1
National v
Academy of
Sciences
National
Research
Council
E
The
Radiocheunistry
of Plutonium
,“.
m
.
COMMlllEE
ON NUCLEAR SCIENCE R. D. Evans, Vice Cluri7man Massachusetts Institute of Technology
~. A. Bromley, Chainmm Yale University
Lewis Slack, Secrekq National Rese=ch COunCtl E. C. Anderson Los Afamo6 Scientific Laboratory
Jerry B. Marion University of Maryland
N. E. Baflou U. S. Naval Radiological Defense Labomto~
R. L. PLatman Argonne National Laboratory
Martin J. Barger National Bureau of Standards C. J. Borkowski Oak Ridge National Laboratory
Ernest C. Pollard Pennsylvania State University
,
Katharine Way Oak Ridge National Laboratory George W. Wetherill University of California
Herbert Goldstein Columbia Uoivereity Bemd Kahn Taft Sanitary Engineering Center
Marvin E. Wyman University of Illinois
William S. Rodney National Science Foundation
Harold Glsser Office of Navsl Reeearch
George A. Kolstad Atomic Energy Commission
SllWllMMITIEEON RADIOCNEMiSTSY Nathao E. Ballou, Chaivman U. S. Naval Radiolostcal Defense Lain-atow G. R. Chq@n Florida State University Herbert M. Clark Rensselaer Polytechnic Institute Richard M. Diamond IJmrence Radiation Laboratory Jerome Hudla Brookhaven National Laboratory Jere D. Knight Los Alsmos Scientific Laboratow W. E. Nervik Lawrence Radiation Laborstory
Julian M. Nielsen Battefle Pacific Northwest G. D. O’Ke!.ley Oak Ridge National Laboratory E. P. Steinberg Argonne Nationaf Laboratory D. N. Sunderman Battelle Memoriel
Institute
John W. Winchester Massachusetts Institute of Technology R. P. Schuman, Consultant Sri Venkateswara University Tirupati, AndhI= Pradesh, India
The
Radiochemistry George”
of
H.
Coleman
September
UN17JERSITY Lawrence
1, 1965
OF CALIFORNIA
Radiation
Livermore, AEC
Contract
Subcommittee National
Academy
Plutonium.
Laboratory
California No.
W-7405 -eng-48
on Radiochemistry
of Sciences—National
Reaearcb
Council
Prfmtedin USA. Frice82.00. Available from the Cles.rinfm Federal SciemUficondTechnical Information,National Bureauof Standards,U. S. Depnrbnentof CommercerSpringfield,Virginia.
i
FOREWORD
The Subcommittee on Rsdiochemistry is one of a number of subcommittees working under the Committee on Nuclear Science within the National Academy of Sciences - Natioml I&aarch Its members represent government, Induetrlal, and council. unlverslt.y leti=tories In the areas of mmilochemistry and nucl-r chemistry. Support for the activities of this and other subcomnlttees of the Ccmuoittee on Nuclear Science is provided by a gmnt from the National Science Foundation. The Subcomnlttee has concerned Itself with preparation of publications, encouraging and appotiing activities in nuclear education, 6ponsoring sympo~ti on selected cum-ent topics in radlochemistry and nuclear chemistry, and investigating special A series of monographs on the mdioproblems as they arise. chemistry of essentially all the elements and on mdioclwnical techniques is being published. Initiation and encouragement of publication of artlcleB on nuclear education in various subject areas of chemistry have occurred, and development and improvement of certain educational activities (e.g., laboreto~ and demonstmtion experiments with mdioectivity) have been encouraged and assisted. Radioactive contamination of reagents and materials has been investigated and specific recommendations rmde. This series of monographs has resulted from the need for comprehensive compilations of mdiochemical and nuclaar chemical Each monogmph collects in one volume the pertinent tifommtion. Information required for mdlochemlcal work with an tiditidul element or with a specialized technique. The U. S. Atomic Energy Commission has sponsored the printing of the series. Ccumnents and suggestions for further publications activities of value to persons working with radioactivity welcomed by the Subcommittee.
M. E. &llou, Subcommittee
iii
and are
Chairman on Rsdiochemistry
PREFACE This
report
chemistry on IWmlear review
has been
Science
the radiochemist,
The
literature
The
author
The
staff
search
would
was
appreciate
in possible
author card
of the LRL
future
wishes file
Library�
competently
edit ed the final
especially C.
typed
Dr.
R.
made
aware
of this
thanks
W. for
Hoff, his
draft
for
conthued
aaaisted
Earl
through
September
to serve
Hyde,
for
to Carl
Vivian
of the
that they
might
the loan
of his
Wenari&h
and the to Mrs.
Mendenhall
who
the bibliography.
and support
Radiation
Laboratory,
the manuscript, during
and Dr.
the writing
monograph.
George
iv
and
o~tted.
search,
R.
at the Lawrence
Lawrence Radiation Laboratory University of Caltiornia Livermore, California
to
1964.
the needs were
in the literature
and criticizing
interest
techniques,
of such omissions,
and to Mra.
and prepared
reading
a
interest
monograph.
to Dr.
his colleagues
is included
plutonium.
references
of plutonium,
draft,
There
of particular
extensive
that important
editions
the first
the auf.bor thanks
Stevenson
being
on the radioof the Committee
“&d counting
for
apprmdmately
is sufficiently
who greatly
*O
P.
disacilution
completed
to express
of Sciences.
of plutonium
procedures
on the rmiiochemietry
Shauna Ness
I%mlly
of sample
of radiochemical
of monographs
on RadioChemistry
Academy
features
but it is to be expected
be included
extensive
the National
and chernic~
that the bibliography
radiochemiet,
as one of a series
the Subcommittee
a discussion
a collection
It is hoped
for
within
of the nuclear
finally,
prepared
of the elements
H.
Coleman
of this
CONTENTS
I.
General
Reviews
of Plutonium II.
General
.
.
Reviews
III.
Table
rv.
Chemistry A.
of the Inorganic .
Physical
c.
Plutonium
D.
Ions
VI.
.
.
.
.
3
,
.
4
.
.
4
.
in Solution .
Reduction
.
.
.
4
.
.
.
4
.
.
.
6
.
.
.
8
.
.
.
8
Reactions Reactions
C. 4
Radiolytic
Reduction
of Pu Solutions
C. 5
Hydrolytic
Reactions
of Plutonium
C. 6
Pu(IV)
C. 7
Complex
Polymer
.
Ion Formation
Methods
D. 2
Solvent
D. 3
Ion Exchange
.
Metallic Other
c.
Biological
Source
Preparation
B.
Criticality
Collection
Methods .
Safety Safety
Introduction
B.
Listing Procedure Procedure
1. 2.
17
.
.
.
24 24 28
.
.,
75
for
Analysis
96
.
.
.
.
.
.
96
Samples
.
96
.
96 96
Methods
96
.
.
.
.
.
.
.
.
97
.
.
.
.
97
.
.
.
.
.
99
.
.
.
.
.
99
.
.
.
.
.
102
.
.
,
.
.
102
.
.
of Contents
.
.
.
.
.
.
103
.
.
.
.
105
.
.
.
.
.
105
.
.
.
.
.
105
of Procedures
A.
.
.
.
Considerations
Radioactive
.
.
Electrodeposition
A.
.
.
Evaporation
.
16
.
.
and Counting
Counting
Safety
15
.
.
and Environmental
A. 3 Other
15
.
Samples
Plutonium
Preparation
9 9
Methods .
Compounds
Source
.
. .
and Precipitation
Extraction
of Plutonium
B.
4
.
Disproportionation
Separation
.
to the Radiochemist
C. 3
A. 2
VIII.
2
.
C. 2 Oxidation
A.
B.
1
.
.
States
A. 1 Direct
VII.
.
.
.
C. 1 Oxidation
Dissolution
A.
.
.
.
D. 1 Co-precipitation
v.
. .
.
.
.
Properties
of Pu
.
Chemistry
of Plutonium
Interest
Properties
A. 3 Chemical Compounds
.
.
of Special
Plutonium
B.
.
of Plutonium
of Plutonium
A. 1 Preparation A. 2
.
of the Radiochemistry
of Isotopes
Metallic
.
and Analytical
Determination of Pu in solutions amounts of Feand Cr . . Separation extraction
and determination . . v
containing , .
of Pu by TTA . . .
large .
.
108
.
.
112
CONTENTS
(Continued) Page
Procedures
Glossary References
(Continued)
Procedure
3.
Separation U – fission
Procedure
4.
Plutonium
.
.
Procedure
5.
Plutonium
.
.
Procedure
6.
Separation of Plutonium from Fission Products in Irradiated Targets . . . .
Uranium Reactor . .
and determination product mixtures
of Pu in .
.
.
114
.
.
.
.
.
116
.
.
.
.
.
118
.
.
122
.
.
.
124
Analysis
.
.
126
.
129
Metal
130
and .
131
.
132
.
134
.
137
and
Procedure
7.
Determination
Procedure
8.
Uranium
Procedure
9a. Separation Uranium.
of Plutonium . . .
from .
Irradiated . .
of Plutonium
from
Uranium
of Pu
.
and Plutonium
Procedure
9b. Separation
“Procedure
10. Purification of Plutonium Fission Products .
Procedure
11. Uranium Samples
Procedure
12. Plutonium Samples
from .
Environmental . .
Procedure
13. Plutonium Samples
from
Environmental
from .
Uranium . . .
and Plutonium from Environmental of SO1l, Vegetation and Water Water . Water . .
Procedure
14. Separation of Plutonium Fission Element Alloys from Chloride Solutions
Procedure
15. Separation of Pu before Spectrographic of Lrnpurities Anion Exchange Method
.
in Uranium-Plutonium by TBP Extraction . . . .
Procedure
16. Separation of Plutonium Analysis of Impurities. Chromatography Method
Procedure
17. Separation
Procedure
18. Separation of Np and Pu by Cation Chromatography . . .
Procedure
19. Determination
of Plutonium
Procedure
20. Determination Electrodeposition
of PU239 in Urine Procedure)
Procedure
21. Determination
of Plutonium
Procedure
22. Determination of Americium Presence of Plutonium .
Analysis . .
Before Spectrographic Extraction Using TBP . .
of Np and Pu by Anion
Exchange Exchange . . .
.
140
.
142
.
144
.
148
.
149
.
.
150
(Small Area . . .
in Urine
.
153
.
.
155
in the . .
.
156
by Anion . .
.
161
.
164
in Urine in Urine . .
Procedure
23. Determination Exchange .
of Plutonium . . .
Procedure
24. Determination crystallization
of Plutonium in Urine by Cowith Potassium Rhodizonate
Procedure
25. Determination of Plutonium in Urine and Bone Ash by Extraction with Primary Amines .
.
No.
in Urine . .
.
166
.
.
.
.
.
.
.
.
.
.
.
.
.
.
167
.
.
.
.
.
.
.
.
.
.
.
.
.
.
169
vi
The
Radiochemistry
of
GEORGE Lawrence
Radiation
H.
COLEMAhT
Laboratory,
University
Livermore,
I.
GENERAL
REVIEWS
OF
J.
J. Katz
VII, 2.
Complex
THE
M.
1962
5.
R.
and Z.
E.
Eds. 6.
J.
7,
B.
9.
and T.
Nanowski)
Chap.
llo~dation
Book
Elements,
Statea,
and
Vol.
Metz,
D. Nebel, Service
“The NYC,
14A,
I.
Turton). New
Vol.
A.
D.
Gellman, Bureau,
1964; transl.
New
by E.
Chap.
and Oxidation-Reduction
Natl.
Nucl.
8, G.
T.
Energy
Seaborg
Series,
Div.
and J. J. Katz,
in Qe
10, pp 371-434.
14A,
Chap.
Chemistry
of the Compo~ds
of Plutonium,
JPRS - 11689.
of Plutonium,
”
10, pp 371-434. ” Anal.
of Plutonium,
Chemistry
Report
Ed.
1962) pp 324-864.
Equilibria,
Elements,
14A;
Chap.
Vol.
Analytical
Genl.
(Consultants
York,
and Properties
Analytical
AEC
Pascal,
Paris,
Mefod’eva
Co.,
” Chap.
Co., Inc., N-ew York, 1954) pp 221-300. Molecular Species of PlutOnium in Solution, ”
Elements, “The
Paul
ElementsJ”
potentials,
Vol.
Cuntigham,r’Preparation
F.
et Cie,
Elements,
239-325.
2, pp 39-84.
Record
llIoni~
pp.
Minerale,
P.
”in The Actinide
Project
Hindma-n,
B.
N.
(Macmillan
in The Actinide C.
by C.
and M.
Plutonium,
ANALYTICAL
of the Actinide
1957),
of the Transtiranium
Zaitsev,
of Plutonium,
Actinide
8.
M.
(McGraw-Hill
c.
York,
(Masson
L.
Plutonium
Chemistry
New
et Transuraniens” Compounds
Connick,
Reactions IV,
, “The
AND
PLUTONIUM
de Chimie
transl.
Taube,
Lepa
Seaborg,
INORGANIC
OF
Traite
I. Moskvin,
York,
T.
and Sons Inc.,
in Nouveau
“Uranium
“The A.
4,
Wiley
“Plutonium,” xv,
3.
and G.
(John
of California
California
CHEMISTRY
1.
Plutonium
transl.
” Joint from
Chem.
29,
Publications
Chem.
Tech.
1748 (1957).
Research Leipzig,
~
522 (1961), 10.
P,
N.
Palei,
“Analytical
AERE-LIB/TRANS11.
A. Co.,
12.
A.
J. Moses, New
K.
W.
Zeit.
Bagnall,
(See
Analytical
of the Actinides,
also
J. Anal.
Chemistry
Chem.
” transl. USSR
by S. BotcharskyJ
~
of the Actinide
663 (1957 ).)
Elements”
(Macmillan
1963). “Plutonium,
Schiffers,
Chemiker 13.
“The
York,
Chemistry
787.
seine
chemischen
und physillilischen
Eigenschaften,
”
86, 656 (1962). “The
Transuranium
Elements,
” Sci.
Progr.
(London)
52,
66-83
(1964). 14.
V.
I. Kuznetsov,
Chemistry 15.
R.
Kraft,
C.
and Plutonium University
S. B.
Sawin,
of Uranium, J. Wensrich Alloys:
of California,
and V.
Thorium and A.
Methods
A.
Mikhailov,
and Plutonium, L.
Langhorst,
and Technique
Livermore,
Calif.
1
s,”
“Progress
” Russ.
Chem.
“Chemical Lawrence
UCRL-6873,
in the Analytical Rev.
Analysis Radiation 1962.
29,
243 (1960).
of Plutonium Laboratory,
IL
GENEWL
REVDZWS
OF THE
RADIWHEMISTRY
OF PLUTONIUM 16.
E.
K.
Hyde,
Acthide
Elements,
Project
E.
Record CO. , New
Book 1’7.
K.
Hyde,
in Proc.
1955, 728.
M.
Faugeraa,
Nouveau
Traite
“Uranimn 19.
M.
National
Vol.
14,
York.
Nuclear G.
1954)
A/CONF.
Z. Nanowdi).
Series,
and J.
(United
“Radiochemical
Div.
J. Katz,
Methods
Nations,
Paul
( ~sson
Methods
New
IV,
in The
plutonium
Eds.
(McGraw-Hill
the Actinide Uses
York.
Gen.
Paris,
York,
of Analysis,
Elements,
of Atomic
1956)
des Isotopee, PaBcal,
et Cie,
Co. , New
2
for
on the Peaceftd
et Purification Minerale}
(Macmillan
Elementfi~’
15.
Separations
“Separation
Plutonium
Energy
Conference 8/7,
de Chemie
of the Actinide
Seaborg
Chap.
et !lh%sura.niens,”
Taube,
T.
“Radiochemical
Paper P.
Separations
of the International
Geneva,
18.
“Radiochemical
pp 261-303,
(of Plutonium), Ed.,
Vol.
” in
IV,
1962)
PP 339-385.
1984; transl.
by E.
” pp 78-84.
”
Energy,
Lepa
and
~ - TABLE
Isotope ~u232
PU23 3
~u234
PU235
PU236
~u237
.,
~u238
Pu
239
PU240
Half
Life
Specific Activity (d/m/pg)
OF ISOTOPES
OF
pLuTo~M*
a Particle Energy (MeV)
Type of Decay
Method
36 min
0’270, EC 98$
6.58
20 min
--
ao.lye, EC99+7’0
6.30
9,0 hr
.-
067’0, EC 9470
6.19
a3 x 10-37., EC 99 + ~.
5.85
c1
5.763 5.716
ao. oo370, EC 99+%
5.36 (797’0) 5.65 (217’0)
3.88 X 107
a
5.495 5.452
(72~0) (28%)
1.36 X 105
a
5.147 5.134 5.096
(737’0) (1770) (10~0)
5.00 x 105
c1
5.162 5.118
(76%) (24%)
--
26 min
2.85 yr
1.18X
45.6 days
86.4 yr
24,360
yr
6,580 yr
109
--
of Preparation
U235
--
+ 100 MeV particles ~233
+ 40 MeV particles U233, 235 particles Cm238 U233, 235
PU242
PU243 PU244
13,0 y-r
2.57 X 108
a4 X 10-370, ,B-99+7’O
4.89
3,79 x 105 w
8.65 X 103
(Y
4.898 4.858
4.98 hr
--
7.6X107
42.8
D
+ 40 MeV Daughter
+ 20-30
a of
MeV
a particles (69~o) (317’0)
~235
+ 40 MeV a particles Daughter Np23 6 Daughter Cm240
U235
+ 40 MeV
P-
---
(2
---
Q particles
~238
+ deuterons Dau hter Cm242 Pu2 $ 9 + high energy neutrons Np237 + neutrons U238
~238 PU239
+ neutrons
+ neutrons + neutrons
Daughter PU241
a
of Cm244
U238
+ neutrons Dau hter of Cm245 u23 i? + a particles (767. ) (2470)
U238 Am241
+ neutrons + neutrons
PU242 + neutrona
w~u245 PU246
--
10.6 hr 10.85
days
Pfl-
--
---
PU244
---
~238
+ neutrons + neutrons
(ther -
% The should
data for
this
be consulted
table for
were
further
taken details
from
the recent
and references
3
review
of Hyde. 192
to the literature.
Tfiis
work
IV.
CHEMISTRY
OF PLUTONIUM
OF SPECIAL A.
A.1
INTEREST
Metallic
TO THE
RADIOCHEMIST
Plutonium
Preparation Plutonium
metal
electropositive of halide
discussed
A.2
metal
reduced
Physical
the melting
Table
IV-1
point,
the oxide
coating
Pu metal
slowly.
The
which of five
negative
scale,
while
Anselin,
scale.
has a number allotropic
coefficients
physical
intermetallic
behavior
or less
the underlying
acids.
of peculiar
modifications
of thermal
expansion.
properties.
However,
and alkaline of Pu toward
metal
dissolves
simple
easily
with
volubility
earth
metals.
prepared
cerium
and in several
and the oxidation
and rapidly
in moderately
solid are
usually
the liquid
is given
made
or solid
in Table
IV-2.
However, proceeds
gases;
solutions
in its
in a few
days the
is complete.
by most
series
(Cc)
occurs
temperatures
mixtures
-4-
in the EMF
surface
to PU02
in dry air.
in either
solutions
(Th)
snd resembles
adherent,
+ e- is
Pu = PU*+
and thorium U,
intermediate
eutectic
little
various
the couple
the oxidation
at elevated
compounds
and very
(Se)
of a freshly
is more
is attacked
for
than does
until finally
Pu metal
by alkali
scandium
readily
oxide
etc.
elements.
potential
oxidation
halogen
S02,
Va and VIa ‘“metals, hibited
more
accelerates protects
The
it between
The
air.
reaction
Pu forms
have
metal a total
important
metal.
Superficial
in normal
metallic
the more
places
in air.
HC1 and other
undergoes
two of which
Pu oxidizes
oxidation
halogens,
on an industrial on a gram
appearing
metal
reactive
which
of elements.
more
and Reas
Properties
Pu is a very
hours
The
summarizes
Chemical
reactions
to metal
by a more
combinations
satisfactory reactions were PuF3, 164 and 0rth306 have
Harmon
the conversion
silver-white
properties.
2.03 volts,
for
,of a halide various
Properties
below
A.3
the reduction has compared
Connor
and found that the only
of Pu salts
a method
Pu is a typically physical
prepare~8by
with Ca metal.
the conversion describe
et al.30
commonly
such as calcium.
and reducing
, and PuC13
PuF
is most
metal
Hz,
N2,
concentrated
with most with the group state
is ex-
:
TABLE A.
Appearance
Silvery
IV- 1. Physical
white;
B.
Melting
point
639.5° C
c.
Boiling
point
3508 * 19° C
D.
Properties allotropic
of the various modifications
0?
Metal’:<
in air
6-
?’
e
125
210
315
460
475
640
Density (at T“C)
(g/cm3)
19.82 (25)
17.82 (133)
17.14 (235)
15.92 (320)
16,00 (465)
16.48 (510)
Crystal
structure
Bodycentered monoclinic
Orthorhombic
Facecentered
Body-or facecentered tetragonsl
Bodycentered cubic
67 X 10-6
41 X1 O-6
35 x 10-6
-8.6 x 10-6
(-_---.------)
(80-120)
(160-200)
(220-280)
(340-440)
(---. --------)
490-550
958
140
156
17
470
940
Latent heat of transformation to next higher phase (cal/g-atom) E.
oxidizes
of Plu\onium
Transition temperature to next higher phase PC)
Coefficient of linear expansion (“C-l) (in temp range 0C)
m
quickly
Properties
Electrical (at 25” C)
1?.
Self heating Ionization
coefficient
(1.923
+ 0.019)
X 10-3 W/g
.!,
from
15
5.1 * 0.5 eV
potential
““Data compiled
cubic
68.5M’i2- cm
resistivity
G.
Monoclinic
various
secondary
sources,
including
Francis,
137
Co ffiriberry
and Walciron,
94
and Jette.
211
TABLE
IV-2.
Behavior
of PU Metal
H20
Very
Salt water
Rapidly
HC1,
HI,
slowly
Rapid
HBr
attacked
attacked
after
induction
Rapid
HNo3-
Very alow attack, limited surface is passivated Rapid
H~S04”
Very
Sdfamic
dissolution
in concentrated
HC104
H3P04
with
II through
compounds
VI oxidation
describe
states
the data by relating actinide
The
the insoluble
hydroxides,
and are
described
in Pu chemistry
or neutral
The
to HN03
of those
detail
solutions.
in that
The polymeric
to destroy.
which
and attempt
numbers
states are
The
can be quite on hydrolytic
and peroxides
the
Of these of the reactions
complicating
by hydrolysis
intractable reactions
compounds
with which
and co-precipitation
form
prepared.
to systematize
interest.
One of the great
in dilute
in msny
reactions,
of Pu gives
details. Table
117-3 lists
have been
volubility
information
for
the more
stable
Pu compounds
which
prepared. TABLE
IV- 3.
%lubility
of Plutonium
Compounds* Reference
PuH2 -PuH3 “PuF3-PuF4
‘u02F2 NaPuF5
s. **
HC1,
H2S04,
i.
decomposes in fluoride i. H20, mineral acids i.
HN03,
decomp.
completing
in H20
agents;
e. g.
s1. s.
dilute
PuF6
decomposes
PUC13
s.
HN03HF, violently
i.
NaF-HF
in H20
H20, acid
CS2PUC16
S. acid,
PuBr3
s , H20
H3J303 27
HZO
H20
6
s.
H3B03
128
table.
are the ones
of primary
of a polymeric form
been
of the complex
phosphates
section.
section
have
of the periodic
in precipitation
is the formation
and Heuberger
compounds
and oxalates,
interest
of Pu in the
compounds
regions
compounds
Compounds and Faugeras
Cunningham,7
as to other
fluorides,
in more
and may be difficult
coating.
acid
of elements.
IV and VI oxidation
of major
factors acid
number
and the insoluble
are
to the otide
behavior
and coordination
as well
of the III,
deals,
in
of Pu
the data on complex
the structures
radiochemist
III and IV states
a large
and properties
elements,
compounds
Compounds
are known.
3 emphasize
~.
dissolution
dissolution
with
the preparation
Gel! man,
principally
similar
slow
acid
in concentrated
attack
B. Pu forms
acid;
in concentrated
dissolution slow
Rapid
acid
period
dissolution
No visible reactio,n dilute acid
acid
to other
Solutions
Behavior
Solution
Acetic
in Various
TABLE
IV-3
(Cont. ) Reference
s.
PU13
H20
PU(103)3
s. HN03, mo3
i.
PU(103)4
s.
decomposed
PU02
s. slowly in boiling mineral acids; reaction speeded by fusion with NaHS04 or HF added to HN03; solubilit y is more cliff icult if ignited above 500°
PU(OH)3
s. mineral
acid
PU(OH)4
s.
mineral
acid
PU02(OH)2
s.
mineral
acid,
PU peroxide
s,
cone.
i.
M2S04-H2S04,
M=Na,
MPU(S04)2>
K,
Rb,
CS,
PU(S04)2 M4Pu(S04)4,
M=K,
Rb,
NH4
M2Pu(N03),6,
M=K,
Rb,
Cs,
POP04
Put,
yH20
S. H20
H20,
i.
alcohol
s.
H20,
i.
alcohol
cone. HTJ03,
i.
mineral
alcohol
Pu forms in HN03, ether,
acetone
‘. H20’ ‘il acid S. hot cone. mineral acid; s1. S. NaOH; i. HC2H302 H3P04,
s.
acid
- H3P04
HC1,
H2S04, i. cold HN03-NaF2
cone
HN03
S. hot cone.
PUOC03 K6[pu(co3)510
mH20
K4[Pu(C03)41.
mH20
i.
