discussed the
and Ghiorso
when
the target
or catcher
is dissolved are
the tranacurium ment, target itself Since they decay the Pb such
elements boxes,
as glove
may
although are
be needed The is
retain
charges
in helium
as thin samples
without a-decay chemistry; half-lives alone Walton, are classic
energies
a particle
measurements Sikkeland,
done
by Ghiorso, 102
(nobelium)
of these
nonchemical
techniques.
material,
dissolution
of the plate.
19
The nuclear
second
source Es
elements first
is the debris
from
thermo
discovered
thermonuclear capture in U
had been
and finally
last The
of organic perchloric
material acid
diluted
more
of
6N HC1, was
similar
VII)
massive
This
of sample
special
handling
equipment
is unnecessary.
and most
generally
source or
uranium,
curium
to large
integrated techniques
The
production 3 The
discussed
and Muga.
produced material.
in an aluminum-clad Dissolution
of an otide by removing
or metal
of target in due
6MNaO&M containing
the insoluble
residue of
a trace
and
HN03).
These since
operations
by remote
equipment while
the target
and intermediate are rare are being -earth usually formed. fraction
fission
separations, of the
Ianthanide Procedure
included
operation.
typical.
VI.
COUNTING C Ounting
AND
SOURCE
elements no stable
IImaaa-freel!
carriers,
20
vACUUM
Fig. are
9.
Schematic
diagram
of vacuum filament,
evaporated
transcurium ,short-duration
volatilized pulse
counting
by passing
high-current
the tungsten
filament.
some
useful sample
involve
the
which a
short or
ranges.
prepared
either
several
drops
on a plate
of platinum
metal
operations,
the pure
onto
wide,
30 to 50 mm
electrodes counting
in a vacuum disc,
millimeters 9,
away
oxides) of current
counting for
by allowing tenths
to flow
through
a few
of a sec-
current all
raises
the filament
above
vaporizes
the transcurium
material.
Very
thin uniform
21
plates
can be prepared ,.
in this
way; rate
however, unless
material
will
recoil
at an appreciable
heated
to about
500 C
special or
counting
is used work
for
detection with
of
~,
electron-
a particles.
ie done of these
that
isotopes
elements
procese
introducing a specific
amounts,
measured (e. g. ,
longer-lived
isotope
to trace -height
topes)
and submitting
the is ratio of
the recovered
a counts and nearly
samples
analysis.
of several
isotopes. piece
a pulse-height equipment
a valuable
indispensable , rates
of counting
with high
elements -fission
decay
are
utilized
in counting are
sam-
transcurium by taking
elements. advan~age
fission the
counters
easily proby
constructed duced
specific than
ionization
by fission
fragments electrical
gas
is higher from
obtained
a-particle operation
counters is usually an
with with
collector
be -
at which both a-
if found.
counting
counters their
and can
voltages scintillation
with used
ease. for
conductor
detectors
counters
and a particks.
22
VII.
SPECIFIC
SEPARATION
PROCEDURES
Procedure
This fraction
procedure
is for
of an impure
transcurium s lug. 25
from
a pile -irradiated
or americium slug
is designed of target
containing
O. 1 to
and Cm
is placed
pot heater.
heated 6M in
with and
an electric
2M in NaN03
violently
reacts
after
starts ).
The insoluble
to settle and the supernate stick. The precipitate with NH3 gas,
is withdrawn is washed
steel filter
portions
and digesting.
is dissolved,
to 50 ml, to a 4-cm-diam
is heated ) The to 80 C
X 20-cm-long
with a water
Dowex-1
jacket.
10~0
resin
column
which ml.
is -150 two
evaporator of 10M
washed the
50-ml rate
portions of about
is passed metal
and alkali ml of 6~
transplutonium remains
actinides
6N HC1. HC1
Plutonium to 600 20 cm
on the column. through a Dowex-50 washed impurities eluted desired 12~0 with and with ele300
is diluted and
4 cm
in diam which
column
removes
Cr,
converts
The
then The
to a suitable selected
or five
Ilcutstl
on the basis
of the ele -
Procedure
1 (Continued)
desired
for
further
work is
of FCVie transcurium
predicted element
to be processed by a procedure
without similar
remote
equipment cedures
further
purified
to Pro-
Procedure This from These day-old procedure fisaion are which through was devised
to separate containing
samples with
elements
yttrium
or lanthanum in HC1;
fluoride the
dissolved colurrms
several
to remove Zr used
U,
of the -HCl
remaining elution
fission from
products resin
and Te).