H20,
i.
alcohol
s1. s.
cold
mineral
acids
o mH20
K12 [ pu(co3)d M4[Pu02(C03)3]
, M=K,
NH4
xH20
HPUFe(c~)6°
PuFe(CN)6 Pu3[Fe(CN)6]
4. XH20
(Pu02)3[Fe@’)6]
PU(C204)2
H2S04
s.
i.
264
ZH20
PU2C3
PU2(C204)3
T1
= 1.8 X. 10-23
XH20
PU2H(P04)3. PU3(P04)4.
HN03,
excess
in H2S03
Ksp
s. H O, colloidal aque 3 us soln. s.
P;(N03)4
PU(HP04)2.
NH4
HN03,
H2S04-K103,
.xH20
“6H20
2“ ‘H20
:: ~:::$a:~co,, i.
HC1
i.
HC1
i.
HC1
i.
HC1
i. H20, s. (NH4)2C204
NaPu02(C2H302)2
minersl
s.
acid;
S. mineral
HN03 acid;
‘2C 2°4 s1. s. hot H20,
7
-
H20,
s1. S. K2C204.
i. H2Cl, s. H2S04, HN03, acid-K2C204, NH2C 204 in 1.5 ~
PU02(C204)-3H20
d.
HC104 s1- s. minimum s.
0.025 M ‘2c204 s1. s, s.
acid
acid
–
264
*
Compiled primarily from the reviews of Cunningham and Faugeras Unless otherwise specified, the data are taken from these reviews. ** The following abbreviations are used: s.
soluble
i.
insoluble
S1. s.
slightly
soluble
cone.
concentrated
dil.
dilute C.
C.1
Oxidation Plutonium
resembling The taken
both
from
Plutonium
solution
uranium
(U),
oxidation
Latimer.
exists
in Solution
in the +3,
neptunium
potential
(Np)
diagrams
+4,
and
for
+5,
or +6 oxidation
americillm
Pu in acid
(Am)
states,
in this
and basic
respect,
solution
are
2â&#x20AC;&#x2122;0 ACID
SOLUTION
BASIC Pu ~
Ions
States in aqueous
formal
and Heuberger
~(oH1
o 95 PU(OH)4
3
SOLUTION
u
=
PU020H
PU02(OH)2
-0.51
Formal Table
oxidation
IV-.4.
tendencies TABLE
The
potentials
for
displacements
of the anions PJ-4.
with
Formal
Pu couples
are
1~
solutions
are
for
Pu Couples
in Various
Pu(IW)-PU(VI)
Pu(fII)-Pu(VI)
1~
Solutions
Pu(v)
-PU(VI)
HC104
-0.982
-1.043
-1.023
HC1
-0.970
-1.052
-1.024
-0.912
HN03
-0.92
-1.05
-1.04
------
H2S04
-0.74
-1.2- 1.4
------
------
The
lower
oxidation
Am,
and correspondingly
This
effect
of various
is illustrated actinide
ions.
states
shown in
due to the complex-forming
Pu.
Potentials
PU(III)-PU(IV)
in various
of the potentials
become
the higher in Table
more
stable
oxidation
IV-5,
which
-0.92
in the actinide
states
become
shows
the free
more
series
from
difficult
energies
U to
to attain.
of formation
128
TABLE
Free
IY-5. M
Thus
of Actinide
+t++
M
Ions
MO;
(kcal/mole)
MO~
-124.4
-138.4
-237.6
Np
-128.4
-124.9
-221.0
-194,5
Pu
-140.5
-118.2
-204.9
-183.5
Am
-160.5
-110.2
(-194.5)
-156.7
the most
stable
+3 ion in this
Pu is the first
enough
in aqueous fact
selectively
member
solution
is taken
in which
in the radiochemistry
oxidation-reduction
behavior
stable
+6 ion is
state
is stable
chemistry.
the +3 or +4 oxidation in many
the most
the tripositive
importance
ability
-236,4
, wliie
is Am+
series
in separation
in either
of this
series
of this
to be useful
is of supreme maintained
Advantage The
+++
of Formation
u
uo~.
This
Energy
of Pu,
states
of the collected
since
procedures
of Pu is complicated
Pu can be
in separation
schemes.
in section
by several
VI.
factors:
(1) f/0~
disproportionates into PU+4 and PuO~ and under certain conditions PU+3, ++ +4 and PU02 can all exist in equilibrium; Pu. m a small, highly , Puo;,
Pu
charged many
ion and therefore
stable
Pu(IV)
complex
forms
polymer
undergoes
ions.
This
a long-chain
extensive
tendency
compound
is one of the more
hydrcdysis
at low
is a dominant
feature
or polymer
by hydrolytic
aspects
of Pu chemistry
unpleasant
acidity
and forms
of Pu(IV)
chemistry.
reactions. from
Pu(IV)
the standpoint
of
the radiochemist. C. 2 Oxidation-Reduction Table
IV-6
Pu ions.
lists
Reactions
reagents
produce
a large
reactions
may
be taken
change proceed
as a guide
In general, one electron
the change is invalved
bond are
usually
which
C. 3
The
with acid,
proceed
state
potentials oxidation
respect
considered
change.
However,
in oxidation
state
in conditions
for
may
of the oxidation-reduction the listed
reactions
should
+3 and +4 is rapid, since only ++ changes are rapid. PuO~ and PU02
involve the making 184 m a general
Hindman, gives
as some
reviewed
examples
involving
only
the kinetics
of actinide
Pu couples
are
or breaking review
of reactions electron
of a Pu -O
of the kinetics involving
transfer.
oxidation-reduction
of
M-O
Newton
and
reactions.
Reactions
of the various may
exist
to disproportionation
for
some
between
Similarly
reactions,
states
uncompleted
change
Therefore,
state
of Pu which
as rapi~y
slso
Disproportionation
several
in this
slower.
have
listed.
in oxidation
oxidation-reduction
Rabideau302
those
changes
small
and that
in the equilibrium, beyond
in the oxidation
actinide
to effect
that a relatively
only.
Changes
bonds
and conditions
It must be emphasized
media.
There
an understanding
in equilibrium. into higher are
several
such that appreciable Pu(IV)
and Pu(V)
and lower
oxidation
important
eqtiibria
of Pu oxidation-reduction
quantities
states
chemistry,
of
are both unstable
which
in weakly must be
TABLE
IV-6.
Oxidation-Reduction A.
Reagents
Solution
of Plutonium
Ions*
R(m)
Temp.
Rate
Reference
Very
rapid
1,5 ~HCl
R.T.
Very
rapid
6~
R.T.
Very
rapid
R.T.
Very
rapid
0.5 &lHCl
R.T.
Slow
R-6 ~
R.T.
Equilibrium at 907’” Pu(N) in several hours
145
R.T.
Equilibrium at 80 -90~0 Pu(~) in several hours
145
rapid
acid
HC1,
dilute
H202
-
R.T.**
Dilute
C12
Reactions Pu(IH)
H2S04
HC1
4-8 &l HC104
235 235
(tllz
>9
hr)
cr207 H103
Dilute
acid
R.T.
Extremely
Dilute
acid
R.T.
Extremely
rapid
mo~
Dilute
acid
R.T.
Extremely
rapid
115 ~
HC1
R.T.
No oxidation
02
97” c NO;
2.5~0 oxidized
more
rapid rapid
ITN03
R.T.
Very
0.4 – 2 ~ HN03J Fe(H) Sulfamate,
R.T.
Complete
0.1 ~
79
in 42 hr. in 4 hr, in higher 63
in few
minutes
63
HN02
“This table is an enlarged version o~ the one given by Katz and Seaborgl which was compiled from data given by Connick. Unless otherwise specified, the data were obtained from this source. ** R. T. = room temperature.
10
B. Reagents
Pu(~)~
Pu(LU)
Temp.
Solution
Rate
Hydroquinone
mute
HN03
R.T.
Rapid
H2, Pt
0.5 g
- 4. O~HCl
R.T.
> 9~0
reduced
Reference
in 40 min
I-
0.1 yKI+
0.4 ~
HC1 R.T.
Hso;
0.05 ~ NH4HS03, 0.3 ~ mo~
R.T.
NH30H+
0.5 M HN03 NH36H+
+ 0.1 ~
R.T.
HC1
----
-----------------------
R.T.
Rapid
NH20H. Zn S02 Ti#
.0.5
~
HC1, HC1
‘1/2 ‘1/2
1~
HN03
R.T.
6 ~
HC1,
R.T.
tl] 2 Very
R.T.
Very
dilute
H2S04
1 ~ HN03 Dilute
HC1 or H2S04
Ascorbic
HN03
Acid
0.5 ~HN03, 0.01 ~ Ascorbic acid
= -2 min -40
65
min
< 1 min rapid
235
rapid
235
Rapid
+ 1 ~H2S04R.T.
Cr++
H202
‘1/2
=2min
R.T.
103
Rapid
235, 449
Rapid
416,402
Rapid
R.T.
6 MHN03 O.1~ A s~orbic acid, Fe(II) Sulf amat e
R.T.
Rapid
7J~HCl
R.T.
Complete
11
65
65 in several
hr
145
c..
85” c
99~0 oxidized
R.T.
Complete
in 15 min
pH 4.5, -8,2, 0.1 ~ HOC1
80” c
Complete
in 15 rnin
Complete
in 5-10
BrO~
0:1 ~ BrO~, 1 ~ HN03
C e+4
0.1 ~ HN03
HOC1
+ 0.84
Ce+4,
0.5 ~
45y’ K2C03
4@ c
H5106
0.02 y H5106, o.22&JHN03
R.T.
Ml-lo;
l~HNo3, MnO~
25” C
0,001 y
or Ag+
Ce+3
catalyst
0.25 ~ HzSO+ catalyst 0.25 ;M_H2S04, catalyst 2 ~ HC1,
no no
no catalyst
Ag+ + S20~, HN03
1.1 ~
0.5 N H2S04, Ag(ti) cr207
0.05 ~ dilute
HN03
0.55 ~ 1X
Clz
Solid
tl/2 tl/2
HN03,
than
in 4 hr
min
= 100 min = 50 min
Complete
in 30 min
19=C
Complete
in 15 hr
150
65° C
Complete
in 1-1/2 hr
150
R.T.
2-8 hr depending concentration of
25” C
Complete
on Pu
275, 276
in 1 rnin
O
361,
R.T.
= 15 min ‘1/2 Complete in 9 hr
129
98 * 1“
8CF7Lcomplete
301
25° C
HC104, H2S04
in less
@ C
in 2 hr
10-3 MPu
0.03 ~ H S04 + saturate 7 C12
800 C
0.1 ~
22 c
~ Electrolysis
Reference
Complete 5 min
5 M HN03 g/Xt er
Ag*
Rate
R.T.
NaBi03
03
Pu(VI)
Temp.
Solution
Reagents
Pu(IV)+
Clz
0.5 ~
HC104,
0.025
‘1/2, tl/2
= 35 rnin =2hr
0.056 &l ClHC104
R. T.
Complete
12
in 30 min
454
39
D. Solution
Reagents HCOOH
HN03
Pu(VI)
s
Pu(~) Rate
Temp. slow
R.T.
C20;
0.02 ~
I-
2.3~EU, HN03
H2C204
Fe~
75° C ?
tl/2 Rapid
HC1
R.T.
Rapid
2-6 ~ HN03. 1~ Ferrous Sulfmate
R.T.
Rapid
3.1 ~
Reference
= 60 m.in
75
2-4 ~’ H2S04
R.T.
Fairly
NO;
HN03
?
?
H202
HN03
R.T.
Fast, reduction continues to PU(III)
E. Reagents HN02
--------------0,5 M HC1, NH3mH+
R.T.
slow
~
R.T.
slow
F.
Pu(VI)~
0.015
Solution
Reagents I-
pH 2
R.T.
0.5 M Cl.. 0.05 ~ NH2XH ?
25” C
S02
pH -2
Fe+
0.05 – 2 ~ ~=2.
The
first
of these + 2H20
3PU+4 for
which
. (Pu+3)2
Rate
Reference
Rate
Reference
‘1/2
= 180 min
25” C
Complete
0-25° C
---------------------
in 5 min
of Pu(137) according
301
to the reaction
++ + AH+ + PU02
= 2Pu ‘3
(PuO~+)
295
Instantaneous
is the disproportionation
the concentration
~
HC104,
96
Pu(V)
Temp.
NH2NHj
361, 39
+Pu(IV)
Temp.
Solution
NH30H+
Pu(V)
fast
equilibrium
constant
may be written
(H+)4
c (Pu~)3 Table strength
IV-7 for
lists
different
Kc for
this
reaction
under
similar
acids.
13
conditions
of acidity
and ionic
of
Concentration Equilibrium Acidm at 25°C*
Constant
P~%EV~;k
H+~
Acid
for
the Disproportionation
1.0 M; ~=l.O 9X1
HC104
O-3
HC1
2x
10-3
HN03
4x
10-7
H2S04
Very
low
**
3 *~Taken from Gel ‘man ~. Appreciable quantities of Pu(III), Pu(IV), and Pu(VI) cannot efist together in H2S04 s olution9. These The
data
show that strong
equilibrium
strong
markedly
formed
by Pu(IW).
complexes
lowering
the concentration
hydrolysis The
Puo; firat
reaction order
reaction only
is slow
sequence PU+4
PuOH+3 PuOH+3
range
concentration ia 1.5 ~
while
The
second
unstable
Conrdckgg
acid
describes
this
solution
2 PuO~
(B)
PuO~
by the
to the right
until the onset of
Pu(IV). of bimolecular
reactions.
is involved,
while
reaction
the second
is secondThe
in H+ concentration. discrepancies
+ H+ + H+ H.O
amount
+ H+
of each oxidation
concentration.
concentration
in a 4 X 10’3
of acid
respect
present
over
M Pu(IV) —
solution
is 8 — M.
is the diaproportionation with
state
He found that the minimum
of Pu(VI)
of Pu(V),
which
is
to the reaction
+ PU(VI) overall
reaction
as proceeding
reactions (A)
at least
stabilize
of the first
third-order
formation
equilibrium
rate
with these
the relative
at 98” C the required
= Pu(rv)
The
PU+3 + PuOT+
and ~03
important
bond formation
and inverae
PU(OH)2H
in moderately 2 Pu(v)
Pu-O
transfer,
to prevent
anion,
strengths
is shifted
(Fast)
+ H20
of HN03
again
+3
PuOH+3
of temperature
ionic
(slow)
+ H20
+ Pu(OH)~
forming
reactions
is consistent
determined
Crocker’O’ wide
because
concentration
reaction
on the equilibrium.
low
the equilibrium
+ PU02+
electron
medium
at these
probably occurs as a series 100 the reaction path may be
= PU02++ + Pu
requires
in Pu(IV)
following
reaction
. pu+3
+ PU+4
even
Conversely,
hydrolytic
and McVey,
2pu+4
The
The
disproportionation to Connick
of the anionic
to the left
of the acid and complex
at pH 1-1,5.
According
iniluence
is shifted
+ 4H+ = Pu+4
+ PuO~
+ Pu+3 + 4H+ = 2Pu+4
+ 2H20
+ 2H20
14
by either
of the two
slow
a
by
followed
by the fast (c)
Reactions
Puo;
+ PU+4
only
more
by other
alpha particles
not.
reaction
Reaction
A
B to occur,
followed
first,
in oxidation-reduction
oxidation
in the decay of Pu 239 of Pu by radiolysis.
solutions depending
the Pu, effect
reduction
of Pu(VI)
of acidity
over
was
on the nature
first
described
to Pu(IV)
a range cases
per
or reduction,
by direct
oxidation
the
oxidation
or reduction
proceeds
to Pu(V),
The
rate
radiolysis
acid
energy
to the medi-
products
salution
of reduction to allow
The
to be present.
and the lower
enough
then oxidize
and the oxidation state of 215 who noticed 0.670 and Sheline
by Kasha
The
supply
of the solution
is S1OW enotigh
states
239
day in perchloric
0.1 to 2 ~.
the reaction
of the various first
of direct
emitted
urn to decompose
II-I both
C does
for
of Pu Solutions
or reduce
less.
may be involved
Instead can occur
Reduction
This
while
is formed
product.
Radiolytic
the Pu.
bonds,
PU+3
than A.
reactions
reaction
of the appropriate
of Pu-O
sufficient
probable
reagents.
disproportionation
The
until
disproportionation
reactions
+ PU+3
the breaking
important
B is kinetically
These
C.4
= PU02*
A and B involve
is probably since
reaction
states
h
was
independent
considerably
the equilibrium
reduction
obtained
which
HC1 was
of Pu(VI)
quantities probably
by disproportionation
of this
ion. Rabideau rates
confirmed
~.326
of HC104
the above
and HC1 reduction
production
of Cl-
to HC104
solutions,
in HC104
qualitative
results
concerning
and found that the situation
solutions
a net oxidation
and C12 in HC1 solutions. instead
is initiaJly approximately 4. x308 and Page; and Haissinsky Pages
of reduction
the relative
is complicated Also,
occurs
by the
if Br - is added
if the mean
ofidation
number
very
strongly
induced clo~
on the nature
reduction ~ so~
by alpha Popov
increase
of NO~
The lesson
C, 5
rates
These
external
and total
in a study
of external
of reduction
results
of reduction
depended
gamma-radiation
decreased
presumably
hand found
only
x-radiation.
also
in the order apply
to auto-reduction
The
oxidation rate
by irradiation
of oxidation
of HN03
decreased
with
an
states
of old Pu
acidity.
to the radiochemist
particularly
low
acidity
is clear: HC104
The
stated
oxidation
and H2S04
solutions,
sho~d
in aqueous
solutions
as highly
be viewed
suspicion. Hydrolytic
Reactions
Pu in all of its and therefore for
>> NO;.
et al. 320 on the other of Pu with
with
The
found that the rate
particles.
solutions
salutions,
of the anion
of Pu(VI).
> Cl-
309
these
tendency
undergoes
thus increases series
states
exists
hydrolysis
ions to undergo
of the actitide
of Plutonium
otidation
hydrolysis with
reactions
is dependent
increasing
and in the case
in dilute
atomic
solutions.
on the charge number
of Pu increases
15
acid
for
charged The
and ionic
radius.
all the oxidation
in the order
PuO~
ions
tendencies
states +++
< Pu
The
<Pu
+4
.
PU+4 has approximately +4 . Hf+4 and Zr The
constant
the same
for
along
with the volubility
Table
IV- 8.
the first
tendency
to hydrolyze
displacement
of a proton
(H20)X 2+ + H20
PU02
hydrolyzes
Puo;+ radius,
showing
TABLE
IV- 8.
(H20)$-~1)+
First
= PU020H
to a greater
the effect
+ H30+
Hydroxide
PU+3
Pu(OH)
(H20);-
efient
of the highly
Hydrolysis
Ion
Constants
central
s
the most
of colloidal polymer
The
is apparently
completion.
*
7.37 @ = 0.034,
HC1)
7x
10-’6
*
markedly
aggregates
adsorption
spectra
Pu(IV) polymer
can be formed
is favored
by an increase
in the acidi~.
oxygen
forma
of the free
from
a radiochemical
brown
ion.
standpoint
by successive
or hydroxyl
remains
to and has
concentrations
green
has an entirely
and the
proceeds
in solution
In macro
to bright
hydrolysis
bridges
when the reaction
the colloid
of polymer
from
many
solutions.
the
when the solution
different
character
The formation
in the Pu concentration
As the total
than
nitrate
concentration
of Pu(l_V)
and temperature increases
or by a
the polymer
The presence of strong completing at 2-3 — M N03-. 104 Nevertheless, the presence of polymeric Pu 327 Polymer is be suspected whenever the acid concentration is below 0.5 — M. when solutions are diluted with water because of the existence of transient up to a maximum
anions
the formation
inhibit
of high pH, even 327, 64
of the polymer. metric
(244)
solutions.
precipitates,
regions
those
changes
from solutions
with
however,
from
solution
The
should
in Pu(IV)
PU(OH)4
stages,
cliff erent
reaction
y forms
irreversible.
of a 0.3 — M HN03 The
hydrolytic
monomeric
formed
x 10-’5
(3 * 1)
3
presurnabl
In intermediate
decrease
Ref.
10-’0
important
reactions.
polymer
of Hydroxide
2x
et al.
is the formation
is heated.
Ions.
Polymer
By far
color
Plutonium
HC104)
1.27 (u = 2.0)
in Gel! man
for
7.22 (u = 0.069,
3.33 (1.86 X 10-4 ~HN03)
quoted
ion of the same
Products
‘SP
PU(OH)4
Pu(IV)
in
.
dipositive
‘KH
PU02 (OH)2
properties
sphere,
Pu ion
and Volubility
PU+4
reaction
the hydration
;
~ + H30+
than a simple
charged
Puo~
C. 6
than that of
-1+ of PU02
or in the case
As
from
but leas
product for the hydroxide of the various Pu ions, is given +3 +4 and Pu , the hydrolysis reaction may be written In the case of Pu
PU (H20)X ‘+ + H20 = PuOH
*
as Ce ‘4
quantity
of acid
of polymer.
though The
the final
polymer
in the dissolution
acidity
is also
may
formed
of PU(OH)4 16
be high enough
to prevent
by adding
than a stoichio-
precipitate.
less
Fortunately,
formation
PU(OH)4
can be precipitated appreciable
from
formation
be completely
originally
precipitated
(approximately
0.15 equivalents phenomenon
fact
was
form
utilized
of cation
The
rate
strong
completing Care
example Pu(IV) does
agents
Costanzo
avoidance
Polymeric positively
charged.
was necessary
from
are
ability
concentraof
for
The
example,
but
formation of polymer 407
in
observed.
of polymerization
concerning
suggestions
macro
paper,
the
of Pu.
indicating
that it is
1 ~g/ cm2.
than on glass,
10-8 to 5 X 10-10
con-
of
for
amounts
etc.,
on silica
and de-
and salt
the formation
give
at approximately
is greater
The
given
Pu concentration,
onto glass,
reversible
been
(TBP),
the rate
occurs
in radio chemical
of the polymer.
The
references
with
polymer
has been
and shipping
on glass
was
acid
and addition
M Pu(lV) â&#x20AC;&#x201D;
that
5 to 8
solutions,
at pH < 4.
399 and (VI)346
on platinum
(Pt)
has been
17. to 4~0 of the Pu(IV)
such as TBP,
tri-n-octylamine,
of the extractant
or the aqueous
phase
the adsorption.
decreased
studied
can adsorb (TOA),
nitric
acid
from
on a Pt 399 etc.
phase
in
Ion Formation
feature
of complex
ions
of the aqueous
reactions
and may
in the hydration
of an ion to form may
This
the colloidal
in moderate
phosphate,
information
strongly
extractants
with the organic
competing
which
for
charges.
concentration,
(DBP).46
the above
It was found that from
The formation
molecules
Pu from
has already
temperature,
equilibrium
of Pu(IV)
organic
Complex
important
n -butyl
in handling
Saturation
the concentration
equilibrium C. 7
Both
adsorbs
on glass
adsorption
solution.
Increasing
of acidity,
to reach
and that adsorption
ionic
properties
resin
acid,
found that the adsorption
Samartseva345
The
into tri-
formation
Pu(IV) 78
few
lmay
amounts
and phosphate,
of Pu(IV)
chemical
dibutyl ether (butex) 104 have determined
solutions.
of polymer
polymer
and sulfate.
exchange
has summarized
Miner278 in nitrate
surface
glycol
acid
the formation
phosphoric
as a function
centration. polymer
aqueous
not extract
and Biggers
polymerization
without
contains
temperature
stronger
different
on cation
into di-n-butyl
of diethylene
iodate,
to remove
at room
to prevent
of non-adsorption
solutions
slow
by heating,
of the very
does
of oxalate,
solved Pu(IV)
than stoichiometric
that the complex
such as fluoride
be taken
polymer
hours
is very
because
extract
of anion)
and redis 239
reagents.
by much less
and Welch305
is increased
must
separations
solutions
excess
exchange.
Depolymerization tions.
solution
indicates
by Ockenden
by means
by using
from
example.
This
monomeric
of polymer
be defined
sphere
in aqueous
chemistry be looked
with anionic
Complex
formation
upon as the displacement
by the anionic
complexes
solutions
of Pu.
is dependent
ligand
or by OH-,
on the magnitude
ligands
is an
and hydrolysis of the H20
respectively. of the ionic
The potential
by the equation
d=zjr. z is the charge of Pu in different
on the ion and r is the ionic oxidation
states
are
given
radius. in Table
17
The
values
IV- 9.
of the ionic
potentials
TABLE
IV- 9.
Ionic
Ionic
Cation PU+4
Gel, For
potential
2.91
0.81
2+
2.47
0.87
1+
1.15
3
relative
tendency > Pu(HI)
of Pu ions to form > Pu(VI)
the positions
complexes
then is
> Pu(V)
3 show that the anionic
& alt
example,
Ionic
1.03
et al.
ma
Charge
(~)
States*
4.44
Gel! man
Pu(IV)
Oxidatioh
3+
PU02+
The
in Various
4+
+2
*After
radius
of Plutonium
, 0.90
PU+3 PU02
Potential
of Pu(HI)
ligand
and Pu(VI)
has some
are
effect
interchanged
on this
series.
in the case
of onlate
complexes. Singly multiply
charged
charged CO;
Tables
> C20;
IV- 10, IW - 11,
Pu(III), Gel! man also
anions
anions.
Pu(l_V), ~.
reviewed
of several
weaker
order
list
and Pu(VI),
complexes
of complex
> SOâ&#x20AC;?; > F->
and IV-12
Pu(V), 3
form The
NO;
> Cl-
available respectively,
for
comparison.
18
ability
> C1O;
stability which
chemistry of complex compounds 97 by Comyns. Table IV- 13 lists stability
actinides
The
with actinides
forming
generally
with
some
than do anions
is
.
constants are
based
and ions constants
for
complexes
on the review of the actinides for
some
of of was
complexes
.-
TABLE
Complex-formation PU+3 + N03-
IV-10.
Stability
Constants
uf Pu(III)
Ions*
Ionic strength
reaction
K
= ~0~2
Ref.
5.9 *0.5
PU+3 + 2NO;
= PU(N03);
14.3 * 0.8
PU+3 + 3NO~
= PU(N03)f
14.4 * 0.8
PU+3
+ cl-
+2
= pucl
0.5 1.0
0.58 1.1
PU+3 + S04-2 = Puso:
10
PU+3 + 2s04-2
50
= Pll(so4)2-
*3
3.6 x 1011 PU+3
Pu
-2 = PU(C204);
+ 2c204
2.0 x 109 1.4 x 109
+3
‘2=
+ 3c204
PU(C204)3
-3
2.4 X 109 4.5 x 1010
PU+3 + 4c20~2
= PU(C204)4-5
4.2 X 1011 8.3 x 109
PU+3
PU+3
+ 4HC204 - = Pu(Hc204)~ +7 -4 _-Puy
1.0
-4**
9.1 X101O 1.OX
1.0 -3
(1.3-3.9)
= Pll&”
7.7x 1.0
PU+3 + %27
-2
‘2 = PU(C4H406)6
Pu ‘3 + 5C2H302 ‘=
-9
of Geli man
ionic
1011
5X1O’5
Pu(C2H302)~2
on the review
at zero
lx
-9
unless otherwise specified. **7-4 . “ m the anion of ‘kthylenediaminet *3Values
1.6 X 109
= ;%
+ 6c4H406
*Baaed
x 1018
1011*3
+2 + H+
Pu ‘3 + 4C6H507 “3 = fi(C6H507)4 PU+3
1021=
2.3 X 1017
0.1 PU+3 + H7
*3
6.3 x 1012
5X1016
et al. 3 The
etraacdi
strength
19
data are
c acid.
*en
from
this
511
source
TABLE
IV- 11.
Complex-formation ~u+4
+ cl-
Stabflity
Conetants
reaction
= PUC1+3
PU+4 + 2C1-
+2 = PUC12
PU+4 + NO;
= PU(N03)+3
of Pu(IV) Complexes* Ionic strength
K
1
1.38 0.67
2.0 6.0 1.0
PU(N03) ‘3
+ NO;
PU(N03)2 ‘2
+ NO;
❑
PU(N03)2
+2
= PU(N03):
PU(N03);
+ NO;
= PU(N03):
PU(N03):
+ NO;
= Pu(N03)-
Pu(N03)~
+ NO;
= Pu(N03)~2
PU+4 +HF=~+3+H+ = PUF2 +2+
PU+4 + 2= Pu “+3
HF=~;+9H+
Pu “+4
HF=m4+4H+
PU+4 + S04-2 = PU(S04) Pu ‘4+
-2
2s04
PUM
+2
6.0
0.96
6.0
0.33
1
1.7X
104
2
1.1X
104
1.0
4.6 X 103
-2
= PU(C03)+2
10.0
1.0 Pu ‘4
+ 2C204
-2
= PU(C204):
+ 3c204
-2 = PU(C204);2 1.0
Pu ‘4
+ 4C204-2
1011**
3.6 X 108 3.2 X 1020**
1.0 ~+4
9.1 x 1046 1.3X
-2 = PU(C204)+2
+ c204
4.7 3.46 + 0.06
~H+
= PU(S04)3
+ CO;2
2.9 + 0.6
= Pu@04):
PU+4 + 3s04 ‘2
~+4
Ref.
= R(C204);4
6.3X1016 1.OX
1027**
2.5X
1023
6.0 X 1029** 1.0
3.OX
1027
9.1X1027 PU(HP04)2 ❑
+ (n + 4 - 3m)H+
—
Pu(P04)mH;w
where
m=l,2,
2Pu+4
+ H202
+ 3H+ (brown 2Pu+4
+ 2H202
- 3m +(2..5andn= + H20
m) H3P04, 0,1, 2,. .3m
= PU(OO)(OH)PU+5
0.5
6.8 x 106
0.5
6.3x
complex) = Pti (00)2
PU+4 + 4H+
(red complex)
20
106
TABLE
Complex-formation Pu
+4
+-f
Pu “++ Pu ‘4
-4**
IV- 11.
(Continued) Ionic strength
reaction
0.1
= Puy 0
H27=;
Pu2y
+ 4C6H507
-3
K
Ref.
1.58X
1024
1.4
x 1026
1.7
x 102’
2.0
x 103’
+ H+
= Pu(C6H507)~
8
‘2 = Pu(C4H406)~8 + 6c4H406 - *3 = PU(ACAC)+3 PU+4 + ACAC
0.1
3.16x
1010
Pu (ACAc) ‘3
0.1
1.58X
109
0.1
2.51X
108
0.1
1.0
x 106
2.0
x 105
359
1 x 109
359
8 X 1013
359
2 X1018
359
PU+4
PU(ACAC)2 Pu(AcAc);
+ AC.AC-
‘2 i- AcAc+ AcAc-
PU+4 + C2H30~
= PU(ACAC)2+2 = PU(ACAC)3 ‘ %@cAc)/
= PU(C2H302)+3
PU+4 + 2C2H30~
= Pu(C2H302)~2
PU+4
= PU(C2H302)3
PU+4
+ 3c2H302 + 4c2H302
PU+4 + 5C2H302
;
+1
- = PU(C2H302)4
4X1O
= PU(C2H302):1
22
359
NOTES: *
Based
on the review
iess otherwise specified”. ** Values at zero ionic *3 Abbreviations are:
of Geli man et al.
3
The
data are taken
strengtk
1.
y-b” m the anion
2.
AcAc
of ethylenediaminetetraacetic
- = [CH3COCHC~H3]-.
21
acid.
from
this
source
un-
TABLE
IV- 12.
Complex-formation P.@;
+ cl-
Constants
of Pu(V)
ati
Pu(VD
-2=
+ c204
‘o;
+ 2c204
Puo;
+ y-4 +2
Puo2c20~ -3
-2 = PU02(C204)2
0,05
3.3 x 104
0.05
2.4 X 107 7.9 x 1010-
. P@27-4**
+ NO;
Pu02NO~ ~02 ‘2
+ cl-
1.6 x 1010 72
= Pu02NO~
+ NO;
K 0.67
0.05 Pu02
complexes*
Ionic strength
reaction
= PU02C10
+ ’02
Stability
= Pu02(N03)~
36 & 0.3
= mo2cl+
1.0
1.25 0.73 * 0.07
PUO;2
+ 2C1-
PUO;2
+ 7
PUO;2 ~o+2
= PU02C1;
-4.
~027-2
+ c20p
z
+ 2C204
= PU02(C204)2
+ CH3C~”-
PUO;2
+ 2CH3COO+ 3CH3C00-
‘2 ‘2+
-2
*
2CO;2
Taken from
1.75X
= PU02C20:
PUO;2
-2
0.35
= Pu02(CH3COO)+
■
1016
6.9
X 107*3
1.0
4.3
x 106
5.0
x 1012*3
1.0
3.”0 x 1011 1.9
x 103
= Pu02(CH3COO):
2.0
x 106
= Pu02(CH3COO)3-
2.3
X 107
1
x 1015*3
P@2(co3
the review
)2-2
of Gel lman
et al.3
**Y’4 is the anion of ethylenediaminetetraacetic *3 Values at zero ionic strength.
22
acid.
TABLE
IV- 13.
Stability
Complex-formation ~e+3+
~c
Me+3+ Me+4 Me+4 Me+4 Me+4
y
~ 24 -4.
+ c204
reaction
‘2
= Me(C204
‘2
+ 4c204 + C20~2
-4
8.54
+ 2c204
Me02+ 2 + 3CH3C00 MeO~2
+ C20~2
Me02+2
+ 2C20~2 + 2C03 ‘2
Pu
11.46*3
21.0*3
20.6*3
8.74 16.9
22.7
24.0
23.4
27.7
27.4
27.5
5.04
4,52
7.36
7.38
2.7
3.31
3.27
= Me02(CH3COO)20
5.10
5.83
6.29
- = Me02(CH3COC))3-
6.41
7.90
7.36
= Me02(C204)2
= Me02(CH3COO)+
6.77
= Me02C20f = Me02(C204)~2 = Me02(C03)2
-2
values
calculated
by A.
23
6.64
12.0
11.5
14.0
15.0
Taken from the review by Gellman et al.3 -4. m the anion of ethylenediaminetetraacetic
acid. I. Moskvin.
Am
11.55*3
17.54
-3
7
Thermodynamic
Actinides*
16.9
= Me02(C204)-2
+ 2CH3C00-
*3
-2
‘2 = Me(C204)4
Me02+2
**
Np
8.61
r2
‘2 = Me(C204)3
+ C!H3C00-
*
u
= Me(C204)20
Me02+2
MeO~2
of Several
~q-4**
+ 3c204
Me02+
of Complexes
‘2 = Me(C204)2-
+ 2c204
Me02+
Constants
D. D. 1 Co-precipitation
common
the insoluble
reactions
reactions,
and Pu(IV) trace
snd precipitation
in general,
in precipitation
important
are
only
by LaF3
quantities
Methods
and Precipitation
Co-precipitation because,
Separation
are
not those
and will
different
have
and PuF4
volume,
be considered
properties
reactions.
Of the
and co-precipitation
the radiochemist
large
to the radiochemist
desirable
in co-precipitation
of PuF3 Since
problems
of Pu which
formed
precipitation analogous.
of Pu in a relatively
to him,
present
compounds
is likely
of Pu(III)
to have
co-precipitation
small
reactions
or
are
more
first.
Co-precipitation Co-precipitation of Pu.
Indeed,
the first
co-precipitation method
for The
shown
with
arises
selective
precipitant
discussion
The
separation
illustrated
with the carrying
Only similar
as many
method
1949.
The
have
The
usually
of absorption
review
takes
degree
advantage
reduction
a thorough
of the afore-
The procedure
cycle
of purity.
and volume
and a
of Pu has been
and the non-carrying
oxidation-
elements
of co-precipitation
behavior
purification.
is
of separa-
states,
be repeated
use of LaF3
reduction
be
on
behavior
may
The
may
of Pu(VI)
and oxidation-reduction
separation
acid-insoluble
otidation 49 . gives
and Kahn
co-precipitation
co-precipitation
step,
pre-
since
not
fluorides.
radiochemical procedures, 191, 83, 82, 446 Chenley
of the thickness
separate
and a good
and Pu(IV)
LaF3
the Pu. because
ti
to effect
to get any desired group
by
radiochemical
The possibility
state.
of Bonner
cycles
with
a valuable
elements
In many
function
review
of Pu(III)
elements
accomplished
the “classic”
oxidation
of co-precipitation
and reduction
as needed
is also
many
determine
in a given
to that of Pu interfere.
times
cipitation very
those
has become
of Pu by co-precipitation
oxidation
in the radiochemistry was
of Np and Pu toward a number of precipitant 16 the review of Hyde. The behavior of these
The
is used.
important
of the element
can be maintained
of the mechanism
mentioned
very
from
all the elements through 253 by Leader.
discussed
LaF3.
method
“of the actinides
when the elements
extremely
used.
behavior
IV- 14, taken
are
and isolation
This widely
co-precipitation
in Table
data for
LaF3.
Pu and is still
is representative tion
reactions separation
et al.
of the alpha
of the counting
is mounted for alpha counting to 83 report a 2.6 q. negative bias by this
particles
sample
in the LaF3.
and must
This
bias
is a
be determined
for
each
pro-
cedure. Calcium since
is one of the elements
the fluoride
Ca concentrations Pu is oxidized duction,
is moderately
which
insoluble.
the Pu can either
and CaF2
with
One method
( >200 mg/ 1 ) is reported to Pu(VI)
interferes
by Scheichauer
is precipitated
be co-precipitated
away
from
or separated
24
LaF3
co-precipitation,
of solving
the problem
and Messainguiral. the Pu. by other
Following means,
of high 351 The re-
TABLE Neptunium Carrier
lV - 14. Co-precipitation Behavior in Principal Valence States. 16
Lanthanum
fluoride
Amounts
of Plutonium
and
Pu(rv)
Pu(VI)
NP(IV)
hTp(V )
C*
c
c
c
c
c
c
c
NC**
C
c
NC
c
Pu(III)
compound
Hydroxides
of Trace
Np(VI)
Phosphates: phosphate
NC
c
NC
Thorium
pyrophosphate
NC
c
NC
Thorium
hypophosphate
c
NC
c
NC
c
c
NC
U(IV ) oxalate
c
c
NC
Bismuth
c
c
NC
c
c
NC
Zirconium
U(IV ) hypophosphate
NC
Oxalates: Thorium
oxalate
oxalate
Lanthanum
oxalate
c
NC
Iodates: Zirconium Thorium
c
NC
c
NC
c
NC
NC
NC
c
NC
Poor*3
C
NC
c
NC
c
Poor
NC
iodate iodate
Ceric
iodate
Sodium
uranyl
Zirconium
acetate
phenylarsonate
Thorium
peroxide
c
Bismuth
arsonate
c
c
NC
c NC
*
The letter “C” indicates that the co-precipitation has been observed to be nearly quantitative under proper conditions. ** The letters “NC” mean that co-precipitate’on may be made less than 1 to 2 percent under proper conditions. *3 “Poor” indicates an intermediate percentage of carrying. Co-precipitation of Pu with LaF3 ia a common 360, 349, 257, 125, 208, 53 for Pu .
step in the analysis
of biological
material
Bismuth widely
phosphate.
used methods
of the process
The
of separating
is reported
carrying
Pu from
by Thompson
both Pu(III)
and Pu(IV ) when precipitated
peculiarity
is the fact
conditions 1)
for
agents,
from
BiP04
precipitation,
The
LaF3,
reported
development
by Adsmson.
digestion
after
carries
nitric
than Pu(III).
2) the absence
4) minimum
of the early,
BiP04
concentrated
carried
volubility,
and
Like
moderately
been
is another
products.
401
efficiently
of Pu have
at the minimum 3) slow
and Seaborg.
is more
the co-precipitation
co-precipitation
pleting
that Pu(IV)
of Pu on BiP04 U and fission
acid.
A
The optimum 20
These
of strong
are:
com-
precipitation
is
complete. In addition cipitations Pu from Rydberg
to being
very
successful
in the large
processing PUP BiP04 pre341,415 procedures to cone entr ate 126 Pu in urine, The procedure of
have been used in general radiochemical 237 and to determine large volumes of water 341 uses the familiar oxidation-reduction cycle 25
scale
to effect
purification.
Plutonium
is first
oxidized
to Pu(VI)
HN03,
then reduced
Pu(IV),
in contrast
Zirconium
a NP-Pu
zirconium
phosphate. inor ganic
of actinides
were
in the tetravalent
made
little
equally
A mixture
BiP04
precipitated
based
phosphate
which
carry
co-precipitants.
peroxide,
uranium
of Pu(IH)
peroxide and Pu(IY
is a specific
118
and Aten
co-precipitant
elements.
which
has a similar
which
has a different
described
) has been
carried
the co-
All
the elements
the crystal For
crystal
for 16
Hyde
precipitating
peroxide.
found, that in general, of these
0.1 — N
and Pu(lV). before
and uranium
They
state.
in the co-precipitation
from
with BiP04.
to Pu(III)
Dupetit
peroxide
precipitated
both Pu(III)
on the reduction
with thorium
with thorium
and with
bismuthate, and finally
Zirconium
oxidation
difference
well
ion,
and LaF3,
separation
Other
peroxide,
sodium
phosphate.
to BiP04
describes
precipitation
with
with ferrous
type
example,
structure
Pu carried
to plutonium
structure.
on lanthanum
iodate
from
dilute
HC1 solution.2’3 Plutonium
can be separated directly 102, 74 ammonium phosphate.
calcium
Pu(fV) and Pu(IV) which
and Am(III) and Np(lV)
are
have have
been
been
from
quantitatively
separated
unsaturated
in K2S04.
Organic
co-precipitants.
The
a urine
sample
co-precipitated
by precipitation
minimum
by co-precipitation
with
with K5La(S04)4,
of the Pu from
Pu volubility
in this
151
solutions
system
occurs
at
o.7g.152 Zirconium
phenylarsonate
is a specific
carrier
for Pu(IY) and has been used in analytical procedures to determine the oxidation state 193, 414, 227 227 and to separate Np and Pu after reduction with NH20H.392 King , used
2 X 10-4 ~ NH20H
the same
time
Pu is nearly so from
to prevent
not oxidizing quantitative
from,
Voigt
a formate
Ice 1‘3
HC1 solutions.
the reduction
the Pu(III).
buffer
got quantitative
of Pu(IY ) during the analysis, while 414 et al. found that the precipitation of pH approximately recovery
2, and slightly
in precipitations
from
at of less
1~
HC1 solutions. used mandelic
Merz273 Pu(IH)
quantitatively
acidities.
at pH 2-4
The precipitation
bromomandelic
acid
and p-bromomsndelic
and above.
was about
Zirconium
85 ~.
acid,
and somewhat lower 422 quantitatively and Shipman
Weiss
by the formation
of oxine
homogeneously
acid
complete than this recovered
in solution
with
Y(HI)
was used for at 1 ~ for
Pu(IV
) at higher
HC1 and HN03
mandelic
Fe,
to carry
Pu,
for
p-
acid. C e,
and Pr
by the hydrolysis
from
solution
of 8- acetoxy-
quinoline. These
workers
rhodizonate.421’
374
HN-03 solutions all elements Other
dyes
with butyl
except were
determined Kuznetsov
Th(lV
Pu in urine
rhodamine. ) and U(VI).
successfully
by co-crystallization 247 co-precipitated
and Akimova The
method
Repeated
used to separate
26
with potassium Pu(IV)
is quantitative
precipitations Pu by the same
from
3~
and separates
effect
from
the separation.
procedure.
Precipitation Precipitation and radiochemical useful
in practice
purification factors most
will
steps
for
of macro
procedures. be reviewed
for
Pu from
quantities
The
in this
Pu is illustrated Fe,
Co,
Zr,
section.
by Table
Mo,
reactions
Ru,
The
in many
which
have
analytical been
use of various
found
precipitates
as
IV- 15, which gives decontamination 431 As usual, Zr and Ru give the
and Ce.
trouble.
TABLE
IY - 15.
Decontamination
Factors
Plutonium peroxide
Element
for
50
33
co
30
47
Zr
1
Mo
>140
Ru
>14
Hydroxide. solution
by sodium,
hydrous
oxides.
vent formation dissolution. subject
Both
Care
must
Once
formed, more
of excess
HF.
precipitate
precipitate
is kept
compounds
dissolve
but if heated sodium PuF3
to 500â&#x20AC;?
33 1
was
several
suitable
months.
for
in nitric
in contrast
acid,
oxidant
only
of PU(III)J
and a reductant.
with
to the findings particle
slowly
Pu(IV)
peroxide
Pu(IV)
peroxide
precipitate.
anion
or less
random
from
acid
forms
Metathesis
standard widely
solution
a more
always
placement
ion,
by
tractable,
Pu,
Jones214 at least
This in this
incorporates suggested7 between
a period
was readily volubility
peroxide
H202
to soluble
is attrib-
some
is added
to
can act as both an of the anion pres-
that the presence sheets
of
work.
when hydrogen because
for
with
found that
It is interesthg
in oxygen
workers. prepared
such as H3B03,
to the hydroxide
however.
at 500â&#x20AC;?C
and Pu(VI),
It has been
for
used,
PuF3
27
This
Pu(IV).
of solution.
is formed
Pu(V),
solutions.
the
fluoride
of PU02
Pu(IV),
in acid
to pre-
during
solution.
of other
size
in acid
concentration
acid or
complex
method
of this
mineral
is stable to oxidation if the 323 The freshly precipitated
difficulty.
has not been
ent into the crystalline is due to a more
very
compound
which
is another
by ignition
fine
Peroxides. solutions
in reagents
use as a gravimetric
prepared
acid
et al. 325 found that PuF3 The
from
hydroxides
Pu(I17) hydroxide a high
dissolves
PuF4.
1.1
as hydrated
be precipitated
method
note that PU02
uted to the extremely
in redissolving
may
36
be precipitated
and PuF4
hydroxide
This
) may
hydroxide
on polymeric
dissolve
or potassium
8.6
1
in the supernatant
readily
> 95
> 38
by maintaining
than does
slurried
1.4
1.1
in the section
Prevot
10
1.1
the polymer
fully
Plutonium (Hf) fluoride
> 15
be taken
PuF3
crystalline
Plutonium (IV) oxalate
> 13
and Pu(IY
431
Methods.
>44
or ammonium
polymer,
Fluoride. addition
Pu(IIZ)
potassium
of Pu(IY)
is treated
by Precipitation
3.5
6,
Ce
Plutonium
Plutonium (IH) oxalate
Fe
acid
of Pu is necessary
precipitation
of the
of Pu and peroxide
oxygen ratio
in the ratio may
1:3.
be lower.
If an excess
The
extra
of peroxide
peroxide
also
is used
serves
in the precipitation,
to hold the sheets
the
together.
Precipitation
of plutonium peroxide has been used as a purification step for Pu 72, 158, 329, 425 from most other cations and as a step in the preparation of high purity 329 Pu compounds and solutions. This precipitation has been used to separate Pu from 72 277 ~ Am, the Am remaining in the supernatant solution, and to separate Pu and U. the latter
procedure
as a holding were
the Pu was
oxidized
and uranyl
peroxide
oxidant,
Oxalates. used
separation
filter
from
precipitation
and work
own alpha
with.
which
factors
served
of 2-4
obtained
after
five
a gravimetric Dicesium
Solvent The
This
handling
facilities,
separations
carried
written a recent
deal
for
carbonate
and CO,
(IV)
sulfate
tetrahydrate
use as a gravimetric
a product
solution,
This
standard
of 99. 98~, purity
compound
is suitably
was
stable
as
448
has also
been
proposed
can be prepared
of reactor
These
for
as a primary
by precipitation
and ease
for
from
an 8
carried
easily
of handling
equally
in this
was taken
section
specific
extractants, properties
thoroughly
a good
have
reviewed
of this to remote
to laboratory
important. systems
for
and a large
Pu has portion
under
the spur
better
radiation
of a given
or industrial
principles of solvent extraction 292 and Freiser, and in a comprehensive
over
extraction processes,
in the laboratory
been
are
adaptability
of large-scale
general
Pu have
properties
are
on liquid-liquid
more
done by liquid-liquid
of desirable easy
data on the extractive
applicable
is largely
U and Pu,
advantages
of research
quest
targets
of a combination
data reported
The basic
data for
into
to
of their
of C sC1 in HC1.
specificity
specificity
never-ending
equally
The
Methods
etc.
extraction
and the like.
extraction
compound
out in the development
the solvent
The
hexachoride
The
great
great
solution 265
by the action
of plutonium
18-months,
(IV)
is so because
where
A very
for
processing
example,
acidic
or metal.
is decomposed
Pu compotmd
impure
) by addition
large-scale
for
dilute
or Pu(IY).
recrystallization.
at least
Extraction
extraction.
Morrison
successive
of Pu(lY
from
to oxide
decomposition
The precipitation
a grossly
plutonium
method;
seemingly
with
standard.27g
HC1 solution
Pu(VI)
a high purity
standard
gravimetric
course,
either
compounds.
Starting
oxalate
conversion
elements are not so great in some cases as in the 431, 141 procedure (Table W- 14), but the precipitate is easy
used to prepare
Pu.424
been
bromate
Separation
other
reduce
Other has been
of plutonium step before
The se compounds undergo 134, 389, 216 The oxalate
radioactivity.
and the CO may
D. 2
Precipitation
as a concentration
factors
peroxide
~
by potassium
precipitated.
obtained.
has been
for
to Pu(VI)
solvent
stability, are,
of
situation, been
review
put forth
by Marcus. 388
by Smith.
iâ&#x20AC;&#x2122;n the book by 267 The solvent
Carleson77
has
general survey of the processing chemistry of nuclear fuel for Pu, 450 contained much of interest concerning the newer extraction symposium
systems. 28
of
of the
while
In this coefficient
save
is defined
which
concentration concentration
D.
To
the data will
section
D,
space,
most
often
of the solute of the solute “Dx”
the notation
be given
in terms
of the distribution
by the equation
for
in the or~anic in the aqueous
“the
distribution
phase phase
coefficient
of species
x“
will
be used in the text. Organo
Phosphorous This
acidic
esters
phosphinates acidic
large
of ortho
extract
while
some
class
acid
oxides.
of a neutral
the acidic
an extractable
extraction
Neutral
complex
species.
is beyond
the scope earlier
type.
as an extracting
of this
agent
have
neutral
organo-phosphorous
be discussed
of metal
rium
molecule
phase,
constant,
The
compounds
by the phosphoryl
by an ion-exchange
may
occur
reaction
in the organic
phase
in
more
summarized followed
recent
will
serve
on TBP
papers
by McKay
by other
Hesford
nitrates
into
+ q TBP(0)
on the metal in the organic
and species neglecting
(C4H90)3P0,
of the literature
will
as the typical
extraction
of Pu
be emphasized,
necessarily be included. A summary of early work 143 The physical and chemical p~5~rties of TBP
systems.
p is the charge
organic
and
neutral
The
and Healy.
aqueous
systems,
TBP-nitrate
and finally
other
compounds.