a cation
to remove
columns,
the column
tips
are
with
sand.
several free
of
the column. is
bubbles 1. To
to a successful in a 40-ml
of the Te,
centrifuge of
each Using
of
10 mg/ml
and 1 drop
Y carrier. Cen-
phenolphthalein discard
indicator,
to precipitate
Y(OH)3. with
trifuge,
ml
the supernate,
the precipitate
O. 5- 1.0
H20. 2. Dissolve the precipitate test tube. a large in a minimum Add 2 drops of Fe cone or amount HF U, of per 3M ml HC1 and trans -
fer
to a polyethylene solution
of solution, HF to de-
(If the
contains
amount
add enough
24
Procedure
2 (Continued)
the
solution,
then
2 drops discard
per the
ml
in addition.
Let
the
solution
stand
5 minutes, O. 5 ml 3, of
centrifuge,
supernate,
and wash
the precipitate
stirring, glass
solution
centrifuge
tube.
Add
2 drops the
carrier
briefly.
NH40H, with
the precipitate in 3 X
O. 5- 1.0
the precipitate
ml 10M HC1.
Dowex - 1 AG
Add
anion of
Transfer
which has
2-cm
several through
column with
volumes pressure.
After
carriers, which
pass have
10-cm containing
X 8-cm
columns
O. lM I+UJ03 (the
small
column
contains
Pu
if present
solution). 5. Add NH40H to the combined discard the 10M HC1 solution to precipitate the precipitate twice
Y(OH)3 with
supernate,
and wash
0.,5
6.
pass which Wash HC1
amount AG
of O. 1~ cation volumes
HC1
and
resin
column HC1.
previously with 1 ml
column 2 ml
of O. 1~
of O. lM HC1, O. 5M HC1.
of the
O. 006M HF 0, lM
1 ml pipet
and a minimum
of H20, X 2-cm
transfer Dowex-50
resin column
from
column
which
been
previously After
column withdraw
volumes
-HCl
elutriant.
and. wash
above
the resin
a small
portion
25
Procedure
2 (Continued) ethanol every -HCl solution, uBing Collect tube. sufficient the de(See Fig. 1
HC1.
with
approximately drops
45 seconds. centrifuge
fraction
(usually
in a 40-ml
typical This
elution solution
positions. will
be free for
of most co rn@ete
lanthanide Procedure
separated
from
Note: Some 7.
Several
variations
reported bed
prefer
loading prefer
the resin
resin
Others
to run the
6 directly
it with
10 to 20 column moves
volumes
of 2M HC1, elements
2M wash length
down
the column
by the shrinkage
and accidental
of the
resin
otherwise.
Procedure This tions similar isobutyric tions. 27 1, Preparation A. (obtained is further and from of resin eluant free procedure ia for separating mass
of lanthanides,
other
6.
consequently
gives
better
, Richmond, settles
graded
size
by selecting . resin
that
between
O. 25 cm/min B.
water
graded stored
is washed
alternately form.
with
NH40H
and finally
in the ammonium
26
Procedure
3 (Continued)
c. acid diluted
The
eluant
is prepared the pH
from
commercial 3.8 7. )
adjusted
between Fig.
denired until
elution
separation.
(See the
be added
the solution D.
growth 5.
Apparatus 10 cm
region.
tip is plugged -
glass
. The
column with
is heated distilled
is filled
slurry settled
is obtained. is added
is removed Just
to further
impurities.
to using
reservoir
is washed
and a drop
is allowed 2. is
solution
containing
evaporated of hot
to near 0.05
centrifuge
MHC1. The 50 pl
to the above
resin the
cone
and sides
of
solution
is allowed
washing cone
is repeated. with 50 pl of eluant column. elution. with hot eluant is which The is then drop
centrifuge
the
first
after
The
above
so as to avoid
eluant
reservoir
separations
1/2
1 drop
per
Each
drop
on a platinum in an induction
plate
heat
lamp
and heated
heater
to remove
Procedure9
tiacem of organic The material. Phton
(Comtinu@
are ready to co~tn
.,
q pprokte
.
Fig.
elution pomitionp can b. predicted from the curve in . ~, assuming a 3-&op free column volume; however,
..
q light
to Ilcalibrtitefi bdore
eech are
cepi of
of
q oma
trensplutamium
q eparationfi
If cirrterm
but tie. for eech col~
me
sarne procedure
to provide
0.4
Cmz
q rea
milhquinlent the
should be at leant
10 timeh
diameter.
Rocedure
.,
This
re~in dde
procedure
e~ratem
the actinidm
Dowexlantlm-
end qbout
A. graded water. by
Dowex-1
im dne ia NH40H
q electkg
commercial
in roo=tempermture
The find
caacentrmtion
by
q ttaching
qectiom of 3-mm-diem
* . tip with glmm wool, . The columa uee.
cap-
tubing to
15-ml . .
teat.Afage
cone,
p8cMng
8nd filling
the bcke
to m height with
-bould
be alterxmtely
washed
elumit
before
qir jet in
5-ml
cone
in an ice -&ater
bath
aa
Procedure
4 (Continued)
with is is
HC1
from
a gas
transferred drop
after
called
is rinsed is then
of eluant
ia transferred
to the column.
One milliliter
are collected per
of eluant is carefully
through drop 3. with drop 12. The
placed
flow
rate
minutes
syringe fallen,
After
is removed
a 15-ml is placed
centrifuge
on top of the
resin.
is passed Cm,
elements. Pu
in drops resin
on the
and may
be subsequently
of Es actinide
It is typical
chemical handled. ,
foil.
gold
target
foil foil.
Ilknock
atoms
Ilcatcherri dissolved
catcher liquid
was
in aqua for
with
an equal 2. The
acetate
passed
through (see
-diam
X l-cm-long of about
bed five
of Dowex 30-pl
to 87 C original
drops
volume
plus with
containing
the actinide
elements
collected
and evaporated
of hot air.
Procedure
5 (Continued)
Tracer
Es
253
was bed
added
and the
solution
was
passed
a resin
-diam
by 5-cm-long The
to 87 C. of
adsorbed
a 0.4M
adjusted through
pH s=4. O colurr&at a
ammonium rate
eluant
of approximately in drops
four 20-pl
8-13, Fm
minute. Es
Md
fractione and
collected
in drops
in drops
27-31,
Cf in drops
39-47.
Procedure This containing 1. 16M HN03 added volume 2. times each with time. 3. step procedure lanthanides The . solution After the the is for oxidation
and extraction
No
to near the
is diluted
to make of the V ml
Eolution is
and
(Note
solution
of O. 15~
mote
is washed for
V ml The The
of freHhly aqueous
prepared are
KBr03,
phases step
solution
from
1 is contacted are
step
3 is washed lM KBr03.
V ml
of freshly
prepared
10M
HN03
di.qcarded. 5. utes into The V ml phaae washed organic phase from 10M step HN03 4 is back-extracted 1. 5M H202 for 3 min The
prepared
solution.
organic
6.
The
phaee
from
Step
5 is washed,
first
with
V ml of
O. 15M
90
Procedure
6 (Continued)
heptane
for
3 minutes, are
and then
with
V ml
of heptane containB
for
3 minute of the
B.
organic
phaEeB
dimcarded; of of
_97~0
and actin3.)
Cm
Note B 1. with little 2. PH(OH), O. lM _ KBr03 may be substituted at all points calling for 1~ KBr03
or no decrease HDEP
is di(kthylhexyl) in impure
and iB available
[1
c8H170 Chemical and H. W. similar Cf and Cm.
2 Works. Crandall,
reported (1951). 11
by D. C.
and Wallmann
have
used
a procedure
to Solution
submicrogram
quantitie8
of Bk from
volumes
reduced
to Bubmicroliter
quantities.
of macro
samples.
A jacketed
for
operation rate
at 87C
is prepared.
(settling
O. 5 to O. 25 cm/min) otherwise
as in Procedure
1A and num
The
column
in diam
of a platiThie
rod fused
capillary drope.
and bored
64 drill.
to be purified
is prepared
so as The
to be O. lM wallB
in HC1 rinBed
allowed
the column.
column
are
several 3.