M+p + p N03-
the nitrate
been
first,
TBP-nitrate
where
will
by Geary.
will
reaction
solvation
survey
review.
work
given
system
traction
into neutral The
phase
operate
(TBP),
A complete
project
has been
in the organic
and
type.
Tri-n-butylphosphate of this
although
naturally
mechanism.
in general,
Further
of this
dividea
the neutral
the phosphonates,
Compounds
compound
on TBP
class
ants includes
compounds,
in extraction
compoumds,
systems
of extract
and related
The
by the differences
by solvation
to form
and important phosphoric
and phosphine
compounds
oxygen,
Compounds
withofit activity
and McKay
TBP
178
= M (N03)P
The
subscripts coefficients,
formulated
the ex-
(1)
“ q TBP(0)
ion and q is the number phase.
have
as
subscript are
of TBP (o)
refers
in the aqueous
molecules
solvating
to species
in the
The
equilib-
phase.
is then
(2) and the distribution
coefficient (3)
Under diluent
constant to make
aqueous Eq.
conditions,
(2) valid,
and at a sufficient
the distribution
29
will
dilution
of TBP
be proportional
in an inert
to the qth power
of
the TBP
cone entration.
system
on a semi-empirical Tetra-
solvates for
complex
shown
and does from
that Pu(IV)
not exist
several
the organic Typical into are
data for
19 volume shown
~. TBP
in Fig.
concentrations passes elements
1.
because
through (e. g.
and obtained
The
. 2 TBP
in 2-4 ~
There
the extraction ‘in kerosene The
nitric
Th and Y) pass
coefficients
through
an average
rises effect
steeply
I
Zr
I I
40~. TBP
other
in kerosene
attention
pure
Pu(IY)
disproportionated
CONCENTRATION,
HN03,
but fails
at higher
30
acidities.
ion plus hydrazine
ylamine
fail
Br03-
after
and hydrox-
the reduction
lower
acidities.
found that solid Pu(IV)
at room
the oxidation Fig. 1, Extraction of mtrates at trace concentration mt~ 19 volume ~0 TBP in 258 solutions kerosene at 25oC from nitric aci The inTaken from McKay and Healy. dividual reference’s are: ~trium350; thorium 179. zirconium2 , uranium and neptunium2d: and plutonium44~ 258.
re-
at up to 2 ~
Ferrous
did not oxidize AQUEOUSJM)
Pu(llI) with added
complete
) to Pu(IH)
HN03
in the ex-
for
of Pu(IV
to complete
KBr03
to Pu(VI)
in 1.55
temperature,
was
quantitative
heating
2
Pu solution,
duction
at progressively
HN03
Figure
concentration
sulfamate effects
to
an equilibrium
agents
curve
Ferrous
state.
was necessary from
reducing
also
to main-
oxidation
of an equilibrium
hydroxylamine
~
solutions 76 used
and paid partic-
of HN03
and the extraction
E(XJl LlBRi8M
acid
mixture.
the effect
on several
of the ex-
to requirements
that NaN03
prepare
Carleson
1),
Some
Carleson
Pu in the desired
alone.
acid
(Eq.
nitric
reported.
ular
He found
,o-’o&u+dLu+
concentrations
studies
tain
traction
concentration
ion
of Pu from
been
shows
in
again.
traction
I
un-ionized
concentrations.
and rise
ions
data
at low nitric
of the nitrate acid
have
are
of various
Several
I
extraction
at trace
solution
at higher
minima
r 2 TBP
of 2.6 nitrate
solvent
of elements acid
salting-out
and then falls
a maximum,
data.
to be di-
then PU(N03)4
that the complexes
of a number
distribution
of the strong
with
by combining
evidence
from
shown
with trivalent Pu has shown that 252 372 Laxminarayanan et al. 3 TBP.
Pu(N03)3
is direct
this
experimental
been
are
for
Work
HTT03 is associated Pu(N03)4
with
have
complexes
Pu(VI).
coefficients
agreement
actinides
extracted
is tri-solvated,
distribution
good
as other
for
as undissociated
solvents. 170 phase.
has calculated
Pu as well
phase. 44
and PU02(N03)2
the extracted have
basis
and hexavalent
in the organic
Pu(IV)
391
Solovkin
but that in 0.1 ~
to 95°C for
several
hours. -
Codding TBP
et al.
in kerosene,
92, 93
Rozen
used
307.
and Moiseenko
334
/2
*/3
1.0 4
/ I
/ , I
/ 1
10-1
;
/ /
function
/ ,1
acid
of Pu(IV
concentration
U(VI)
equilibrium (2)) for /
0.18, ‘1.2
and3
I
--2
/
PUUII) 0.005 MFe(ll)
sulphOm GtO(+ 0.006
-0.02
M hydr,oxylamlne)
0.005-o.02M
-.-3 ,.-2 -..-4
!
0.005
Fe OTl+hydrazlne;
-0.04Mhydroxyla
1
Fig. 2. Distribution of Pu(III) and equilibrium Pu(lII), Pu(IV), and Pu(VI), mixtures in the presences of several reducing agents in 40~0 TBP in kerosene and nitric acid; after Carleson.76
decreases
Moiseenko Pu(lV)
3, 4, and 5).
In the absence
temperature explained
below
ions
with This
at higher
at nitric
acid
) in the simultaneous species,
lanthanides
from
6 plotted ~.
approximately This
illustrates
while
nitric
acid
the importance
trace
nitrate
below
The
order
TBP
from
nitric
acid
solutions of atomic
The
acidities for
of ionic
is made
elements. 31
coefficient
of Pu(IW)
is with
of Pu(IY)
studied
with
effect
reaction
coefficient
of
(Figs.
decreases This
the distribution
tripo sitive Some
along for
on the extraction
at higher
with nitrate
the same
system
results.
of several
radius
increases
concentration
it increases.
have
1007. TBP.
if adjustment
extractability
actinides
nitrate
as:j:iation
similar
curves
The
of temperature
and Federov
number,
the
> M(VI)
258’26
in the activity
into
into for
that of the hexavalent 44 < Np(VI) < U(VI).
Pu(VI)
constant
with
solutions
while
to a decreased
4 ~
of re-
coefficients
of extractability
is M(IV)
the distribution
the distribution
in a large
5).
and uranyl
at higher
Shevchenko
comparison.
superimposable
over
of the Pu distribution
Fig.
the effect
increase
is ascribed
as a function
’77 for
i. e.,
in the equilibrium
a compensating
measured
of 22, Rozen
extraction
resulting
(see
< Pu(IV),
concentration
of uranyl
concentrations
e~.43
in Fig.
acid
temperatures.
U(VI)
Pu(IV
>> M(III)?4’
< Np(lY)
HN03,
increase
Best
Hesford
5 ~
by a decrease
temperature, acidities.
Th(lY)
of nitric
by Eq.
while
these
actinides
with atomic number, 281 and Rozen measured
as a function
of
and Pu(IY)
of macro
of the tetravalent
actinides
results,
the effect
and 3 respectively,
duction
3 M(HN03)\20
i. e.,
similar
(defined
HN03,
competition
1
number,
nitric
mine.
/
with atomic
as a
aqueous,
and Moiseenko334 and Codding et al 92, 93 get about 1.5 for Pu(IY). —“ These values illustrate the effective
I —
the
on the extraction of 132 Flanary derived
constants
U(VI),
All
) and Pu(VI)
studied
competition
20’7.
and
the distribution
with
also
Pu(IV ) and Pu(VI).
D
//
measured
of equilibrium
and several
/
1007. TBP.
workers
coefficients
!
used
and Bernstrom
41 used
Rydberg
364
and Federov
in kerosene,
above
I
i I
!
TBP
r
i
I
and Shevchenko
actinides
of their
data are
with the lanthanide
the two homologous to compare
on the chemical
ions behavior
and shown
data of series
are
of the same of these
radius
l?
I
()
3
n Ic
D
.Ib
n .
20
30
40
50
Tempera
0
5 Concentration of HN03 In aqueous @ase,
10 &
Fig. 3. Dependence of distribution coefficient of Pu(IV) into TBP on concentration of nitric acid in aqueous phase (for 281 solutions not containing uranyl nitrate). Curve 1-20°, curve 2-30”. curve 3-50°, and curve 4-70°
60
70
°C
Fig. 4. Dependence of distribution coefficient of Pu(IV) into TBP on temper in solutions not containing uranium. tiYe Concentration of HNO : curve 1- O.5N, curve 2- lhT, curve 3- 2N, curve 4-3N, curve 5-4N, curve 6-1 ON, curve 7-5N, and curve 8-6 to 8N.
I
O LA NTHANIDES
A
[02
1.0
ture,
~
TRIPOSITIVE ACTINIOES
~
# 5*I HNO~
# #
D,
I:L
Tempera ture, °C Fig. 5. Dependence of distribution coefficient of Pu(lV) into TBP on temperature with a uranium content of 0.42 M in the aqueoua phase. 281 concentrati~n of HN03: curve 1-0. 5N, curve 2-IN, curve 3-2N, curve 4-3N, curve 5-4N, curve 6-6N, curve 7-8N, and curve 8-1 ON.
LaCe Pr Ndpm-u
GdTb Oy HoEr
TmYb
Fig. 6. Distribution coefficient as a function of position in the lanthanide and actinide series. 43. 177 0 Lanthanid A Tripositive 32
es actinides
n
The salts
,02
ceived
results
Na(N03) Pu(IV
are
is used
). 44, 258
centration
10
effect
considerable
Typical
D
salting-out
on the extraction
shown
as the salting
At a constant
as the proportion
‘o
5 10 Aqueous nltrlc acid concentratlankJ
Fig. 7. Effect of NaN03 on the distribution of Pu(IV) between lg~o TBP in kerosene and nitric acid solutions.44. 258
of TBP-nitrate
molecules
by the lowering
nitric
concentration.
Aluminum salting-
nitrate
out agent
for
processes.
systems.
Many
away
stripping
the Pu into a relatively
and finally
from
fission
stripping
products
nitric
This
effect for
of the extract-
has been
have
involves
from acid
is increased,
used
as a
Pu in several TBP 149, 165, 52, 354
papers
into TBP-kerosene
concentrated
con-
decreases
of competition
able
acid
for
nitrate
is always
HN03.
by the reduction
the application of TBP to the processing of irradiated U for PU195, 132, 93, 148,325, 114, 202,365, 109, 133 The process and U(VI)
acid
TBP
traction
Applications
agent total
coefficient
than that of pure
is caused
7 in which
coefficient
of nitric
but the distribution
I
in Fig.
the distribution
greater
of non-extractable
of Pu and U has reattention. 165, 43, 149,52
written
extracting
nitric
solution
been
acid
ex-
about
Pu(IV
)
solutions,
by reduction
to Pu(IIf),
with water. Nitrous acid is added to the feed solution in 76 the first extraction to stabilize Pu(IV). Ferrous sulfamate was first used as a re 335, 195, 132 although U(IV) as a reductant has been exductant in the Pu stripping stage, 209, 221, 67.385, 353, 342, 38 tensively studied. This reagent can be generated from U(VI)
and stabilized
scale
processing
waste
streams,
ducts
and other
the U(VI)
by volatile plants
reductants,
of not introducing
thus permitting
a smaller
elements in this process 88,161,431,133,367 and others.
papers products,
Pu and U,
ing of the acid
are
successively 203 concentration.
TBP
was used in the isolation 362 and radiochemical Analytical traction
from
HN03
have
An interesting various Pu(IV)
heavy
and Pu(VI)
TBP
from
– other
volume.
has received A variant stripped
of naturally 144, 114
has been
described
occurring
phase
Pu. for
in large-
irorr)
into the
of fission
attention,
the TBP
procedures
(e. g.
The behavior
much
from
is the use of TBP
separations, 380 in HN03.
moderately
waste
advantage
materials
pro-
both in the primary in which
the fission
by stepwise
lower-
315 Pu based
on TBP
ex-
given.
application
element
TBP into
been
with the considerable non-volatile
aqueous
in reversed-phase
124’ 156’157’190
systems.
concentrated
Tetra-
and for
and hexavalent
HC1 solutions,
33
while
chromatography
the separation
actinides
trivalent
for
of Pu(IIT),
species
extract are
well
essentially
Larsen
unextractable. measured
Seils249
and
the extraction
of U
and Pu into 30% TEIP in CC14 (Fig. and used this analytical Pu (m)
/
Pu(m)
,.2 _
and Pu(VI)
extract
and “U(VI).
while
/
for
10
the same
Am
cause
and Seils
report
HC1
The value reliable
be-
oxidation
of
HC1 is much
than HN03
less
into TBP.
Larsen
D = 0.01 at 6 — M HC1 and
HC1 into
TBP
3070
in
CC14.2’4’ Solovkin extraction TBP
H
efficients
AQUEOUS
CON:ENTR:TION
I-&
([j)
from
trichloro
decrease
TBP
with
increasing
The varied
efficients
for
both Pu(IV)
CF3COOH
at low
The
Pu(VI), effect
are
diluent)
f> m
complex
co-
was
by TBP
Pu(IV) 183 The
distribution The
as great of Pu(IV)
concentration
was
at 0.4 .M The
determined dilution
and Pu(VI)
increase.
extraction
an initial
acid
0.0045
about 4 to 5 times For
perchloric distribution
ex-
to be
experiments.
extract
well
coefficients distribution
for
CC13COOH
into
30~0 TBP
coas in
of 0.5 — M CC13COOH,
D = 4. of addition
sulfate
and phosphate
Pu(VI),
and at lower
0.08 M in H2S04
acids.
1.1 &l (3070)
HC104.
than the usual
concentrations.
type
nitric acid — TE3P systems sulfuric439 – phosphoric.
corresponding
rather
and Pu(VI)
acid
125 (a kerosene
D = 21; for
acidity,
found that the
from
di-solvated
- and trifluoroacetic
into
to 0.9 at 6.4 ~
tracted Fig. 8. Extraction of U and Pub TBP in CC14 from HC1 solutions .24 $3070
Amsco-
of Pu(IV)
in CC14 from
HC104
390
et al.
appreciable.
,0-1 ~
for
partial
at
in 8 ~
more
to Pu(IV).
0.12 at 8&l
into
Am(III)
5-6
report a -3 for 10
of about
is considered
extractable
is true
conditions.
of possible
co-
above
authors
coefficient
the Pu(III)
I
These
and 10-4 for
Pu(III)
distribution
the reverse
acidities.
Pu(IV)
quadrivalent
than the hexavalent
HC1,
higher,
elements
at all acidities
The
efficients
under
>U(m)
better
of an
Both
have
distribution
j’
these
VIII).
actinides
lower
P
D
for
15, Sect.
than U(IV)
~
/pU(m)
8),
as the basis
procedure
(Procedure
103 ~
system
of sulfuric is invariably This
effect
complexes nitric
lowered
decrease
of Pu.
acid D for
and phosphoric
to lower
The
from
9 to 1.4.
acid
the distribution
is presumably
concentrations.
Pu(IY)
was from
acid
effect
to l%(~) coefficient
due to the formation is more For
pronounced
example,
making
or Pu(VI) – 438, 440>437 of unextractable
in Pu(IV)
than in
the aqueous
phase
16 to 9.5 in 4 JYJHN03; in 2 ~ HN03 the 437 On the other hand the lowering of D for
34
—
Pu(VI)
by the addition
of enough
H2S04
was only
2.6 to 2.2.
Sulfuric
from
acid
solutions.441
also
decreases
A solution
throughout
a change Other
H2 SO ~ to 2 — M HN03
1~
the extraction
in H2S04
neutral
of Pu(lY)
lowered
in HC1 concentration
to make
Dpu
the solution
into TBP
O. 1 M in —
from
approximately
HC1
a factor
of 10
of 3-8 — M.
phosphorous
compounds.
A wide
variety
of organo-phosphorous
compounds
has been studied in an attempt to find other extractants for Pu and U, 181 et al. working with the butyl series found the order to be phosphate
Higgins (( RO)3PO) (R3PO).
< phosphonate
(R(RO)2PO)
< phosphinate
(R2(RO)PO)
< phosphine
ThUS the extracting power increases with the number 69, 70 corrfirmed this series and correlated the extracting
Burger
of C-P power
with the basisity 69, 70 Burger,
of the phosphoryl oxygen as measured by the P-O stretching frequency. and Petrov et al? 18 found that electronegative substituents in the alkyl phenyl
strongly
the alkyl
chain
quadrivalent crease
in the phosphate
the extraction
tractant
Np,
effects
etiraction
little
The
effect
and Pu,
found
such as Cl and
the length
up to 8 carbon
of branching
the alkyl
depress
tri- solvation
chain
that increasing
difference
but to strongly
and possible
mechanism
but not necessarily
oct ylphosphine
oxide
as the di - solvate.
10 for
extraction
of several Pu(IV)
HC1 solutions. by 0.3 ~
TOP0.187
is similar
acid
extractive
the U with
TOPO
atoms
chain
that of Th.
of the Th complex
ant by using
of for
is to in-
This
effect
at high
ex-
possible, noted.
of this the
series
under
the same
case.
extractant
(TBPO)
well
while
from
(D = 4-30)
from
of nitric
acid
that for
written
as that for 267 Tri-n-
extract Pu(IV ) and 269. 1s ~ven in Figs. 9 and
in cyclohexane
) as a function
higher,
U(VI)
HN03
3 ~
and
H2S04
concentration
and Pu(VI)
a general
conditions
from
large
amounts
2 ~
HN03.
34
from
of data for
the extraction
coefficients
law, ” that is by assuming The
in which
stated
separated
The extraction
power
of experiments
generally
TOPO
and ROSS427 have
been
reducing
type.
extractive
same
coefficients
of U have
“square
but cases The
extractant
White
oxide
the same
all elements.
and Ockenden
both extracted
much
for
review
show
of the
of TOPO.
under
in every
is generally
number
O. 1 ~
of Pu(lV
IV- 16 is a compilation
of compounds
solvated
are
but very
dependencies.
quantities
Table
compounds solvation
into
extraction
TBP,
properties
Trace
elements
and U(VI) The
to that for
different
of these
with the same
(!TOPO) and tri-n-butylphosphine 269, 408 The data of Martin
Pu(VI)
low
made
actinides.
of U,
to steric
series
Siddal~76
concentrations.
The
,.i
the extraction.
and hexavalent
is attributed
TBP,
depressed
oxide
bonds.
distribution other
where
concentrations. and the relative
were
possible,
large For extractive
this
conversion
reason power
35
were
taken
complex
since
are
only
different
to other
values
approximate.
where
comparison
oxide
the experiments
the numerical
is di-
HN03
was
by direct
of the phosphine
number
to 1 — M extract-
at 1 ~
or the acidity
calculated
or by comparison
extrapolations,
by a large
converted
that the extracted
present was
of Pu(IV)
were
coefficients
to TBP
The
conditions. required
ions
relative
of Pu by extracting
TBP
are in the
data taken
data to 1 ~ were
done at
of the distribution
100
100(
I0( Ic
1( I & D
1.(
D
1. 0.
0 0.0
Hydrochloric
Fig. 10. Extraction of metal hydrochloric acid by 0.1 ~TOPO cyclohexane.269
0.00 Nltrlc
acid
Fig. 9. Extraction nitri~ acid by 0.1 ~ hexane.269
Acidic
in recent
years
these
chelation.
In many
organic
phase.
cl-,
and possibly
compoundfi
phosphonates
In general,
his- 2- ethylhexyl
molarlty
Compounds
and related
attention
ions from in
of metal ions from TOPO in cyclo -
These acid
acid molarlty
during
compounds
For
cases
example
Mono-acidic ethylhexyl
phosphoric
attention.
They
and di - acidic
for
compound
from
compounds. (HDEHP)
They more
have
complex
several from
type
thus formed
acids
involves
phosphoric
are the compounds
of phosphoric considerable
or specific reaction
extractants.
analogous
is further
in the extraction
the respective
Di-n-butyl
esters
recieved
versatile
by an ion exchange
the extracted acid
in extractions
acid
the mono-
the search
extract
the chelate
phosphoric C104-
are
and phospbinates.
of Th(IV)
the anions 312 acids. acid
that have
to
solvated
(DBP)
in the with
such as N03-,
and bis-2-
received
most
been shown to be dimeric in the organic phase in a non-polar 310 solvent such as benzene. The dimerization is presumably due to hydrogen bonding 130 the phosphoryl oxygen. The extraction reaction can be formulated as M â&#x20AC;&#x2DC;p
have
+ P(HA)2(0)
- M(HA2)P(0)
+ PH+. 36
to
(1)
TABLE
IV- 16.
Extractant Phosphatea Tribut yl (TBP)
Data on Extraction
Extractant Concentration Vol. Y, (M)
Ililuent Kerosene Gulf BT
Compiled
19 (0.69) â&#x20AC;&#x153;
of Pu(IV)
Nitric Acid Concentration (M) (a) 1.0
30 (1.09)
Kerosene
40 (1.46)
Kcroaene
20 (0.73)
Benzene
20 (0.73)
by Neutral Pu Cone. (M) , â&#x20AC;&#x201C;. T(d)
~rgano-phosphorous
D Given in Paper
Compounds
Datl M Extracta~t (b)
Relative Extractability (TBP = I. O)(c) 1.0
Reference
1.5
3.2
T
3.0
2.5
92, 93
T
3.5
1.6
76
.9X1 O-4
44
2.6
281
14.1
26.3
364
Mesitylene
6.4
11.9
364
Heptane
4.72
8.8
Nonane
5.46
10.2
------
100 (3,65)
-3.0
1.0
T
1.36
36.
1,0
I
364 364 41
(1)
1.0
T
3.0
3.0
n -Dodecane
30 (1.09)
3.0
T
16.1
13.5
Dibut yl methyl
Carbon tctrachloride
(o. 5)
2 (initial)
0.0038
0.71
2.8
0.45
69
Dibutyl - decyl
Carbon tetrachloride
(o. 5)
2 (initial)
0.0036
2.3
9.2
1.26
69
Triisobutyl
n -Dodecane
(1.09)
3
T
11.8
9.9
0.73
376
Tri-
Xylene
187 376
n -Dodecane
(1.09)
3
T
15.6
13.1
0.97
376
Tri-iaoamyl
n -Dode cane
(1.09)
3
T
17.8
15.0
1.10
376
Tri-
n -hexyl
n -Dodecane
(1.09)
3
T
15.6
13.1
0.97
376
n -octyl
n -Dodccane
(1,09)
3
T
15.3
12.9
0.95
376
Tri-
n-amyl
NOTES: (a) (b) (c) (d)
Equilibrium agueous concentration are listed except as noted. Calculated by aaaurning di- solvation and ideality in the organic phaae; i. e., the extractant. Calculated by comparing to TBP under the same conditions under the same wise the comparison is made indirectly. These caaea are noted. T representa tracer quantities of Pu.
D1 ~
= Dfl
ev~rime~al
()
~ 2 where conditions
x is the concentration where
poaaible.
of Other-
Table Extractant Phosphates
w m
Extractant Concentration vol. 7â&#x20AC;&#x2122;0(I@
Diluent
IV- 16.
Nitric Acid Concentration (.&l) (a)
(Continued) Pu Cone. (M)
Tri-2-ethyl hexyl
n -Dodecane
(1.09)
3
Tri-2-butyl
n -Dodecane
(1.09)
3
Tri-3-amyl
n- Dodecane
(1.09)
3
T
Tri- 3 -methyl2-butyl
n -Dodecanc
(1.09)
3
Tri-4-methyl2- amyl
n -Dodecane
(1.09)
3
Tri-sec-butyl
Amsco
125-82
(0.3)
Tri-2-octyl
Amsco
125-82
(o. 3)
Dibutyl
ethyl
Carbon tetrachloride
Diethyl
a.myl
Diethyl
n -butyl
Diethyl
isobutyl
Pho sphomt es Dibutyl butyl
(o. 5)
Relative Extractability (TBP = I.o)(c)
Reference
21
28
23.5
1.74
376
18.1
15.2
1.12
376
T
24
20
1.49
376
T
22
18.5
1.36
376
0.5+ 0.5 M Al (N03)~
7.1X
5
56
3.85
187, 420
4
44
3.07
187, 420
0.8M Al(N~3)3
4.2 X
2.62
10.5
0.62
I 0.75 ~
Datl M Extra cta=t (b)
25
1).6+ CC14
D Given in Paper
0,1M
T T(d)
1.55
376
10-5
182
10-4
I
T(d)
U02(N03~
3.76
15.0
0.89
3.73
14.9
0.88
3.69
14.8
0.87
1.23
2.2
17.3
181
CC14
0.5
2 (e)
0.0038
32
128
20.4
69
Dibutyl
methyl
CC14
0.5
2 (c)
0.0038
29
116
20.0
69
Dibutyl
decyl
CC14
0.5
2 (e)
0,0038
35
140
22.3
69
Di- n -butyl phenyl
(f)
1.0
1.0
T
3.2
3.2
1.0
187
Di-sec-butyl Phenvl
(f)
1.0
1.0
T
5.1
5.1
1,6
187
k)
Initial
(f)
Diluent
aqueous
concentration,
not stated,
probably
kerosene.
Table Extractant Concentration vol. 70 (M)
Extractant Phosphonat
es
Diluent
IV-16.
Nitric Acid Concentration (!4) (a)
(Continued) Pu Cone. (M)
D Given in Paper
Datl M Extracta~t (b)
Relative Extractability (TBP = lo)(C)
Reference
r -.
Dibut yl but yl
n-Dodecane
1.08
1.0
T
160
137
22.o~~l
Di-2-amyl 2 -but yl
n- Dodecane
1.096
1.0
T
53
44
14.7@)
379
11.15
44.6
16.6
318
7.43
29.7
11.1
Di- n-hexyl methyl
11.65
46,6
17.4
Di- n -hcptyl methyl
10.95
43.8
16.3
Di- n-octyl methyl
13,65
54,6
20.3
Di- n -nonyl methyl
24.15
96.6
36.0
Di- n-decyl methyl
21.65
86.6
33.3
17.35
69.4
25.9
1.34
5.4
2.0
11.60
46.4
17.3
17.85
71.4
26.6
7.58
30.3
11.3
7.67
30.7
11.4
Dibutyl
methyl
0.5 — M
CC14
I.O(e)
+ 0.21
0.004
Di-isoamyl methyl
u w
Di- cyclohexyl methyl
C(
Diphenyl
methyl
n -butyl n -hexyl
methyl
0.:
4
n -butyl nheptyl methyl Di- n-but yl ethyl Di-isobutyl ethyl (g)
Indirect
comparison,
i. e.,
to TBP
under
M —
~,o(e) ~
+ 0.21 U02(N03)2
‘i the same
stated
0.004
conditions,
but determined
in a different
experiment.
375
318
Table Extr actant Phosphomtes
Nitric Acid Concentration (M) (a) I.O(e)
+ o-21
(Continued) Pu Cone. (M)
D Given in Paper
Datl M Extracta~t (b)
Relative Extractibilit y (TBP = I.o)(c)
8,65
34.6
12.9
Di-isoamyl n - propyl
7.46
29.8
11.1
Di- n -butyl n - but yl
9,46
37.8
14.1
Di- n -butyl n - amyl
8.91
35.6
13.3
Di-isoamyl n - amyl
9.00
36.0
13.4
Di-isoamyl isoam yl
7.69
30.8
11.5
Di-isoamyl n - oct yl
8,92
35.7
13.3
Di- n -butyl benzyl
1.91
7.6
2.8
Di- n -butyl methoxymethyl
1.16
4.6
1.7
Di–n -butyl ethoxymethyl
1.50
6.0
2.2
Di 2-(n -butoxy) - ethyl- 1
3.26
13.0
4.9
Di l-methyl-2(n -butylcarbo~) - ethyl- 1
2.35
9.4
3.5
Di 2-(n -butylcarboxy)ethyl-1
2.38
9.5
3.5
Tetra- n -butyl methylene diphos phonate
6.72
Di- n -butyl n -propyl
!+ o
Diluent
Extract ant Concentrate ion vol. 70 (M)
IV-16.
CC14
0.5 — M
~
0.004
Reference 318
U02(N03)2
10.0
,
Table Extractant Phosphonates Tetra-isoarnyl methylene
Diluent
Extractant Concentration vol. ~O(M)
CC14
0.5 — M
IV- 16.
(Cent inued)
Nitric Acid Concentration (M) (a)
Pu Cone. (M)
l-o(e)
0.004
~
+ O*2I
D Given in Paper
Datl M Extract~t (b)
8.45
Relative Extractability (TBP = I.o)(c)
Reference
12.6
316
69
161
U02(N03)2
Phosphinates Butyl
dibut yl
0.75 — M
CC14
0.6 + 0.1
T (d)
49
87
U02(N03)2 Butyl
dibutyl
CC14
0.50
2 (e)
0.0036
170
510
108
69
Ethyl
dihexyl
CC14
0.50
2 (e)
0.0038
200
800
127
69
Butyl
dibutyl
1.08
1.0
T
160
137
499
686
703
181
T
236
23,600
-Ioofg)
269
0.004
299
1,196
446
318
Phosphine
m- Dodecane
Oxides
A F
Tri-n-but
yl
0.75 — M
CC14
0.6 + 0.1
T(d)
U02(N03)2 Tri-octyl Tri-n-butyl
C yclohexane
0.1 0.5
CC14
1.0 1.0 + 0.21 (U02)(N03)2
Tri-isobutyl
0.5
CC14
1.0 + 0.21
0.004
21.9
32.6
876
318
(U02)(N03)2 Tri-butyl Tri
octyl
Tri-2-ethylhexyl
CC14
0.01
1.0
T
110
1.1X106
-3 x ~05@
406
T
100
I,ox
-3X105
187
T
200
2.0 X104
‘6000
187
Amsco
125-62
0.01
0.8
Amsco
125-62
0.1
0.6
106
In this
equation, This
valent times
HA represents
equation
ions
has been
in general
further
may
conditions
employed.
shown
complex
in the organic
be involved
phase
no general
behavior. 238 et al. studied
of phosphoric
for
di-
behavior.
ions,
extracted
chloride,
but tetra-
complex
and even
depending
reaction,
reaction
acid.
and trivalent The
and nitrate,
in the extraction
Thus,
ester
to be correct
show a more
solvated
complexes
for
any monoacidic
is some-
perchlorate
on the specific
can be proposed
which
will
aqueous
account
all of the observed Kosyakov
nitric
acid
shown
in Fig.
solutions 11.
by several The
the extraction
of Pu(IV)
dialkylphosphoric
distribution
acids.
coefficient
and other Their
increases
results
as the length
Dlbutyl phosphoric
acid
(HDBP)
2.
Dloctylphosphoric
acid
(HOOP)
1.
\
actinides
3.
Dinonylphogpharlc
acid
(HDNP)
4.
Dldecylphosphorlc
acid
(HDDP)
5.
Di-2-ethylhexyl
phosphoric
for
from
Pu(IV)
are
of the normal
(HDEHP)
4.0
a : J
3.5
3.0
2.5
I I .0
I o
) LOG HN03
Fig. 11. Extraction HN03 solutionsâ&#x20AC;&#x2122;. 238 alkyl
chain
is increased
any of these. nitrate
The
completing
extraction
of Pu(IV)
from
butyl
from
first
The
extracted
Pu is probably
coefficient
to decyl,
of the slope
in the extracted
found to be inverse
distribution
by dialkylphosphoric
non-linearity
into HDEHP
CONCENTRATION
species.
HC 104 solutions
power
in the region as a hydrolyzed
was found to vary
acids
but that for of these The
(~) (0.5 ~
2-ethylhexyl
extraction
acid
approximately
species
directly
ionic
at low
as the square
was
than
is ascribed
to
determined
by
strength
of 1.0 and
0.05 to 1.0 ~
acid
from
is greater
curves
dependency
at a constant from
in isooctane)
H+.
concentrations. of the HDEHP
The con-
centration. The U(VI)
distribution
into HDEHP
from
coefficients nitric
acid
for are
the extraction ahown 42
in Fig.
of Am(III), 12.
The
Pu(IV
), Np(V ) and
discontinuity y in the NP(V )
5
4
3
~-
2
x
a ml 0 -1
I
0
-1 \
-2 I -1
-3 Log Fig. 12. Extraction HN03 solutions.238 curve
at high acid
Np(VI),
at high
acid
are
CONCENTRATION
actinides
concentrations
both of which
curve Am
HN03
of various
\ \
I 0
I 1,
w)
into 0.5 â&#x20AC;&#x201D; M HDEHP
(isooctane
is due to disproportionation
more
extractable
concentrations
than Np(V).
is probably
diluent)
of Np(V ) into Np(lY
The minimum
due to nitrate
from
) and
in the Am(lII)
completing
of the extracted
species. Horner
HDEHP. HN03 tion
and Coleman
As
shown
power
using
are
dependence
0.01 ~
very
much
HDEHP
larger
on the extractant
ference
is the decreased
ascribe
this
to hydrolysis
to Pu(IIf)
with hydroxylamine
with
nitrite,
is concave 125-82.
at 0.1 ~
of Pu(lV
downward
with increasing
into account. acid.
Horner
) by
The magnitude of distribu238 ~ the second ~.,
of Kosyakov
of the Pu(IV).
Kosyakov
the extraction
is taken
coefficient
decrease
while
curve
concentration
distribution
for
in Amsco
than those
by reduction sodium
result
13, the extraction
in Fig.
concentration coefficients
187 get a different
Homer
Another
dif-
and Coleman
and Coleman
prepared
Pu(IY)
and reoxidation and stabilization nitrate, 238 dld not state their method of preparation et al.
of
Pu(lv). Dreze phosphoric nitrate are
(HDBP)
concentration,
stability They
acid
shown
in Figs.
constants
consider
which
they
from HDBP
of Pu(IV
+ 2(N03
calculate
investigated
nitrate
the extraction
solutions
concentration,
14 and 15.
the extraction
PU+4
for
121
and Duyckaerts
These
) nitrate
as a function
and ionic
experimenters complexes
reaction
of nitric
strength. were
by di - n-butyl acid
concentration,
Representative
able
to invoke
to fit the various
fwctional
results
the known dependencies.
to be
)- + 2(HDBP)2(0) the equilibrium
of Pu(IY)
- PU(N03)2 constant 43
(H(DBP)2)2(0)
+ 2H+
to be (1.7 + 0.3) X 109 (m/1 )2.
(2)
X[N05]
=
[HN03]
~[N03] 6 ~
‘(
= (HN03
+
NaN03)
~ 10 HN03
(equlllbrlum),
~
Fig. 13. Pu(IV ) extraction by di(2-ethylhexyl) -phosphoric acid: effect of nitric acid and sodium nitrate concentration. ● 0.01 ~ D2EHPA; O 0.1 JvJD2EHPA; diluent, Amsco 125-82. Plutonium reduced with hydroxylamine nitrate,’ deoxidized and stabilized with 0.1-0.5 — M NaN02.187 I
I
I
I
I
I -2.5
I -3.0
I -3.5
I -4.0
3 2.0 –4
lo –5 o so J
–
-1.0 / -?0
–
-3.0 –
I -2.0
Lag 2~2 Fig. 14. Variation of centration of the dirner, centrations: Curve Curve Curve
A2]
the distribution coefficient (HDBP)2 in benzene. 121 1-0.5 2-1 3-2
of Pu(IY ) as a function of the conHN03 + NaN03 = 6 ~; HN03 con-
Curve Curve
~ ~
44
4-4 ~ 5-6 ~
On the other
1“’’’’’’’’’”1 I .0
same
system
complex 0.5
by assuming
Early
work
HhT03 system
Zo J
Hicks,
o
0.2 0.4 0.6 Log [H N03]
0.8
Lo
extraction
are
= 4 ~
+ NahT03
included
a strong
and
lowering
when dibutyl instead used
of the ether
of hexane.
as the extractant 241 by Pu
to determine
and counting
pendency many
in a liquid
also.
A later
from
the form
similar
determined
of the distribution
elements
HDEHP
Fig. workers
done by Stewart
has been
Kimura225
other
the extracted
scintil-
later.256
Fig. 15. Variation of the distribution coefficient of Pu(IV) from nitrate solutions by HDBP as a function of HN03 concentration. 121 ● HN03 + NaN03 = 6 ~
■ HN03
on the
on the Pu(lY)-HDBP-
as the diluent
in a procedure
~
and
results
free.
coefficient
used
HDBP -1.0 1
was
394 who found
distribution was
Shevchenko
their
to be nitrate
0
-0.5
hand,
interpreted
Srnelov3’8
extracted
T
table,
comparison.
study
was made
de-
coefficients from
HC1 solutions.
of a periodic
16 for
the acid
of
50 volume His
results,
are
shown
Some
results
on the solvent
~. in in
from con-
II I 1[ 3 m
ml
Eir’lFIFT$$l[ 7FT T P.
Am
Bk
DFl)\
Fig. function
16. Extraction of elements of acid concentration.225
from
7[
HC1 solution
45
Ho .
Yb
E
No
7[
by 50~0 HDEHP
in toluene
as a
Di-acidic extensively
studied
a non-polar
solvent,
compounds.
Mono-2-
ethylhexylphosphoric
of this type of compound. such as ~enzene310, 130
It is polymeric and extracts
acid
has
been
in the orgamic
primarily
most
phase
in
by the ion exchange
re-
action. Kos yakov by mono-2shown
17.
The
conditions
by washing
studied
ethylhexylphosphoric
in Fig.
aqueous
et al. 238
acid
distribution
than those
with a 5 ~.
the extraction (H2MEHP)
from
coefficients
of HDEHP.
solution
of Am(III),
are
Pu(IV)
of potassium
Pu(l!V),
nitric
in general
acid
NP(V), solutions
higher
can be returned
and U(VI)
for
with results the same
to the aqueous
phase
oxalate.
5.0 -
4.0 t NP(E)
~ 2.0 : -1 I .0 â&#x20AC;&#x201C;
o -
-1.0 -
I
1
-2.o~ -1.0
-0.5 Log HN03
Fig. 17. Extraction HN03 solutions.238 Peppard
et al,
of various
313, 270
from
HC1 solutions
over
103 and is a factor
Separation Gindler
~.
be returned in a great antagonistic)
from
(Fig.
from
The
14â&#x20AC;&#x2122;
used this
reduction effect
the extraction
actinides
of several
than the other
to purify
reagents,
of acidic
H2MEHP
coefficient
for
(isooctane
actinides Np(IV)
diluent ) from
by H2MEHP at 12 ~
non-tetravalent
species
HC1 is studied.
of the Pu to the tripositive state. 236 Pu for fission counting. The Np(IV)
by the addition
in the distribution of these
0.2 ~
(M)
by. reduction
method phase
into
distribution
of 104 greater
to the aqueous
applications other
studied
18).
Pu is accomplished
Applications several
CONCENTRATION
actinides
I 1.0
I 0.5
0
coefficient (cf Mixed
compounds. Kosyakov
of higher
state, 46
to the organic
because
can
resulting (or
p. 71).
compounds
have
et al. 238 used HDEHP
and accomplish
phase,
of anti- synergistic
ExtractantsJ Acidic
in Pu chemistry. valence
of TBP
their
been
used in
to purify
mutual
Am(lII)
separation
G .
Am(III),
Pu,
~
after
HN03
and U,
pentavalent oxidized
4
3
with
to Np(VI)
phase
washing
with
n2 w
\
:
extraction is returned
extraction
is back-
by 3 ~
HN03,
by reduction
and back
to Pu(HI)
with
3 — M HN03. to the aqueous
with
-1 ~
the
and
Am(III)
the HDEHP
and
from
to Np(V)
O. 1 — M HN03.
the U(VI) back
I
agent
and recovered
and the Pu recovered
0.01
Np(V ) is then
by an oxidizing
by reduction
from
from
of the Np in the
NaN02.
by HDEHP,
organic
extracted
\
stabilization
state
extracted
ax-e extracted
Finally, phase
by
ammonium
carbonate. Chudinov c
from
preliminary
step in the
They
89
Ifp(V ) with
of Np(lY
extracted
HDEHP
U
as a
calorimetric ) with
arsenazo
(Il_f).
a Np sensitivity y of 0.04 ?/ml
by
method.
I
4
6 ~
10
8
DBP
12
HCI
to prepare
Fig. 18. Extraction of some actinide cations into 0.48 F H2MEHP in toluene as a function of H~l concentration.313
Pu(VI) is thus driven
+ Pu(IIf)
= Pu(IV)
to effect
was used a pure
.
from
a mixture
by Markin
Pu(V)
The method
HN03
and McKay
solution
in 0.2 — M
was ta extract
of Pu(IIf)
268
Pu(IV )
and Pu(VI).
The
reaction
+ Pu(V)
to completion leaving a pure Pu(V) 311 et al. used H MEHP in various 2 a sequential separation of various
Peppard oxide
state
this
1 z
Yakovlev
and Pu away
determination
-1
-2
and
solution
in the aqueous
diluents, tri-,
phase.
and tri-n-octyl
tetra-,
phosphine
and hexavalent
ions from
urine. Peppard and from away
et al.
Pu.
from
The
Amine
HDEHP
actinides.
‘2°2 “ phase.
to separate
to Bk(lY) The
Bk(lY)
Pu is not reduced
Bk from
other
in 10 — M HN03 is then back
to Pu(III)
under
tripositive
by 1 — M KBr03 extracted these
into
conditions
actinides and extracted 8 ~
HN03
by
and remains
Extractants These
given
used
Bk is oxidized
tripositive
‘eduction ‘ith in the organic
tertiary
314
amines, general
compounds
reviews
amines
react
organic
phase,
are
and quaternary
of the extraction
with acids illustrated
R3N(0)
long- chain amine
to form
alkyl
of inorganic
an ion-association
by a tertiary
or aryl
Moore286
salts.
primary, and Coleman
species complex
by these which
secondary, and 95 et al. have compounds.
is soluble
The
in the
amine
+H++A-=R3NH+...A-
(0) 47
(1)
A may be either may
undergo
a simple
anion . reaction
a further
or the anion
of a complex
with
anion
another
metal
acid.
in a manner
This, complex
analogous
to anion
ex-
change
R3NH+ Much process
work
“ “ “ *-(0) has been
and analytical
than TBP
for
due to high extractant
U and Pu(lY
radiation
“ B-(o)
because
will
actinides
have
deleterious
the radiolysis
products
mixtues,
( cf Mixed
be in the order
nitrate,
exert
effects
on the distribution
p.
with the
71).
sulfate,
influence
in
coefficients
do not interact
chloride,
a great
compounds,
distribution
Extractants,
relative
> Pu(III)
extractability
and other.
on the extractability
of Pu in nitrate
and the extractive
power
Id , I
I I
P cm : u“(m)
1
I [
solutions
of the amines
quaternary I I
with these
much higher
less
of the amine
(2)
+ ‘-
of Pu.
Systems The
> Pu(VI)
They
and show much
synergistic
and nature Nitrate
Pu(IV)
),
here
“
done on Pu and other
fields
to produce
structure
= R3NH+
applications.
The treatment The
+ ‘-
is in the order
varies
in the order
> tertiary > secondary 187 Pu(IW ) extracts very
> primary.
and selectively
in analogy
strongly
with anion
ex-
change. reported
Keder~.2° of several solutions
,
10
t
I
Lo
* w
A—
I
I
I
I
species
I
concentration.
much
more
also
20 and 21.
much
less
than for
from
other
actinide
dependencies mitting curve
The maximum
was unit y, was
and Np(IV
of the distribution
no unambiguous while
For
of nitric
distribution
power
are
depen-
was
where
all these
can
in the
first
1.5.
shown
species
is very
elements
concentration
and second The
trivalent
results
of these
the amine
complex.
approximately
species
with
separation
species, between
M is any
of hexavalent,
concentration,
an easy
were
48
the M(N03)6=
however.
for
of the extracted
two amine
1 and 2, the
No conclusions
coefficients
), indicating
Pu(III)
involves
actinide.
indicating
involves
to Eqs.
properties
acid
the hexavalent
given.
complex
about the nitrate phase,
the etiraction
coefficients
assignment that for
of
Th and U.
concentration,
complex
aqueous
determined
elements.
) and h’p(IV)
than are
and is (TOA)2M(N03)6,
be drawn
as a function
Pu(IV)
diluted
quadivalent
19 as a function
Pu(IV
According
quadrivalent
Fig. 19. The extraction of the quadravalent actini v/o TOA in xylene. ‘~gtitrates by 10
actinides
for
show a second
extracted
extracted anion
14
in Figs.
on the amine
molecules.
HNO~ Comaentr%on, ~
e~’”
species
dence that tie
024
Keder
These
(TOA)
in Fig.
extractable
HN03
1
I
and pentavalent
the extraction from
results
shown
HN03
.Aqueous
are
\
u
I
Their
\l
[
-1
A
elements
by tri-n-octylamine
with xylene.
D
fact
actinide
slope
power,
per-
of the Am(III)
No explanation
of this
‘“’m!r=%‘“”EsFF?E I
Io+
I
1
f
I
D
lo-
1 i ~ .x
,“* .
1.0
.17F%%F1
/
I I
I
I [
1
I 1
I
2 4 6 Aqueous HN03
I
B 1“ 12 14 Concentrotlon, ~
O
Fig. 20. The extraction of the hexavalent actinide nitrates by 10 v/o TOA in xylene.219 Keder quadrivalent
I
10-3
,O-LLLLLLU 0
I
APa X Ref.(13) ■ Pa (X) vNPCZ) ● PU (m) o Am (~
r A r~[ I *
0
I
I
a
[
AP D
I
7
I
I
I
I
I
-
2 4 6 8 10 12 Aqueous HN03 Concentration, ~
14
Fig. 21. The extraction of pentavalent and trivalent actinide nitrates by 10 v/o ‘roA in xylene. 219
et al. 218
determined
that the extracted
actinides
and M02 (N03 )3- for
complex
hexavalent
is M(N03
actinides
)62-
for
by spectrophotometric
measurements. Homer tribution
coefficients
solutions,
23) although
much
A1(N03)3
(Fig.
with
similar
The
extraction
lower salting
et al.
“tricaprylamine”
36
(TCA, results.
The
concentration.
raises
Their et al.
The
coefficients
the D ~u(lll)
determined
from
Pu(IV) results for 219 and Baroncelli
other
with
the dis-
of amines
classes
NaN03
at lower
HN03 unsalted ~.~’
of amines
at a constant
acidities.
with all classes
to a relatively
reached
depressed
a maximum
is confirmed,
of 1.5 ~ of a uranyl
uranyl
high value
but
reach nitrate
Pu(III)
of amines
and (Fig.
with tertiary
trinitrate
100, ”
of the TCA
ion,
which
of the log D Pu vs log
corresponding
complex.
49
slope
for
HN03,
saturates
the formation
solutions
and
and n-decyl-amines),
an aromatic
D = 140 at 4 ~
uranyl
HN03
of n-octyl
in “Solvesso
of macro
but the slope The
of Pu(17J) between a mixture
of approximately
the concentration
ion.
336, ”
was diluted
by the presence
Pu(IV)
complex
the distribution
as “Alamine
amine
varying
mation
and 24. with Keder
distribution
measured sold
In experiments
presence
HN03
have
a number
24).
Baroncelli
strongly
22, 23,
qualitatively
for
9 — M HN03. The effect of salting is to increase the distribution coefficient
show very
amines
at a lower
and Pu(VI)
in Figs.
agree
420
and Homer
at around
concentration Pu(VI)
Pu(III),
shown
(TOA )
the maximum
a maximum
and Weaver
of Pu(IV),
with results
tri-n-octylamine reach
187
and Coleman
naphtha. and was
the extractant.
of the hexanitrato TCA
curve
U is 1, indicating
is 1.4 in the the for-
104
I d
Id
Fig. 22. Pu(lY) extraction by 0.1 ~ amines: effect of nitric acid and sodium nitrate concentrations. Amine class: (Q) quaternary ammonium, (3) tertiary, (2) secondary, (1) primary amine. Pu(IV) stabilized with 0.04- 0.1 ~ NaN02. Amsco 125-82, TDA = branched primary tridecanol. 187
n 10
I
1 [No,] . A M(HN03. I$INOJ 10-1
a
M“
, ,,81
I
0.1
1
&“’’’”!
HN03 (EQuILIMIuM), M
Baroncelli ~
eta136 also
U ion and 4 ~
amine, ” TLA)
in an aromatic
T“) , and found them 5 ~. nomnol plex
in the organic
Other
Np(IV), extraction (TNA,
2 ~
solutions
o
Zr,
and Ru.
Dpu value
The
to strip
Several
mixture.
Pu(IY)
been
from for
proposed,
4 M HN03,
to work
acid 0.04,
(“ Shellsol
had about of the comfrom
U by
is a very
TLA
Wilson42’
good
stripping + 1~
TLA
50
Pu(IV
) in
and 0.8 — M
well
from
Valentini
irradiated
+ 2% Octanol
the Pu by reduction
used the same extraction system, 409 used the TLA-HN03 . Valentini et al.
for
was
~.40g
TNA used
results.
of Pu and U from
gt@.8T
agent
U(VI),
amine
curve
HC104
was not stripped
to expectations.
with good
used
with tri-isononyl
concentration
3 smines.
on other
both in 1 — M HN03
in contrast
the separation
and stripped
~ vs HNO
the DPU(N
42 found that Pu(IV)
HC1 solutions,
processes
have from
Bertocci
was
found that,
Bertocci42
in contrast
found that perchloric
by NH20H.
H2S04
Chesne
diluent
mixture
amine
HN03,
HhT03 + 0.2 — M HC104
Pu(IV)
and a paraffirdc
TLA-Shellsol
1.5
(“tri-lauryl-
phase by increasing the volubility 409 achieve maximum separation et al,
Valentini
U(VI),
at 6 ~
solutions.
amines
The
amine
HN03.
with tertiary
of Pu(IV),
increasing ~i1son43
TOA
100”)
40.
for Pu from” initially
dodecyl
of a third
tri- 3, 5, 5 -trimethylhexylamine),
still
1~
(“ Solvesso around
factors
with tri-n-
nitric acid systems with generally similar restits 116 ‘ 84 on TLA extraction of TL(IV), and Chesne that of de Trentinian and Chesfie 231 232 on tri-iso-octylamine and Knoch and Lindner Np(VI) and Pu(IV); Knoch
includes
work
diluent
formation
phase.