1OO-P1 1 ml
About
of 2M HC1
31
Procedure
7 (Continued)
the
resin
at the rate
of about
6 drops
per
minute
until
collected. 2M HC1 is withdrawn rate and 1 ml per elute the of 6M HC1 minute close until together from is added 30 or 40 arnund 3).
remaining
through collected.
at the
of 6 drops elemente
transcurium
including III.
50 drope
step
in Table
32
Procedure
7 (Contiriued)
Table
III.
Order
of elution of cations
from
resin
column
in Procedure
7.
1
1
==7
13 16 17
22
2.6
of 2MHC1
24
26 28
30
Rb Ni
1
1
and
37
Ca
Al Sr Ba Actinidea Lanthanidea
53
2.8
64
3.6
4.0
70
75-85
96
4,4
-5.1
Zr
a
5.9
The
oxidation
rotate of these
exist,
it can be aesumed
state specified
2N HC1 is the one indicated. 0.2 mg of macro impurities, ima) generally run
half-width
at half data
6-8% under
to free and Pb) depend The
column move
several
of the
in O.1~
position
of the
solution
is adsorbed. affected.
of the actinidee
and lanthanides
similarly
33
REFERENCES
1. S. G. Thompson, History Discovery, Cunningham, Thompson and llThe Discovery of the Transuranium Elements: Used in
Their Their 2. 3. B. S. B. G.
Methods
U. N.
Transuranium Mass. ,
lishing 5, J. K.
, Reading, T.
Katz
and G.
IIchemistry 1957. G. R.
Methuen 6. S. J. 7. S. G. Am. G.
, Ltd. B. Sot. B.
Choppin,
and G.
T.
Seaborg,
76, B.
Gunn&gham,
Chem. 8.
2798 (1950).
& Nuclear W. Moline, Chem. and G. ~, W. 332-8 Mason, (1958). J. Inorg. & Nuclear
J. Fuger,
D. F.
Inorg. J.
9.
Peppard, ~, 344-8
Chem. 10. D. F.
Chem.
and J.
Wallmann, A. C,
Hesford, (1959).
and H.
Inorg,
Chem.
34
13. 14.
E.
K,
Hulet,
U.S.
2, 909,405 L.
L.
B,
Magnussen
Ander~on,
(1954). 15. A. M. Poskanzer Meeting and B. M. Foreman, Chemical Jr. , paper Society, presented New York, at 136th Sept, ,
National
of the American
1959, to be published.
16,
H. L.
(1956).
Smith
and D.
C.
Hoffman,
J.
Inorg.
& Nuclear
Chem.
~,
243-7
17.
J.
P.
Surls
and G.
R.
Choppin,.
J.
Inorg.
& Nuclear
Chem.
~,
62-73
(1957), 18.
E.
K.
Hulet,
R.
G. from
Gutmacher, the
and H.
S.
Coops,
Group
Separation
Lanthanides
by Ion Exchange,
11 UCRL-5639
Atomic to S. and R.
Energy G,
Harwell,
England}
private
Thompson Univ.
in reference.
5 above.
Gatti,
, Berkeley,
unpublished
dab.
66 (1956).
B. Phys. T. Beadle, Chem. J, Inorg. & Nuclear Chem, ~, 248 (1956).
J. Milated
W. E,
and A. J, and
Nervik,
A. Ghiorso
menta, Geneva, + Proc. 1958, Higgins
Sikkeland, Lntern.
U. N.
Con-f,
Peaceful
Atomic
15/P/2440. and W, 2nd, J. W. W. T. Crane, 1958, H. Proc. U.N. Conf. Peaceful Uses
25.
G.
H.
Atomic 26.
Energy,
Geneva, Barnes,
D. C. Hoffman,
published
procedure B. G.
used Harvey,
at Los G. 98,
Alamos R.
Scientific S. G.
Laboratory Thompson,
(1958). and
27.
A. G.
Ghiorso, T. Seaborg,
Choppin,
Phys.
Mmulm, W
Rev.
1518
(1955).
uSMC OHI-
OFTuhnlcal
lnfarwdlm
Rldw, T
?E