Pu from
the separation
extractions
to be similar,
to prevent
extracting
determined
HhT03 by amine
system.
in kerosene
to Pu(IfI)
but stripped
U using
to extract
with ferrous
the Pu(IY)
tertiary
sulfamate.
by a HN03-H2S04
101 0.1 o
M
B-lu
Reogents: in
Amsco
-
w
●
TDA
~-~
*A
in Amsco - 8% TDA .*** .0 in xylene M TI OA ■ V S-24 in Amsco .“ ~.. ~ NBHA in xylene ’”” o Primene JM in Amsca ,c* p--~ 5% TDA Qm ●“ o
TIOA
●
●
\
10
–%
I
[1
Z N03
.0.1
10-1
~
= 6 IV (AI(N03)3
x-
MTIOA
in Amsco - B% TDA
xO. I MTIOA
in xylena
~0.3 MTIOA in xylene ~1).3 M TLA in xylene - H 0.3 itfAlamine 336 in xylene
Ouo
\
+ HN03)
/0~ ,’ ,0’
,0-2 U~ltd
1’
10 2
HN03
(EQUILIBRIUM),
M
Fig. 23. Pu(III) and Pu(VI) extraction by 0,1 ~ amines: effect of nitric acid concentration. Amine class: (Q) quaternary ammoniwn, (3) tertiary, (2) secondary, (1) primary amine. Pu reduced with 0.03 M ferrous su amate plus 0.05 ~ excess sulfamic d{ acid, or oxidize~with AgO. 1
Solutions
x’
/ ,0-3
I
I
I
I
0.1
0.01 HN03
Fig. Pu(III)
I
HN03
(EQUILIBRIUM),
M
24. Extraction by tertiary aminea from solutions in nitric acid with and without aluminum nitrate Plutonium reduced with 0,0 ~ ferrouB sulf~ate ~&%g05 M excess sulfamic acid, 18 ? —
of
The
fact
that Pu(III)
basis
of a Np-Pu
nitric
acid
does not extract into tertiary amines 357 separation. The Np is extracted as Np(IV)
perimental
factors
for
metals
equilibration
a study from
A summary
in Table
from
for
of the decontamination
Fe,
of their
IV-17.
was obtained
process
made
laboratory
extraction.
Pu is given
these
431
and Mararnan
pyrometallurgical
and amine
from
away
made
the
Pu(lTf)
in a
solution.
Winchester
TBP
has been
They
Co,
Mo,
Ru,
in terms
concluded
in the secondary
recovery
Zr,
results
of Pu in an exand Ce by both
of decontamination
that the best
amine
separation
system
and described
scale
in a metallurgical
of Pu on a 300-gram
of Pu a batch
laboratory. The
Pu and U complexes
separate
zs a third
of polar
constituent,
phase e. g.
the extracted
complex.
of the effect
of nitrous
acid
can have
depending
effect.
acid
added
acid
to stabilize
in the organic The
quadrivalent
or depressing
effect
while
molar
acid
nitrous
coefficient
of an alcohol-nitrous Decontamination Processes.43
phase,
addition
and
of a small
acid
for
This
fraction
Impurities
TBP
1.26
74
>42
Secondar amine
is explained
in terms
phase.
in Plutonium
in Various
for(a)
120
--
-.
>60
1.86
> 300
> 31
> 80
0.34
44
> 22
92
Mo
0.17
> 100
Ru
0.98
1.3
12
38
Ce
0.36
2.1
25
> 67
Pu
60.58
> 52 > 52
31 >18
>78
--
effect
has a
in the organic
Quarternary amine
co
--
concentration
factors
$C)
coefficient, always
Tertiary(d) amine
Zr
>8
found that nitrous
alcohol
in the organic
Decontamination Primary(b) amine
They
chain
and alcohol
complex
Factors
Pu.
on the distribution
the long
is at a maximum.
Initial concentration (g/ 1)
Fe
.aolubility
concentration.
concentration,
At equal
TABLE IV- 17. Solvent Extraction
Element
limited
into the organic phase, increafies the volubility of 35 have made a study of this effect, and also et al.
an enhancing
the distribution
of the formation
Octanol,
Baroncelli
on the nitric
depressing phase,
either
have
at high metal
>9
16
--
13
>32
>29
--
--
Notes: (a)” Procedure consisted of 3 equal volume extractions with 35 vol. YO reagent in Gulf BT Solvent (aliphatic hydrocarbon) from 8 ~ HN03 solution (except primary amine extraction in which 6 ~ HN03 was used). The secondary, tertiary, and quaternary amines had 10 vol. ~0 decyl alcohol. The solutions were stripped with 3-1/3 volume portions of O. 1 ~ hydro@amine nitrate. ‘b)Rohm (c) Rohm
and Haas
Company
and Haas
Company
“Primene “Amine
JM-T!’ 9D- 178. ”
(d TIOA . (e)
Sterwin
Chemical
Maeck~.262 quaternary ketone
Company determined
ammonium
(“hexone”
).
The
compounds aqueous
“Roccal.” the distribution between solutions
of a
various considered 52
large
aqueous were
number solutions NaOH,
of elements
for
and methylisobutyl HN03,
H2S04,
HC1,
and HF. NaOH,
No extraction and HF.
extractions
from
periodic
cedure
for
aluminum a better
tainable
nitrate
The
amine
quaternary
solutions
as a salting
as part
amine
is poorly
Plutonium
work
the formation
has been
fission
“Hyamine
in the form nitrate
of a hexanitrate
appears
of
(TBAN)
Pu(IV)
to be stable.
on this
developed
products,
1622”
A pro-
extraction
system 261 et al. They
by Maeck
particularly
Zr,
has been used to extract 48 Pu.
procedure
) and Pu(VI)
extracted,
chloride
chemical
acidity
than is ob-
Pu(IV)
from
HN03
for
Systems
Pu(lV Pu(ITI)
of H2S04,
25 and 26 as percent
systems.
of an analytical
Chloride
of aqueous
of Np and Pu based
agent
from
in Figs.
that tetrabutylammoniurn
the tetranitrate
determination
decontamtiation
in other
caused
of TBAN
at any concentration
given
as a function
into hexone
radiochemical
using
was found
and HC1 are
volumes
in the absence
report
HN03
and Kaplan 40 found
extracted
while
or Pu(VI)
for
phase
Berkman
to Pu(IV)
species,
results
equal
tables.
added
of Pu(IV)
The
systems
rather
extract
in analogy have
well
from
HC1 solutions
with the strong
found
application
than in processes
base
anion
mainly
because
by amines,
exchange
in analytical
of the corrosive
while
system.
and radio-
properties
of HC1
solutions. Keder217
measured
and U from
HC1 solutions
distribution
coefficients
case,
the slope
the extracted more
are
of the log D vs log
Shevchenko distribution
has two
The
is shown
concentration
molecules
for
similar
in Figs. curve
the same in this
results
was approximately
for
0.005 for
and hexavalent
dependence
Iip,
In every
2, indicating
states.
that
Pu(IV ) is much
conditions.
The hexavalent
system.
Pu(IV),
Pu(III)
Pu,
of the
27 and 28.
is near
both valence
than the tetravalent
obtained
et al.366
of tetra-
( TOA ).
and U(IV ) under
extractable
coefficient
TOA
TOA
than is Np(IV)
more
coefficients
on HC1 concentration
complex
extractable
actinides
the distribution
into tri-n-octylamine
and found that the
extracted
into
20% TOA
in
xylene. Moore282, xylene
from
Niobium
283
4.8 ~
extracted
HC1,
and ruthenium
is possible
by scrubbing
trivalent
and lower
has been
used to separate Sulfate
using
~ solutions
molecules. The
decrease
merization.
5 ~. tri-isooctylamine bichromate
extent,
did not extract. Pu(IV)
before
but separation stripping
from
analysis
in
oxidant.
these
of the Pu.
The tri-laurylamine
spectrographic
(TIOA)
as a holding
elements
Th(lV)
(TL4)-HC1 of other
or
system 234
elements.
Systems
sulfuric
and Zhdanov
They acid
showed
from
coefficient
concentration
of an amine
373 . investigated
that the extracted
dependence
in the distribution As the acid
to the formation
to some
with
with .— 5 M HC1 and reductive
speices
by TOA.
The
Pu(VI)
potassium
extracted
Shevchenko H#O
tracer 0.01 ~
bisulfate
0.1 ~
at low
is increased, complex.
53
TOA
acidity
the extraction complex is shown is ascribed
the decrease
of Pu(IV
contains in Table
to Pu(IY
in D
Pu(lv)
) from
2 amine IV- 18. ) polyis ascribed
Fig.
25.
Extraction
of elements
as tetraalkyl
amine
HI
EXTRACTION
)98%
NO
EXTRACTION
( I %
m
complexes
from
nitric
acid, 262
EDEIEI QEIEIEI
HCI SYSTEM
EIElliiiJilk lii!EEIEl (I+OXYI)4
N+ I-
(Butyl)4
N+
(PrOPyl)4
N+
â&#x20AC;&#x201D; Fig.c~6. . .
Extraction
of elements
as tetraalkyl
54
amine
complexes
from
hydrochloric
102
TFEIFI: 10
‘o’~lo
I .0
lo~
10
lo-
I.0
u (Vi)
●
D 1.0 ,
A
:Vll :Vl)
I
~410-2 ,0-1
10-1
I
—
A /l #-l II A
I
IO-3
FPhl-1 “-.
:
flv) ...
;::/;;
10-4
10-2
01
‘0-30~cT-
and by 1. 0~.
Vdovenko extraction
solved
at equilibrium
DPU(IV)
(M) 0.01
11.3
0.037
15.2
0.1
43
0.323
18,2
concentration 0.1 hJ 2.34 X 10-4 — M.
they
that in this
same
amine
increasing effect
Pu sulfate HN03
is illustrated
case
mixtures complex
concentration
Pu(IY
the anion
because
by the data in Table
i, e.
From spectra
exists
complex exchange
process
and HN03
of the formation IV- 19.
55
4
comparisons
conclude
primarily
does
and that the
as a neutral phase.
sulfate
Therefore,
not operate. by the formation
coefficient of mine
of the
of the ad-
in the aqueous they
)4,
dependence
macroscopic
in the aqueous
proceeded
but the distribution
involves
of the stoichiometry
phases,
Pu(IV)
dis-
determined
(RNH3 )4pu(so4
concentration
and by direct
sorption organic )
of H2S04 above,
complex
molecules,
the
of 7 to
amines
They
amine
reaction.
0,008
aliphatic
in chloroform.
method,
2,44
investigated
) by a mixture
that the extracted
measurements
0.415
‘a) Initial TOA concentration
primary
by the amine
0.88
from
9
HCI
-.412
of Pu(IV
9 carbon
Concentration
Extractions
~
67
Fig. 28. Extraction of hexavalent U, Np, and Pu from HC1 solution with 1. 0~. TOA in xvlene.217
TABLE IV- 18. Dependence of the Distribution Coefficient for I%(IY ) Between Aqueous Sulfuric Acid and Tri-n-Octylamine.373
conclude
5
234
5
M HCI
Fig. 27. Extraction of U(IV) h’p(~) by 10~0 TOA and Pu lv) TOA from HC1 solutions.21 $
H2S04
1
I
I
,0-2
decreased
nitrate
complex.
of the with This
TABLE IV- 19. Distribution Coefficients Amines as a Function of Increasing HNOq Concentration
of HN03
(~)
*Amine
concentration
0.06 ~,
By contrast, centration also
0.05
O 66.3
DPU(IV)
for
Homer
amines.
Their
distribution
H2S04
of Pu(IV
distribution results
coefficients
) from
coefficients
are
shown
in going
14.6
concentration 187
to more
into Primary
0.30
0.50
0.90
1.50
0.11
0.01
----
0.2 ~.
H2S04
solutions
Pu(IV)
29,
Solutions
2.08
get a third-power
for
in Fig.
H2~04
0.20
0.10 50.1
63.3
and Coleman
extractions
determined
of Pu(IV ) from Concentration.412
by primary
of several
showing
complex
dependence
amines.
secondary
the successive
amine
on amine
types.
con-
They
and tertiary
lowering
of the
report
variable
They
,04 I / / ,&
I
TZ:3
‘Y$;;
Primem JM/I@ma, 0“5 M 2.0 M
‘2s04 (NH4)2S04
/’
./
A-3
/
,A=
N-ba.zyl ~An-,
[
Fig. 29. Extraction of Pu(lV) from sulfuric acid and acidic sulfate solution by primary, secondary, and tertiary amines. Diluents: xylene, Amsco 125-82, or 957. Amsco 125-82-5~0 tridecanol. For, primary amine extraction, Pu reduced with hydroxylamine sulfate, reoxidized and stabilized at (IV) with 0.5 ~ NaN02. Others stabilized at (IV) with 0.1-0.5 &f NahT02.187
M S04, PH-O.7 NBW/&mm 3 M H2S04 -I -undecyl -lw@/ 3 M ~W4
3 M SO , pH-O.7 Dltddecy f /#bncu-TOA, 3 M
/
‘2s04
Am.inn 5-24/Annce, A3 .uS04, pH-CL7
Tri-lmavl/AmEo, 0 3 MS04, pH -
I 0.I
I
0.00I
0,01 AMINE
distribution ranging
‘5
oxidation
These solutions
authors
based
for
material,
M
Pu(III)
100 with
to Pu(IV
),
propose
on primary
The primary biological
COfWENTk4T10N,
to >>
of Pu(lIf)
I 10
I
coefficients
from
0.7
I
aminee. g.
by primary
0.1 ~
even
amines.
H2S04 urine
for
extraction. system
or
from
This
behavior
in the presence
a process amine
amines
solution
recovery 186
has been
of holding
acid
is attributed
solutions, to partial
reductants.
of Pu from
used for 61 of bone ash.
56
sulfuric
sulfuric
determination
acid
decladding
of Pu in
Other
Systems Moore’”
be quantitatively ~
nitric
acid
ferric
(or
extracted solutions
Nb extracted
ursnyl)
with
NH40H
from
from
acetic
or ammonium
or reductively
since
Ketones,
which
Ethers,
can solvate
popular,
but the newer
attention
in recent
process
separations.
irradiated
U,
the
as the primary extractive many
HC1.
of niobium
carrier
do not extract
and
the insoluble
HN03
by these under
improved
from
dilute
be stripped
– 0.1 Zr,
A preliminary
leached with
acid Ru,
m- HC1,
reagents
these
conditions,
the fact
atom.
that they
This
type
compounds they
are
contain
and amines
still
one of the large-scale
a basic
of extractant
important
oxygen
was once
have
received
more
in laboratory
processes
for
very
and
the processing
of
uses methylisobutylketone (MIBK or “hexone” 251 as do several laboratory procedures. U and Pu
)
process,
extractant
for
of the ethers
Both
systems
Pu(IV)
Pu(III)
species
depends
the extraction
for
b“, Fe,
and other
acid
is predominately than trinitrate
solvation
Similarly,
species
phase
nitric
elements
have
been
The
known for
similarly.
Pu extraction its use in processing.
acidities higher
as PU(N03
for
Pu(IY)
dichloride
)3,
1.5 ~
phase
for
example,
at low
acidities is more must
rather species.
in-
than 267
HN03
and as H2Pu(N0 245,’4636 in between.
at high nitrate
and H PU02(N03)3
for
dinitrate
and finally
)2 PU(N03
extracted
the dibutyl
the extraction
of the dinitrate
of the organic
into triethyleneglycol
(DBC,
plutonyl
(3-6 N),
)4 from
The
at intermediate
acidities
H(DBC
for
or at
shown that,
carbitol
is the neutral
of the extraction
composition
concentrations,
concentration.
and trinitrate
the species
into hexone
foumd to be H2Pu(N03)6
concentration
to form
acid
media
such as aluminum
by dibutyl
species
of dinitrate
as extraction
It has been
solutions
trinitrate at higher 171 At these 6N.
with intermediate
nitric
by a salt
composition.
above
extracts
attention
at any nitrate
acid
the extracted
of a proton
extracted
at high
provided
of the Pu in the case
Pu(IV)
at 6 — M HN03,
behaves
extractable
( < 0.8 IS) is a mixture
the solvation
direct
from
glycol)
the most
inextractable
on the aqueous
of Pu(VI)
of diethylene
volve
are
by far
concentrations
is practically
ether
(0. 8- 3N),
received
and Pu(VI)
nitric
complex
have
high nitrate
nitrate.
been
5 ~
only
could
years.
moderately
The
could
in common
or metal phosphorous
Indeed,
with
be stripped
and Pu(III)
Nevertheless,
“redox”
properties
Ifitrate Pu.
have
organo
Pu(VI)
acetic
products
U and Pu were
could
and Pu(VI)
and Amides
a proton
years.
The
U(VI)
and 1 ~
in the presence
The
Pu(lV)
solutions
be scrubbed
uranium
bicarbonate.
The se compounds atom
could
the se elements. The
actinides
Of the fission
precipitation
acid.
stripped,
Alcohols,
acid
-xylene.
and these
hydroxide
1~
1— M acetic
by 5 ~. TIOA
appreciably,
the decontamination Nb205
found that the hexavalent
Pu(VI).
concentration 76
Dibutyl
have ether
413 by hexone The
has received
extraction
and the concentration
the most
of Pu(IV) of various
groups. 57
attention,
and Pu(VI) salts
undoubtedly
as a function
has been
measured
because
of nitric by several
)
of
acid
10~
Rydberg distribution elements
I~
Pu(VI)
coefficients including
nitrate are
0.001 :
both with
shown
those
&
separated
tion curves
HN03
Pu(lY)
The
enough
from
other
extended
and Pu(VI)
effect all the
but at low high
to higher
results
elements.
the distribu-
aqueous
as shown
acid
to be
acidities
in Fig.
for
32.
Fig. 30. The distribution Pu(IV) and Pu(VI), Th, Zr, La into hexone as” functions
original
was replotted from MacKenzie!s 388 data by Smith because the
:~:;~s
original
was reported
taken
ratios of U, Ce(IV) and of &e “equiin the curve is _] et al. 14
calcium
is to raise
coefficients,
MacKenziez’o
con-
Typical
30 and 31.
of U and Pu are
efficiently
La
and
acid
and without
with Ca(N03)2
distribution 0,0001 .
Pu(IV),
agent.
in Figs.
measured
several
of nitric
as a salting
of salting
for
L’(VI),
as a function
centration
0.01~ D
343
and Bernstrbm
~;~~%i~h~f~~~ from
Glendenin
This
curve
phase a,cid concentration. .’, to aqueous phase original was
made
traction
F
10
‘ D
pass
by using
Both
maxima
aPProximately
u
7 ~
e. g. A1(N03)3,271J NH4N032’0
conversion concentration acid
Pu(IV)
ex-
and Pu(VI)
and decrease
above
salting
t
agents
Ca(N03)2,343,
for
Pu(IV
393 (Fig.
in salting
effectiveness
concentration
ammonium,
similar ether
comparison was made
was
The
nitric
for
order:
acid,
Pu(VI)
resulting
salts
at high
mag-
and manganese.
calcium,
ammonium,
33).
in this
lanthanum,
aluminum,
co-
of various
) into hexone
by Stewart
nitrate
agent,
the distribution comparison
reported
nesium,
(y)
A salting
153
increase total
CONCENTRATION
acid.
increases A useful
efficient.
0.1
HN03
The acid
data on nitric
by hexone.
through
of organic
PU(VIWV]
-z’
AQUEOUS
in terms
A
into diethyl
in this
order:
lanthanum,
nitric
acid. Kooi23’
Fig 31. The distribution ratios’ of U, Pu(IV) and Pu(VI), Th, Zr, La and Ca into hexone as functions of the equilib riurn concentration of HN-03 in the aqueous phase. Concentration of Ca(N03)2 4-3.52.343
curves
for
found that the distribution
extraction
into hexone
did not decrease
concentrations, workers. Pu(IY
His
) reached
approximately
58
of Pu(IV)
in contrast distribution
at high HN03 to other coefficient
the maximum 7 at 8 ~
and Pu(VI)
initial
value
for of
HNC13
I .0
D
Pu (Vl)n
o. I
32.
.
of Pu(IV
concentration.
MacKenzie
Pu(VI)
acid
port
no dependence
of Pu(IV). either
Groot
(). 03 ~
as oxidizing laboratory
260
in the range
extracts
or O.3 ~
and reducing
agents
procedure
is very
low
by hexone
from under
.
,D
into hexone
0,01-2
(Table
..
.
.
aalustoa
from
HN03
coefficient
mg/ml,
while
acid.
These
for
processes.
Rider
Pu and U in reactor
both
Groot
reagents
260
solutions.
et al.
for
the extraction
are are
Pu(IV) and 153 re-
not affected
commonly
by
used
has used hexone
~.332
targets.
Systems reports
from IV-20).
6 ~ HC1, reducing
9ulfOniC in redox
to determine
Aqueous
conditions well
Oadju6tBd
2 mg/ml d.,,
found that the distribution
increased
Stewart3’3
various
“
) and Pu(VI)
Na2Cr207
valence)
# “ ,
on Pu concentration from 0.00003 to 0.5 mg/ml 153 et al. also find that the distribution coefficients
Other
initial
,,
w II
Distribution
in nitric
1,
● Pu CONCENTRATION=
Pu(IV)
K
Fig.
Pu CO NCENTRAT10Nm2mg/ml
o
on the comparative
hydrochloric,
nitric,
Plutonium
but not from conditions
for
(presumably H2S04
or acetic
all these
59
extraction
sulfuric,
acids.
a mixture acid,
of Pu (unspecified
and acetic
acids
of Pu(IV)
while
under
and Pu(VI))
the extraction
in a
1“’’’’’’’”1
of total nitrate Fig. 33. Effect ion concentration on the extraction of Pu(lV) by methyl isobutyl ketone. 393 Curve No. I rI HI iY V VI
Aqueous HN03 only IN HN03 lN HN03 3N HN03 3N HN03 lM HN03
+ + + + +
Phase
NH4N03 Mn(N03)2 Mg(NO )2, P04--A1(N03 ? 3, P04--La(N03)3
loi-
TOTAL INITIAL NO= IN Other
Concentration
AQUEOUS
Extractants compiled
Stewart3’3 ethers,
alcohols,
states
from
ketones,
ammonium
their
entirety
tried
and to indicate
general,
the ability nitrogen
variably
decrease
etc.
for
a table
IV-21,
the types of these
or other
acid
the extractability
These
to show the
of compounds compounds
quadri-
mixtures.
and IV-22,
functional
of extraction
Pu in the tri-,
nitrate-nitric
as Tables
oxygen,
PHASE
which
to extract
group.
e. g.
number
of
oxidation
reproduced
in
of compoumds
efficient
as Pu extractants. with the basicity
electronegative diethyl
a large
data are
variety
correlates
Thus,
of Pu (see
are
data for
and hexavalant
ether
In
of the
substituents
in-
vs dichlorodiethyl-
ether).
TABL,E
IV-20.
Distribution
Composition 1.
Acid
of Aqueous
of Pu Between
Layer
HC1 10
only + 0.7 ~
Various
2.
Acid
3.
Same,
saturated
U02(N03)2
4.
Same,
as 2 + 0.06 ~
with
6H20 S02
hydroquinone
Aqueous
Distribution Extraction HN03 8.3
Phases
and Hexone.
Coefficient for from 8 ~ Acid H2S04
393
CH3COOH
0.06
0.012
0.33
3.3
0.005
-----
0.0012
0.25
-----
-----
0.0033
----
-----
-----
60
TABLE IV-21 , Volume of Various
Extraction of Plutonium Organic Solvents. 393
from
10 ~
NH4N03,
1 ~
HN03
% Pu extracted Solvent Ethers
(IV)
% Pu extracted (VI)
-C ellosolves
Diethyl
<1
ether
Di-isopropyl
ether
ether
<1 ether
Ethyl-n-but Dichloro
ethyl
<1
2-ethyl
but yl c ellosolve
66 6 93
ether ride
<1
ethylene
Anisole
<1
82 14 89
Cyclopentenone
91
Cyclohexanone
72
96
Methylcyclohexanone
82
73
Menthone
13
Isophorone
91(?)
20 <1
47
37
Hydrocarbons 3
3
5
4
Xylene (mixture isomers) 40
60(?)
of 10
Pinene
1.6
Indene
5
Nitro -
Compounds 43
Thiophene
1-
Carbon
6(?)
-
Nitro
1
benzene
Halogenated 1
Alcohols
1
Compounds
Nitroethsne Nitromethane
Disulfide
52
ketone
Acetophenone
12
1
sulfide
79
Cyclohexene
1
Diethyl
Methyl isobutyl (Hexone)
<1 <1
Cyclohexane
p-Fluoranisole
Dimethyldioxane
ketone
Me sit yl oxide
3
ether
n-amyl
73
62
Resorcinildimethyl
ketone
72
O-Nitroanisole
Sulfur
6
71 97
(VI)
Ketones
Methy
4a
Triglycoldichlo
1,5
1.5
21
flfl’ Dibutoxyethyl
5.7
1
cellosolve
Dibut yl cello solve
<1
<1
Methyl ethyl 157’0 Xylene
cellosolve
IRh yl but yl cellosolve
acid
1.5
3
‘ (IV)
but yl acetate
1
Benzyl
Dieth yl cellosolve
butyric
-
Phenyl
<1
2- ethyl
3.4
1
ether
(IH)*
- Esters
4.8( ?)2- ethyl
2
yl ether
Dibuto@etraglycol
50
71
N-but yl ether
Ethylallyl
<1 <1
ether
Hexyl
Solvent Acids
ether
N-propyl
Allyl
(HI)*
by an Equal
Methyl
34
61
58
70
8
28
Compounds
Chloroform
4
3.2(?)
Trichloroethylene
6
12
Hexanol
23
-
Chlorobenzene
4
7
Heptanol
15
-
Bromobenzene
2.6
2.5
10
-
Iodobenzene
1.3
1.7
o- Bichlorobenzene
4
5
m- Dichlorobenzene
4.6
Ethyl
1
1
1.6
1
Heptadecanol
<1
2- ethyl -hexanol
<1
2-ethyl-but
<1
amol
Methyl-isobutyl carbinol Meth yl-amyl
1
alcohol
116
-
42
-
42
-
iodide
Isoamyl
chloride
Tertiary
amyl
chloride
1
Miscellaneous But yl phosphate *(III)
Values
out of 5
F
q Cl,’~~HCl,
Sat’d. 61
with S02.
99
97
TABLE
IV- 22.
Extraction
Ethyl
into Miscellaneous
Composition of aqueous phase before equilibration
Solvent Carbon
of Plutonium
tetra
chloride
acetate
(III)
Organic
393
% Pu extracted by equal volume of solvent (l-v) (VI)
Nearly
saturated
NH4N03
1
1
Nearly
saturated
LiN03
5
25
Chloroform
Nearly
saturated
LiN03
1
Ethylene
Nearly
saturated
KN03
1
dichloride
Solvents.
1.6
Nearly
saturated
LiN03
1.6
Nitromethane
Nearly
saturated
LiN03
7.9 13
71
l- Nitropropane
Nearly
saturated
LiN03
20 30
81 69
Ethyl
bromide
2.1
2- Nitropropane
Nearly
saturated
LiIiT03
39.6
72
Nitroethane
Nearly
saturated
LiN03
72
83
Diethyl
cello solve
207’0 U02(N03)2 6H20, 10~ NHN03 0.5 ~HN03
84
Di-butyl
cellosolve
2 ~
Di-butyl
carbitol
20~o U02(N03)2. 10 ~
2- ethyl-but cellosolve
yl
HN03,
5 ~
NH4N03,
20% U02(N03)2” 10 ~
NH4N03,
Ca(N03)2 6H20, 1~
8
48
0.03
46
48
52
3
88
HN03
6H20, 1y
11 0.05
HN03
Diethyl
cello solve
20% U02(N03)2. 10 — M NH4N03,
6H20, 1 ~ Hh’03
0.3
Dibutyl
cellosolve
20% U02(N03)2” 10 M NH4N03,
6H20, 1 ~ HN03
0.003
20~~U02(N03)2’ 10 ~ NH4N03,
6H30, 1 ~ HN03
0.1
60
Nitromethane
20y0 U02(N03)2” 10 ~ NH4N03,
6H20, 1 y HN03
5.2
67
Methyl-isobutyl carbinol
20% U02(N03)2” 10 y NH4N03,
6H3Q, 1 ~ HN03
0.05
26
20% U02(N03)2. 10 ~ NH4N03>
6H30, 1 ~ HN03
0.03
1
Methyl isobutyl carbinol acetate
20% UO (N03)2 10 ~ NE?4N03,
6H O, 1 &N03
0.1
Xylene
3 g HN03, 5 ~ A1(N03)3. Dissolved BiP04
Nitrobenzene
3 M HN03, 5 ~ A1(N03)3. Dl~solved BiP04
Nitroethane
3 M HN03, 5 ~ A1(N03)3. Di~solved BiP04
47.5
3#
99.8
Ethyl
butyl
2-ethyl
Dibutyl
cello solve
hexoic
acid
carbitol
HN03,
Dissolved Ethylene Anisole
dichloride
2y 10 ~
47
0.001 5
5 ~ A1(N03)3.
5.3
BiP04
HN03,
10 &l NH4N03
NH4N03
1
1 0.003
62
~uca245,246 His results,
shown
decreased
IV- 23,
alpha
and (3) increasing
oxygen
carbon
traction
of Pu(IY)
among
a number
at this
acidity.
traction
of the side chain
side
chain
for
the symmetry
Khalkin
ketones
chain
the seven
carbon
of the
is lengthened,
~.224
in the order
while
for
U(VI)
and Th extract
Pu(VI)
the order
dibutyl
was
DBC
at a lower
carbitol
> hexone
HN03
Ketone
-—
hexone,
1.6
yl
0.12
0.12
of Pu from
point.
along for
quoted
sufficient
is used
ether
or
presumably
process
used
with
are
applications worth
mention-
as one of the ex-
TBP
purification
of HN03
power
reactor
over
hexone
to attack to permit
agent,
as the second
in a two- solvent
of Pu and recovery
advantages resistance
as a salting
450,188
facility. are
by high
(1) con-
use of the
and (2) ‘superior
extractant
because
it gives
decontamination
Vdovenko chloride
of the Pu from Ru. 411 and Kovalskaya used a mixture
diethyl
(e. g.
~, f3! - dibutoxydiethylether
tractants,
The
TBP
U.
of other
) has been
acid
in a Redo-type
process
Dibutoxytetraethylene
with
glycol
satisfactory
(’ ‘pentaether”
of dibutyl
ether
and hexavalent
basicity
analogous
because
to the neutral for
actinides.
of the presence
) has been used 28 mixture.
Typical
resdts
He found that U(VI)
quadrivalent
a number
extracted
species
(Pu,
carbonyl
complex Th,
etc.,
and amides
similarly involves ) are
amides
in extraction
are
two amide
shown
molecules.
with more
180
as extractants
compounds
and therefore
to the phosphorous
extracted
63
tetra-
as an extractant,
in these
nitrogen,
compounds
of elements behaved
oxygen
of the arnido
organo-phosphorous
IV-24.
in that the
The
and carbon
results.
with a 507’0 pentaether - 5 O~o dibut yl ether Sidda11377, 378 has pioneered the use of N, N disubstituted
tetra-
TBP)
the ex-
> hexone,
ethers
are
of extractants
(“Butex”
centrations
factors
results
of U at the Windscale
0.23
Ethyl- n-butyl
class
process
0.62
n-amyl
Di-n-propyl
hanced
for
to Pu also.
ing at this
0.22
for
in branched
(DEE)
cyclic
than with
and these
of this
Methyl-n-hexyl
along
These
of the
and Bona 54 found that
several
A number
2.2
yl
Methyl-t-butyl
separation
effects
ether
Branica with
tetrahydropyran)
10
-n-p ropyl
superior
series.
basicity
coefficient
> diethyl
> DEE.
concentration
applicable
Methyl-
is
series,
and tert-)
atom
decreased
and by steric
(DBC)
Distribution coefficient
Methylisobut
n-alkyl
see-,
found that the distribution
TABLE IV-23. Distribution Coefficients for Pu(IV) Extracted by Various Ketones from 3.2 ~ HN03.245
Methyl-n-but
the methyl(n-,
for
Pu(IV).
of Pu(lT.T ) into hexone
for
the methyl-
by the effect
for
from 5.0 — M HN03 was 11.5 by diethyl ether, and this was the highest of oxygen containing compounds, Pu(IV) was extracted as H2Pu(N03)6 236 Kooi found that for extraction of Pu(IV) from 8 &f HN03 the ex-
decreased
Methyl
as extractants
show that the distribution
explained
as the alkyl
atoms.
of aliphatic
of the side
can be qualitatively
carbonyl
a series
the length
the branching
series,
results
in Table
by (1) increasing
(2) increasing butyl
. investigated
has enshould
properties.
in Fig.
34 and Table
compounds However,
than two amides
(e. g. the per
be
TABLE
IV- 24.
Extraction
of Actinides
and Zirconium
at 3 and 6 ~ ~— Amideb
P (1:)
u (w)
HN03
9.9
N, N-Dibutylpropionamide
4.5
3.5
N, N-Dibutylisobuty
2.4
0.080
0.60
0.0009
N, N-Dibutylbutyramide
5.3
4.0
.63
N, N-Di-isobutylbutyramide
5.1
3.5
0.48
N, N-Di-isobutylisobutyramide
2,0
0.057
14
phase ~
N (1%
HN03
21
9.4
N, N- Dicycloheqlformamide N, N-Dicyclohexylacetamide
NP(IV)
0.23
0.024
.051
~
6.0 ~
~(VI)
Pu(IV)
0.119
3.6
,138
6.4
Amides
HN03 (1$~
4.0 38
.112
4.5
7.2
1.2
.103
3.3
0.21
0.33
.057
1.4
0.0046
0.070
in the aqueous Th
phase= Zr
HN03
0.10
0.54
0.090
,74
.21
.102
.11
.044
.094
.0040
.0026
.083
.0001 <.001
.060 .095
1.0
3,4
.114
4.7
8.7
2.2
.095
.039
0.62
3.0
.108
4.8
7.1
1.6
.028
.046
.088
.100
3.1
0.11
0.037
.0010
0.0012
.085
.150
4.8
11
.21
1.1
.100
.142
6.3
16
.68
0,026
.091
0.0070
9.9 2.2
11
N, N-Disubstituted
379), a
2.4
4.1
N, N- Dibut ylacetamide
ramide
by Various (Ref.
in the aqueous
1+ (~~
N, N-Dihexylformamide
N, N-Dibutylpivalamide
m *
3.0 ~
HN03
N, N-Dicyclohexylbutyramide
7.9
1.7
.148
5.1
5.9
.16
.010
.103
N, N- Dibut yl - 2- ethylhexanamide
4.0
0.19
.125
4.1
0.29
.0043
.0022
.084
N, N-Dimethyldecanamide
4.9
.115
4.4
39
.63
.096
.091 .096
10
N, N-Diethyldecanamide
5.1
6.9
.120
5.0
16
.34
.049
1- Hexanoylpiperidine
7.2
8.7
.115
5.6
20
.32
.077
.096
2,8
0.60
.087
4,2
1.5
.025
.011
.080
1-(2 -Ethylhexanoyl)
- piperidine
N, N-Di-sec-butylhexanamide N, N- Dibutylcyclohexane
carboxamide
5.5
.90
.120
4.0
3.9
.092
.0092
.094
3.1
.19
.103
4.1
1.0
.0040
.0034
.090
,23
.086
2.4
1.,3
.0033
.0099
.085
1.2
0.69
.0099
.0070
.088
4.3
1.0
N-But yl- N-phenylbutyramide
1.4
N, N-Dibutylbenzamide
0.86
N, N-Dibenzylacetamide
3.3
aExtraction coefficient . “All 0.50 M in toluene.
is defined
as moles/liter
.105
.34 0.22
0.077
in the organic
phase
divided
by moles/liter
in aqueous
0.014
phase.
0.021
0.077
metal
atom
efficient
at high nitrate
distribution carbon
coefficient
atom
dihexyloctanamide slightly
inferior
(1) as selective for
U(VI)
and decreases
of quadrivalent
is increased. was for
Zr
concentrations.
at about 7 — M HN03
while
to TBP
extractants
for
is only
branced
N,
Zr-Nb,
of these
alpha
carbon
N-
but
compounds
or (2) as selective
actinides,
with highly
in the
of the alpha
moderately.
of Pu from uses
co-
decrease
as the branching
The potential
quadrivalent
of amides
distribution
A large
decreased
in decontamination
Ru decontamination.
in the case
a maximum
acidities.
Pu and Th occurs
that of U(VI)
superior
exhibits
at higher
atoms
are
extractants (e. g.
N,
N-
dihexyltrialkylacetamide). Chelating
Agents
A large complexes
with
in non-polar aqueous
organic
phase,
number
metal
of hi-functional
ions have solvents
and are
been
reagents
such as benzene
therefore
which
investigated.
or carbon
extractable.
strong
complexes
compounds
salt
soluble
acetone
(TTA
) and
of N-nitrosophenylhydroxyl-
( “Cupferron”
in radiochemical
more
than in the the fluorinated
2 -thenoyltrifluoro
the ammonium
coordination
are
tetrachloride
Of these
13-diketone,
‘amine
form
These
) have
been
and analytical
Thenoyltrifluoro This
used most
widely
applications. acetone
compound
(TTA)
has the structural
formula
_~_cH u and exists aqueous
primarily
forms
ions,
The
in both
solutions,
strong
complexes
particularly
general
written
3
in the enol form
and organic
TTA metal
_~_cF 2
s
reaction
those for
with many
of high valence.
the extraction
can be
as M
+m + m ‘T(o)
and the equilibrium
= ‘Tin(o)
(1)
+ ‘H+
constant
(MT)(0)
(H+)m
K=
(2) (M+m)
where
HN03
CONCENTRATION EQUILIBRIUM (~)
AT
Fig. 34. Extraction of actinides and Zr by 1.09 ~ N, N-dibutyloctanamide in n-dodecane at 30°.378
(H%o)
the quantities
in parentheses
are
activ-
ities. Thus,
if activity
coefficients,
and no aqueous
completing
tion
should
65
coefficient
occurs,
show a direct
are
neglected,
the distribu~th
power
dependence aqueous
on the TTA This
acidity.
The most Foreman’”
concentration
and an inverse~th
expectation
comprehensive
is borne
summary
out for
of TTA
who found that the extraction
power
many
dependence
elements,
on the
including
data is that of Poskanzer
data for
most
elements
could
Pu.
and be fitted
by the
equation [H
K=D
(HT)m in which (HT)
K is a copstant,
activity
dependence coefficient
Equation
[ H+]
These
is extracted of these
of the TTA.
authors
elements
(see
Fig.
while
other
reader
is referred
No
35).
~~
Fig.
phase con-
phase
of TTA (4)
coefficients
of the TTA
phases
into
and the metal
are
paper more
EiEa
pH. OF 50 % EXTRACTIC+J “ PH,O
-
Extraction
all available
at which
chelate
the pH50 value
for
of acids more
They
WITH EQUAL
VOLUME
= - LOG HCI CONCENTRATION
of the elements 66
with
displayed
in extractability
is negative
and acid-salt
detail.
extractable
experimental
50~. of the ion
0.2 — M TTA in benzene. to show the trends
a variety
much
(3) for
pH
table
in which
be for
of Eq.
pH5 o, the
Am COEFFICIENT OF PH OEPENOENCE OF LOG @ D . OX IOATION STATE WHSN NOT IN OICATEO
35.
TTA
228
of a periodic In cases
ions
~=GATIVE
ion in the aqueous
x is the observed
1, and f is the organic
solutions
the parameters
to the original
.
PH..
Mg
volume
data may
that the quadrivalent
JU
benzene
and calculated
the form
given,
~~
m is that of Eq.
For
determined
by equal
phase,
phase.
extractions
data in
of the hydrogen
in the organic
that the activity
in the organic
data on TTA
is the activity
of the TTA of the reaction,
(3) assumes
equal
1
= 1 - 0.24 (HT)0”48
‘HT
are
(3) fH~-
is the concentration
centration
+x
However,
only HC1 data are combinations. this
figure
than others.
DTTI17 FrlrllTl
0.2 ~
TTA
some of the
in benzene.324
The shows
The
extraction
Cunninghsme though
other
aqueous
of Pu(IV
chlorinated
phase
nitrate
) from
nitric
acid
solutions
was
using CC14 and benzene
110’ 111
and Miles
hydrocarbons completing
were
used
of the Pu,
investigated
as solvents
also.
They
by
primarily,
find that,
the equilibrium
al -
by neglecting
can be expressed
by the
equation 4 ‘HN03
They
derive
efficient, tracer
the f‘ s from
of Pu(IV
that the rate
centration
solutions
(1) represents the Pu(III)
used.
by Heisig
co-
benzene,
aqueous
determined
boundary
controls
find that at low nitric
is PuT4,
while
at 4.9 — M total
acid
nitrate
con-
from Other
with
concentrations.
results
0.2 ~
are
shown
Pu from
chemisorption
with
to time
a direct
Since
zero
were
coefficients
that Eq.
coefficients
— 0.01 ~
on hydrogen
however.
of a batch in Fig.
process Their
37.
2.3 power ion.
made, for
for
sulfuric
acid as
dependency
These
the distribution
solutions co-
and the extrap-
Pu(IIT)
scrub
with
Pu recovery
and U of 3000 and 667,
dilute
properties for
and Pu(VI)
the Zr oxidize
HN03,
on a l-gram
of a number
separating
procedure,
is to pre-extract
with hydroxylamine,
a 99.4%
Pu from
ir-
should
be
which from
to Pu(lY)
0.5 ~
with
HN03
with NaN02,
and back-extract scale
of
the Pu into
decontamination
respectively.
on the use of TTA for processing irradiated uranium for Pu are 105 An interesting variation is the use of U(IV) and Culler.lOg
_et al. TTA 342
solutions The
by reduction
application
cedures for Pu has been reported 287,50,356 for rapid analysis step combination
of TTA,
scale,
to Pu(III)
report
reports
and displacement.
obtained
dependency
concentra-
indicating
perchlorate
of the distribution
TTA-benzene,
They
of Crandall
on the TTA
the distribution
They
2.6 power
extrapolations
Plots
to the laboratory
Zr
measured
0.005 — Mferrous
in the development
Their
the Pu is reduced
HN03.
authors
second-power ion concentration,
are shown in Fig. 36. 111 and Miles determined the extraction
impurities
with
direct
from
and Hicks
U.
adaptable
are
in the presence with time,
were
radiated
to strip
They
rates.
species
These
and an inverse
stabilized
possible
those
of the distribution
in sec-butyl
the organic
on the hydrogen
acid and TTA
increased
factors
by TTA,
across
extraction
by reduction
Cunningham
8 ~
back
the extracted
the reaction.
of nitric
values
extract
solutions
the dependencies
concentration never
while
acid
of Pu chelate
second-power
obtained
a function
easily
dependence
partially nitrated complex such as PuN03T3 exists. 174 found that for Pu(VI) extractions into TTA-benzene and Hicks
acid
obtained
nitric
(O. 5 ~)
tion and inverse
efficient
concentration
some
Heisig
olated
f~T
the TTA
and reductive
concentrations
were
) from
of transfer
the forward
on TTA
(HT)4
and find that C is close to 1 X 10+5 over the range from 1 to 10 ~ HN03 for 173 m a very extensive study of the kinetics of the exPu. Heisig and Hicks,
traction
nitric
‘PuT4 (5)
c = DPU(IV)
many (see
times, for
co-precipitation
on a CaF2
to Pu(III)
of TTA
either
example,
steps involving 352 suspension, or other 67
or a combination
to analytical
of reduction
and radiochemical
as the only Procedure
pro-
purification
2, Section VIII) or in 341, 237 136’351’50’284 BiP04, 332,315,168,261 separation steps.
LaF3,
1000
100
10
f)l
o.I
1.0
0.01 D
0.001
0,0001 01234567S9
101112 HN03
MOLARl~
Fig, 37. Distribution coefficients of various ions from nitric acid solutions into 0.2 — M TTA in benzene .ll O. Ill 0.1
—--L~,20 HNOO; CO&NT R’ATION
Fig. 36. Extraction Pu(VI) into TTA-benzene of HN03 concentration nitrate concentration. Pu(VI) TTA cone. (~) 0.74 Total nitrate (M) 0.175 Aqueous condi~ons 2 X 10-4 ~ KMnOy
TTA
(~)
small
of Pu(IIT) and as a function at constant total LiN03 added. 174
vice
has been
amotmt versa,415to
vironmental
and Pu(VI)
are
extracted
are
together
Pu(III)
environmental
1,65 0.096 0.005 M Fem104)2
water.’
then calculated TTA
36
used to separate
In this
procedure
hydroxylamine
and impurity
aqueous
is then oxidized
cedure
phase
both extractable TTA
logical
has been
material,
Procedure
21,
LaF3.
On a second The
relative
state
In the latter
procedure,
0.5 ~
raffinate
sample,
from
the Pu(IV)
amounts
sea Pu(IV)
HC1 and the
adjusted
acetate
en-
of Pu in
including
from
a 194 or
Pu from 352 and to
samples,
is extracted acqueous
Pu,
to pH 4.3 with
which
the Pu(III)
and Pu(III)
of the three
valence
are states
by difference.
has been
411
analysis.
together. with
samples
the oxidation
ammonium
coprecipitated
macro
concentrate
w-ater
determine
used to separate
of b“ from
used for
impurities
an HC1 solution elements
extracted
to Pu(IV)
for
of the metal with
and extracted
and non-extractable
especially Section
Pu from
impurities
TTA
a spectrographic is reduced
in hexone.
into TTA-hexone.
VIII).
68
with
Pu in the By this pro-
can be determined.
several procedures for the determination 125,349, 360,257,56, 316 (see, for
urine
to Pu(III) The
of Pu in bioexample,
Cup ferron If-nitrosophenylhydroxylamine cipitating
agent
for
many
metal
in non-polar
solvents
tion reaction
is analogous
Pu.
et al. 138 have
Furman
out oxidation
for
from
to Eq.
phase
Pu(III)from
is shown
these
in Fig,
Kirk CHC13
Fe,
for
extraction
of reduced
the extraction,
recognized little
the subject four
solutions
to be third
229 U(VI),
Pu(VI),
report
that most
U(IV),
PU is lowered
but a small and Penneman
light
v
a
He ruled molecule
The pH dependence
in accordance
with
of h ydroxylamine
above
Eq.
1.
and Pu(lV
speciesPu(III)
for
pH 0.8 in H2S04.
ammonium
)
They
rePort
and Pu(IV).
Phosphate
of Pu and Am,
sulfate
low
The
interferes
from
based
with
on extraction
1 ~ HC1 solutions.
that the extraction
rate
cooling
temperature
from
room
that oxidation
from
port
a separation
Pu(III)INPRESENCE OF HYOROXYLAMINI
recovery
Pu(lv)
cedure ~,417
of both Am has been
Kooi
by
to 5°C suggests
to Pu(IV ) is taking
of cupferron.
factor
of
The fact
of Pu is slowed
Pu(IIf)
in the presence
u
by cupferron-
is beneficial.
Pu (Ill)
60 -
not extracted
extraction
concentration of iron 304 report a separation
of ferrous
are
as extractable
place
F
power,
elements
complete
100 -
z o
cupferron
sphere.
the presence
and Pu(fV)
but essentially
the Pu in the presence
00 -
and U(VI).
in extractions
(U = 1.0 pH = 4.5 - 5). an “extra”
coordination
and without
extrac-
done on
U(IV)
Pu atom
-
complexes
The
has been
data for
per
as apre
date.
work
given
molecules
and postulated
was found
with
quantitative
cupferron
the eightfold
used
of these
at an early
and have
chloride
has been
and the volubility
38.
extraction
Nigon
solutions
years,
was
by the reagent
of Pu(III)
and Rodden
and listed
required
to complete
The pH dependence
or cupferron
many
1, although
reviewed
HC1-ammonium
of the Pu(III)
in the organic
for
such as chloroform
Kemp 220 found that Pu(III) into chloroform
ions
They
of 105 with
and Pu.
A similar
used to separate
and Hallatein237
re -
quantitative pro-
Pu from
has used cup ferron
1-
x w 8
tractions
(2)
water
40 -
to concentrate
samples.
corporated general
a cup ferron
cedures
determination
t
oo~
Finally, in procedures PH
Fig. 38. Extraction of Pu(IH) ad PU(~-) from 1,0 M chloride into” cup2~ Cmve 1: Pu(III) f erron-CHCl = 2.16 X 10- 2“ ~, cupferron = 3,98 X 10-2 ~; Curve 2: Pu(III) . 3.65 X 10-3 M; cupferron = 3.68 X 10-2 M, 10 w/v~hydroxylamine hydrochlor~de. The curves are ~0 extraction for equal phase volumes vs equilibria PH.
from
biological Chmutova
for
determination
in-
step in a for
Pu.
used in several
pro-
Pu before
of impurity
spectrographic 296,45 elements.
cupferron,
has been widely
used
to separate
and concentrate Pu 102, 387,.248, 272 materials. 87 developed a procedure et al. of Pu by extraction
HN03 by a chloroform . phenylhydroxylamine
69
procedure
has been
to separate
environmental
and Lukens37 extraction
radiochemical Cup ferron
20
Pu from
Beaufait
solution (BPHA
),
from
3~
of N-benzoylan analog
of
ex-
cupferron,
followed
by back
extraction
found that U, Am,
NP(V),
these
The Nb and Zr
conditions. Other
Chelating Many
Project
for
and various
possible other
separated
organic
chelating for
such compounds”
as well are
Code mme
are
into
(except
sulfuric
acid.
Nb and Zr)
in the
back
It was
do not extract
extraction
agents
Pu,
other
in Table
were
including Stewart
diketones.
as many
shown
completing
Substituted group Rl(a)
investigated
acetylaceto,ne, 3’3
in the Manhattan trifluOr
has compiled
agents.
OaCetylacetOne,
extraction
Extraction
data for
of Plutonium 393
Pu(rv) distribution ratio benzene 0.5 — N HhT03
—
Relative concentration needed to give same extraction of Pu(IV)
CH3
1.0
1
PTA
CH3CH2
9.0
1/3
ITA
(CH3)2CHCH2
BTA
c 6H5
TTA
HC - CH
-1oo
1/5
-1oo
1/7 1/15
42
II ,C -
s pFC 6H4
PB TA
03
NTA
CH - CH
F TA
-1oo
1/7
-1oo
1/7
-100
1/7
-100
1
II
II HC,
,C 0
‘a) The
general
formula
for
these
several
into Benzene
TFA
FBTA
data for
IV-25.
Comparison of the Extractability Various Fluorimted Diketones.
II HC,
under
step.
Compounds
fluoridated
TABLE IV- 25. Phases Containing
products
extractants
chelating
agents
of the Pu(IV)
and fission
compounds
70
is R1-C(0)CH2C(0)CF3.
Pu(VI) precipitate with
and Pu(lV)
complexes
at pH 2-3 have
TTA
complex.
solutions
been
with
pyridine-N-oxide -2-carboxylic acid which 176 These compounds are iso-structural
prepared.
A possible
application
is the separation
of U(VI)
and Pu(VI)
from
of salts.
Mixed
Extractants Synergism
traction taken
of metals
synergism extractants,
separately.
This
Pu has received while
The term by mixed
its
not many
be expected
gard,
of phenomena
be found.
types
described
not completely
Influence
of Diluent
TLA,
exerted
and (2) mutual rise
increases
a factor
extractions. hexone, polar
of three
TTA,
complex,
disruption
fraction
Shevchenko
~
of H-type
of the association
tion of the induced
decrease
from
dipoles @@.36gâ&#x20AC;&#x2122;
with
pure
diluent
of the dipoles
37â&#x20AC;&#x2122;
re-
of the
DBC,
TTA,
non-polar
and proposed
(L):
a theory
and the diluent
in the diluent
can be large; benzene
complex
mixt~e
e. g.,
DPu(m)
in TBP
(Pu(IV)
and Pu(VI)
In the case
of the
by a polar The
a maximum. diluent,
diluent;
however,
extraction This
with
highly the
as a function
is explained
followed
by
by participa-
in the extraction.
found that the extractability polarizability
and
in this
of tetra-
TBP,
molecule
diluent.
in the P-type
diluent
The
He found that the nature
dipoles
is favored
as well
etc. complex,
chloroform,
the extraction.
thus exhibits
in the H-type
increasing
(P):
effects
of a non-polar
increases
diluent,
on the effect
hexone,
CHC13 to pure
by a non-polar
the extraction
diluent
studies
of the organic
The
of changed
is excellent
benzene.
permanent
phase.
the extraction
of a polarizable
of the mole
Ce(III)
in going
polar (H):
inert
on the extractability
on the extractability,
between
all cases
discussion.
including
are
the dipole
etc. ) is favored
Pu(IV)-TBAN
presence
used
influence between
in the organic
In general,
TBP.
extractants,
but polarizable
interaction
to structure
extensive
and it is to
TBP-DBP,
of Marcus267
diluents
research,
is thus diverse,
complete
years.
phenomenon,
are
ex-
extractant
in recent
of the supposedly
review
inert
of diluents
a large
section
synergism
conducted
various
non-polar
on (1) the interaction
dipoles, giving
Examples
tetrachloride,
of the diluent
with
in this
a more
of supposedly
actinides
and TBAN.
carbon
based
397, 398
and polarizability
and hexavalent
The
to it for
this
such as TBP-TTA,
the term
understood.
is referred
for
in the nature
depressed)
of the general
appeared
Considered
under
Tatie396,
have
(or
by each
attention
than its share)
of extractants
and the reader
polarity
more
enhanced
the extraction
considerable
applications
due to changes
of different
in general
(perhaps
will
properties
as mixtures range
share
as against
has received
radiochemical
that more
extraction
subject
is used to denote
of the diluent
of U(VI),
Pu(IV),
Zr(IV),
by TBP
solutions
from
and 3
HN03. Far
mixed.
greater The
effects
are
enhancement
(or
observed depression)
when two
different
of the distribution
71
classes
of extractants
coefficients
are
may be 104 or
more.
Siekierski
mixtures (C+).
based
on classification
Anionic
etiractantfi
act as organic TOPO,
.
anions
etc. ) are
and cationic cations
are
neutral
authors
have
similarly
that form
complexes
compounds
In general
class,
and may
define
for
neutral
(B”),
DBP,
extractants
through
a basic
(’I?OA,
TBAN,
be small
effect
or large
coefficient
synergistic or cationic
HDEHP,
neutral
the synergistic
a synergistic
a system
(A-),
such as TTA,
complex;
basic
proposed
as anionic
compounds
strongly
complex.
of the same
These
acidic
compounds are
in the extracted
classes.
and Taube400 of extractors
in the extracted
extractants
of compounds
381
and Taube,
etc.
that
(TBPJ
oxygen
atom,
etc. ) that act as is small
in mixtures
in mixtures
of different
as
‘1 2, ex s = 10g D1’ z adj ,, ‘1,
(1)
is the experimental
2, exp
distribution
is the calculated
and ‘1, 2, add distribution coefficients. tween
the extractants
the two
of different for
types
Additivity occurs,
extractants
are
has made
Taube400
Synergism phosphate
mixed.
and He aly
The
survey
studied
Healy
of y ranged
a y value
found
obtained
at high
Irving depending species
were
M is an actinide.
These
authors
placement
mixtures
classification
system.
systems.
M is an actinide and P is a neutral 196-200 in nitric acid
of participation
(P)y(o)
di-,
tri-,
in the case
of chloride
in the ex-
(2)
+ X H+. and hexavalent
of TOPO
1 or 2 nitrates
concentration.
M(IV)
With
T3(N03)P1, were
Thus
postulate
of a water
found that
they
where
ions.
a value
Th(IV)
had
of 3 was also
M(IH)
the complex
that the reaction
molecule
M(m) T3P2,
could
by P,
P2,
for
otide
and M(~I)
T3(N03)P1,
is influenced mechanism
into the complex,
phosphine
T2(N03)2 M(W)
in the complex
enter
tributyl
hexavalent
T2P1,
strength species
a coordinately
the
T2 (N03)P2,
and M(VI)
by the basic
giving
(TBPO)
of P. is the re-
unsaturated
thus M02T2
In the case with
of synergistic
on this
ion with
extractants
and Edgington,
‘ M (T)x various
except
acid
P = TBP
where
product,
metal when
be-
P concentrations.
on t$e nitric
with
not true
extraction
where
that (1) no interaction
of the extracted
commonly
1 and 2,
of the individual
is thus
1 to 3 for
and Edgington
identified
whereas
from
of mixed
of extractants
on additivity
of examples
no evidence
reaction
of 1 as did U02+,
table
by Irving
‘x +xHT(0) +J’ p(o) Values
complex are
IV- 26, based
M- TTA-P,
has been
based
on the assumption
assumptions
in Table
in the system
extraction
is based
A summary
is given
an extensive
compound 169 inHCl
traction.
Both
of a mixture
coefficient
and (2) no mixed
occurs.
U and Pu extraction
coefficient
distribution
nitrates
of tetravalent added MT4
H20
+ P = M02T2P(0)
one or more
species,
to preserve + mHN03
electrical + mP
chelates
neutrality,
= MT4-m(N03)mPm ’72
(3)
+ H20. are
displaced
by P molecules,
thus + mHT.
(4)
TABLE IV-26. Syner istic U and Pu Extractions. 38 f Synergism or antagonism occurs
System
and Antagonistic
Effects
in Two
Examples for plutonium uranium extraction
Extractant
and
Systems
in
References and remarks
Ai + A; anionic + anionic
S>o S<<o
U(VI),
HG2P0
A-+ B“ anionic + non- ionic
S>>o
U(VI), U(VI), Pu(VI), Pu(VI), Pu(VI),
H S04, D2EHP0 + TBPO HkO , TTA + TBP Hh ,8 3, HDEHP + TBPO H2S04, DNNSA + TBP HN03, TTA + TBP
Blake, 195959 Irving, 1960196 Blake, 195959 Oak Ridge, 1960443 Irving, 1961198 Taube, 1961400
S<<o
U(VI), Pu(VI),
H2S04 DDPA + TBP Pu(IV), H2S04, DBP
Blake, Taube,
‘U(VI),
H2S04,
DBP
U(VI), Pu(VI)
HDEHP H2S04,
+ tertiary amines DBP + TOA
A-+ C+ anionic + cationic
S>>o
BIO + B20 non-ionic non-ionic B“ + C+ non-ionic cationic Cl*
S<o
Pu(IV),
S>o
U(VI),
+ H2GP0
H2S04, TBP,
DBP
Blake,
+ TBP
+ TOA
S<o
s-o
Pu(VI), Pu(VI),
I%@ Y),
+
Taube,
+ TBAN
s-o
PU(IV)J
HN03,
1961400
Siddal 1960376 no data
HN03, HhT03,
PU(~)J
195959 1961400
Deptula Mine 196111~ Blake, 195928 Taube, 1961400
TiBP ?
+
195959
TBP TBP
+ 770A + TBAN
Taube, Taube,
1961400 1961400
Taube,
1961400
+ C2+
cationic cationic
+
+ TBAN
G* general alkyl group D 2 EHPO di-2-ethylhexyl phosphine oxide tri-n-butyl phosphine oxide TBPO DNNSA dinonylnaphthalene sulfonic acid tetrabutyl ammonium nitrate TBAN triisobutyl phosphate TiBP
SYMBOLS
The trivalent P molecules
species
The
are
‘
synergistic
to become
of two water
8-coordinated
molecules.
The
effects
discussed
so far
is increased
are
for
relatively
to about
1~
and above,
or antagonism
systems
as quoted
judicious
addition
the aqueous
by either addition
addition
reaction
of two
is
2P = ‘T3P2”
If the P concentration
synergism
considered
or replacement
‘T3
of P.
TOA
sets in. The P dependencies for 169 by Healy are shown in Table IV-27.
of one of these
compounds
phase.
73
to effect
several Thus
the selective
small
concentrations
a strong
negative-
M/ TTA/P/HCl it is possible return
by
of ions
to
TABLE IV- 27. Slope of the Dependence of the Distribution Coefficient Concentration of the Added Reagent for Mixtures of Phosphorous Esters, Alcohols and Ketones with TTA. 41 Valence
Ion Th Am,
Pm
Uo.
Fused
salts
because
give
a general
U(VI)
+2
-4
+1
-2
of their
(where eutectic
tribution
of otidation
the distribution similarly,
although
Borkowska
U,
system
pair
a maximum
however
of the LiCl
phase
PUC14, actinides
TBP
obtained separation
effect
of TBPJ
chloride
at
The
dis-
as in acqueous distribution
was to lower
to behave
180°
and HDBP
of
of 102 or
the higher
be expected
mixture
TOA,
a factor
dependency
of added
would
‘<
to study the ex-
in diphenyl.
For
similar
of TOA
behavior.
is similar
-50” ‘or ‘(IV)’ the distribution of a number It is perhaps
noted
distributions for
Since
UC14 (for
curve
of ions between
not proper
which
to speak
the SnC12 used to stabilize
case
for
the U(IY)
of
this
system
basis)
U from
Pu and Th is approximately
100,
as
in favor
as a reluctant), tri-
also
and tetravalent reduced
Pu to
separation is possible in this system. Similar results 290 and Lyon for the system KC1-A1C13-A1. In this case the
for
while
that for
were
Th from
Pa is up to 800. Cafasso including Pd:600,
et al.
U and Pu. U:21.5,
73
determined
between
Pu:7.3,
the partition
liquid
Ce:3.4,
lead
and zinc
Sr:O.05, 74
coefficient at 703”C.
is
the immiscible
fraction
SnC12 was added coefficients
at ’40% in this
to TBP.
(Kd > 1 on a mole
of the distribution
occ~s
The maximum
an easy
by -Moore
TOA
‘U(IV)”
HDBP
The ratio
was > 40.
factor
shows
at 650°C.
were
state
The
and
in a mixture
solutions.
is the same,
actinides
< ‘U(III)
significant
and FeC13.
the trivalent
concentration
in the D vs concentration
-3.
LiC1-AlC14-K+
were
nitrate
the
is in the order
at 67% ‘Bp’ ‘here %(IV) measured Moore28’ salt
TBP
effect.
by solutions
< ‘Am(III)
Du(ml
extraction;
aqueous
from between
and NP(VI),
of TBP
coefficients
mechanism
Quadrivalent
and Am
DPu(rrr)
where
the same
salting-in
find the extractability
TOA,
Np(V)
solutions
none was determined. 51 used a KC1- CUC1 eutectic
~.
of Pu,
or lanthanide),
concentrated
that the extraction
coefficients.
coefficients
the distribution
all showed
indicating
in LiN03-KN03
efficiently
the distribution
and dilute
of fused 154 et al.
Gruen
of actinides
of elements
of
mixtures
reactors.
and spectra
actinide 120”C)
than the corresponding
due to the increased
In this
(MP
In general,
coefficients
traction
region
properties
eutectic
power
a number
determined
M is a trivalent mixture
states
extracts
@.20’
extraction
low-temperature
use in homogeneous
that TBP
at 150”C.
solutions,
done on the solvent
in relatively
potential
Isaac
M{III)
103 higher
has been
discussion
mixture.
polyphenyls
they
DI VI
elements
in this
being
-2
and indicate
mixtures,
CO(H),
+1
research
and other
eutectic
Antis ynergism
region
Iv
Salt Systems Some
actinide
Synergism
on the Amides,
of a number The
results
of elements, (Zn/Pb)
are
D.3
Ion Exchange The
phenomenon
tion
of Pu.
Cationic
on cation Pu(VI)
resin
form
of ion exchange Pu in dilute,
in the hydrogen
anionic
and so will
thus both usable
or alkali
complexes
adsorb
on anion
Pu.
in the laboratory
because
and the excellent
decontamination
been
acid form.
The
anion
inorganic
adsorb
will
nitric
and cation
exchange
fission
cation
separa-
solution
On the other
Anion
equipment
from
in the radio chemical
concentrated
re SWS.
of the simple
synthetic
utfiity
required,
exchangers
hand Pu(IV)
and
or hydrochloric exchange
separation
products
readily
is especially
the ease
by the use
acids
methods
are
valuable
of manipulation,
of redox
such as zirconium
cycles.
phosphate
have
developed. A good
Chapter
introduction
7 of Seaborg
separations many
recent
The books
of commercially
available
subject
the ion exchange Cation
equation
Thus,
> Pu(III)
> PU(Vl),
the strong
base
Kraus in 1957,
review
of
and properties
and Nelso:~~’
while
reviewed
Hardy
of these
resin
for
reviewed
an exchanger
in the hydrogen
action
sulfonated for
The
exchange
reaction
is favored
can be used to displace metal
by completing. with
Amberlite
charge
IR - 1:
> CS(I)
concentration, neutral
Th(IV)
> Sr(II)
and are
or anionic
Pu may be desorbed
from
the
ions from” the exchanger
In general,
ticreasing
by a low
the metal
the absorbabilit
and decreasing
on cation exchangers for 358 Schubert found the following
is y of
hydrated
PU is Pu(IV) adsorption
afftiit
y
> Pu(IV) > La(III) Rare ++ . All Pu species are
> U02
desorbed complexes
at high with
by reaction
acid
concentrations.
Pu in all of its oxida-
with the anion
of the acid,
displacement. cross
-ltied
the separation
is Dowex-50.
470 or 12%,
(1)
way to remove +b
Ba~)
form
and therefore
materials
of M
example,
acid
anions
popular
means
site.
high acid
Another
Earths>
at low
The
reaction
of absorbabflity
cation
Rare
many
states,
For
as the mass
which
has a good
of the names
reviewed
references
+ bH+ .
increases
the order
> Y(III) well
exchange
bHR = M%
actiom
as well
Typical
+b +
on ion exchangers
absorbed
materials.
good
in 1958.
or conversely,
radius.
tion
actinides
the concentration
However,
a table
separations
R is an exchanger
by mass
to decrease
Earths
Samuelson
gives
has been are
is
concentration
cations
of ion exchange 348
and Samuelson
Helff erich
cation
general
solution)
exchanger
subject
of ion exchangers.
ion-exchange
in the acttiides is contained in 17 M valuable for ion exchange
of Hyde
Exchange
M
acid
of ion exchange review
general 175
of ion-exchange
data for
The
In this
The
The
done on actinides.
the general
(acid
1
of Helfferich
and applications
work
form
to the subject
and Katz.
of the actinides.
times.
to the theory
for
metal
in moderately
exchange
to separate
Recently
is of great
non-completing,
etc.
This
polystyrene of inorganic resti
resins species,
is usually
divinylberuene
was
75
have been including
specified
added
by far
as “X 4“ or “X
to the styrene
the most
the actinides.
in the
12, ” etc.,
polymerization linked
of the resin
resins
greater
volume
change
As solution, ever, elution
anions
behavior
changing
above,
ionic
under
form
linkage.
In general,
but also
kinetics,
Pu complexes
the low-cross-
have the disadvantage
of
milieu.
non-completing
of Pu is essentially
elution
behavior
the distribution
as a function
the cross
of faster
conditions,
independent
at moderate
i. e.,
of the aniona
concentrate ions,
dilute
acidic How-
present. which
makes
the
of Pu variable.
The where
with
mentioned
the absorption
many
to provide
have the advantage
of Pu on cation
coefficient
of the acid
for
Pu(IU),
resin
Pu(IV),
is summarized and Pu(VI)
in Fig.
on Dowex-
39,
50 is plotted
molarity.
Pu E
k I
103
\
[02
10
103
It //
t 102
/iclo4
HCI
$1
\
10</
‘\HN03
II HN03 c1
j
10
2
46
MO LA RITY Fig. tions.
39.
Typical
These
distribution
data are
coefficients
intended
In general, HC104
than for
acidities
HC1.
is shown for
The tion was
classic
of relative
distribution points
volumes
10 cm long
for
from
on cation
required
plot.
3.2 to 9.3 — M HC1 is undoubtedly
complex.
The
has the highest is in accord
to elute
tetravalent distribution
actinides coefficient
with the decreasing
of Pu.
adjusted
case
were
taken
steeper
for
HN03,
coefficient occurs
solu-
In
to corre
from
-
litera-
H2S04,
and
in HC104
in a great
of the actinide
principal tracer
in diameter.
at high
number
connected
decrease
in this
of
radii
to make
76
in Fig.
Pu,
from
Np,
positon
vs — in going
position
chloride
U, Th;
This Pu to Th.
to the
system.
elution
elution
of an anionic
sequence:
40 as
a Dowex-
proportional in this
a crude
of the Pu(IV)
in going
in HC1 solu-
shown
data are
obtainable
at any HC1 concentration.
hydrated
are
of the ions from
These
due to the formation elute
elements
results
amounts
the separations
“have been extreme
acidic
were
increase
exchange whose
and illustrate
The
50 in common
of the behavior
data in every
This
D
8
U(VI))
in the distribution
et al. 117
the Pu species
HC1 concentration
illustrative
are
6
Pu(IY).
by 1 or 1.5 mm
coefficients,
The
and Pu(VI).
work
24
D
of Pu on Dowex
of the curves
for
AI
(e. g. Am(llI),
increase
also
done by Diamond
50 column
The
Pu(III)
and probably
elements,’oo
a plot
the slopes A strong
OF
to be only
,, some cases, the data of other actinides ‘\ , pond to Pu in the same valance state. ) ture mentioned later in this section.
L 10
8
i. e.,
order Th(IV)
Th
of elution was
not
3.2hJ I I [
I NP(II)
Pyzn
HCI
I II
I
U@U.l Cs
Yk. SrY /
NPCLII
/
I
! II CEI
Pu~a
ThCUZ)~ NPCUZY—
I I
I
LnRa
Ac
PU(.IIZ)
Am
—
/ 0 0
/ /’
/
/
6.2&fiCl
,
/
// I
I
CaYb
Y
I
[ NP~
U(WO
Ill /
I
II
I
IM
Th
(IIZ)_
Pu (ILD
,. t’
I
I
/,
I ‘ ,#
I
i
9.3~
HCI I 1[
I Ill II Pm EU
I
T(W
‘“l~b
Pu m I
N;~Am
Srti
I
Th(IK)—
AC
La
~~
1,
I
I
i 1 N;$
I
1/ I
I
122~ II
1
11
II I
II
RoY
PuflV)W3Am C Yb Puod
C,
HCI I
Th (IX3—
EuEa CaLaSr Ac
P“dIl
I
1
1
I
I
I
1 1 1 II
I
1
I
I
I I I I I
I
1 1 1 1 1-l
1
1000
100
10
I
VOLUME
OF
ELUTRIANT
Fig. 40. Relative elution peak position of actinides and other ions in various concentrations. The positions of the Pu ions have been connected by lines. 117 eluted
at all under
the tetravalent the relative actinides
the conditions
actinides elution
under
position
and lanthanides
lanthanides
the elements
Dowex-
summary
the curves fo~ Th(IV), 117 of Diamond et al. Strelow
with those distribution for
Hg%.
just below
X 8 resin above.
He arranged in 1 ~
distribution
the cation
is in Fig. was
coefficient
separation
exchange
the cation
exchange
The
of Th(IV),
Zr.
77
ranged
of
vs HC1
data for
Pu are
to the data
of 43 elements
on
agreement
of the equilibrium
7250 for
actfide
of the
of most
in general
order from
the OfiY
of Dv
few
a norm~ization
results
in decreasing
values
positions
table
behavior
up to 4 — M with
of
41 to show
of the trivalent
behavior
relatively
Permit
position
in Fig.
in the elution
Although
and Am(m)
the elements HC1.
of the elution is shown
42 as a periodic
used.
at HC1 concentrations
coefficients The
by the increase
U(m),
investigated
3’5
conditions
well-known
summarized
50 X 4 resin
included,
Dowex-50
The
is illustrated
The
in HC1.
concentration
cliff erent
of Th(IV).
at high acidities. 300 Nelson et al.
A plot
of the experiment. slightly
HC1
Zr(IV)
studied,
to 0.3 was
2049J
1000L co ; n z â&#x20AC;&#x201C; z o ~ m o L
100 Fig. 41. tetrapositive molarity.11
u
Elution peak position ions vs hydrochloric 7
of the acid
NP :~
x z
10
Pu
n z o F 3 d 1â&#x20AC;&#x2122;
I
I
I
3
1
12
HCI 6MOLAiiTY
Fig. 42. Volume distribution coefficient of the elements Dowex 50 X 4 cation exchange resin. Tracer concentrations for the most part. 300 78
vs HCI concentration for of the elements were used
Prevot
~.325”.
determined 1171.51
coefficients with
of Pu(III)
other
ions
concentration
very
as a function (Fig.
C. 50 resin Pu(HI)
43).
(similar
strongly
are
below
distribution
out.
A partial
I I
used
expected
~ 4 ~,
and Fe (ILI) curves
ions
1
Of HN03
They
separation
can be achieved
The low
I
at
since
are
I I
to absorb
1 — M acid. is very
coefficient
concentrations
U (VI)
along
to Dowex-50).
and Pu(IV)
HN03
and Pu(IV),
I
the
from
\
D 10
flattening these
in the elution
,i’
of ‘\
the Pu. Nelson used
HC104
their
survey
The
of cation shown
most
elements
tion
coefficients minima.
be made
state
have
coefficients
the basis
for
They
used
acid
decladding
with
in dilute
HN03.
The
primarily
iron
‘simfi~
group
resin
acid
acid,
washed
acid
distribution
The
to demonstrate which
concentration
re suits
a process
contain
staiiiess
contained
to remove
for
The
from
might
Pu(III)
shown
and
in Table
Pu from
Pu is normally
0.5 — M acid,
sulfate,
of the original
5%
for are
recovering
steel.
and is adsorbed
with water
most
common
from
applications
of cation
solution, or 419 Several such as hydra zine.
impurities,
phenomenon
coefficients
Their
solutions.
solutions,
Pu solution
and that this
c- 50
separation.
determined
solutions
to DC)w~~_~O)~I~sin
concentration,
and eluted
stainless
scrubbed with
steel
6 — N
materials,
and chromium.
(1) concentration
processes
in what-
sulfuric
product
d
3
ACID($~NCENTRATION’
Distribution of Pu(HI) and Fig. 43. Pu(I~) and other ions between nitric ‘acid solutions and the catio
state
in sulfuric
Dowex-50
0.5 — M sulfuric
2
NITRIC
appreciable
resins
sulfuric
---Pu m I
at high HC104
Iv-28.
trivalent
some
distribu-
and Higgins299
several
\ FOau)~.
gone
of an actinide
Neill Pu(IV)
having
all the actinides
eve r oxidation
\
9 ~)
The se authors
that essentially
distribution
(>
increasing
after
in
the HC1 data.
concentrations have
\ ,
behavior.
44 show
from
.
1(
medium
exchange
in Fig.
cliff erences
In high HC104
through
also
as the aqueous
results
striking
gt@300
‘\, \
a dilute
of Pu from should
process
as adsorption
solution
of Pu(HI)
HN03
containing
0.3 ~
sulfamic
solvent
be easily
of Pu(llI)
which 0.05 ~
extraction
adapted
processes plants
to the laboratory
from
0.25 ~
HN03
is O. 1 — M in hydroxylamine hydroxylamine
acid to prevent
oxidation
exchange
(2) separation
sulfate,
79
for
scale.
Bruce
purtiication
developed. 60
Pu are
These
X 12 from
washing with reports
and
describes
Bruce
by Dowex-50
and eluting
for
nombsorbable
final
have been
sulfate,
to Pu(IV).
techniques
from
with
5.7 ~
the
a 0.15 g/1
0.1 - 0.25 — M HN03 containing
a concentration
Volume distribution coefficient 4 cation exchange resin.300
Do~~~-%”X TABLE
IV-28.
Distribution
of the elements
Coefficients
in H2S04
for
Solutions
Pu for
vs HC104
Various
concentration
Cation
for
Resins
299
H2S04 Resin Duolite Dowex
Concentration C-65
‘Pu(III)
(M)
0.5
50 X 8
5.3
0.5
50 X 12
0.5
factor
of 330 for
30 for
Zr
Pu in this
and Nb,
and 2.4 to 8 for
During among
these
are
Purex
process,
process.
the entire
Decontamination most
process
(2) oxidation
resin
and (3) Pu(HI)
Q.
325
during
is more
Durham
and Aiken
Lingjaerde
255
easily 119
other
144
--
1470
--
factors
ions were
trivalent adsorption
desorbed, describe
and Sikkeland382
80
of approximately
for
several
as it is stripped
from
liberates
which
permitting
gasses a higher
essentially
the same
elute
6-8 ~
with
20 to
obtained.
the Pu is kept trivalent
(1) the Pu is initially
---
3.6
0.25
(IV) 35
360
3.6 Dowex
‘Pu
reasons;
TBP may
in the channel
concentration process.
the
factor,
Prevot
HC1 in preparation
for
anion
exchange
to elute
the major
and some
contaminating
tisert
VIII).
HN03
was
eluted
with
fission
Den Boer
which
actinides
as a typical solution,
and hydrazine
I
sources.
The
resin
(KU-1
by elution
KU-2.
The
with
with
436
of 1 ~
of cation
resin
beads
with this
resin
Several
Rapid
a very
of Np from HN03
NP(VI)
HN03,
dilute
from
HC1
U,
Pu and
the cation
is reduced
to NP(V)
and counted
applications preparation
of concentration
qualitative
analysis
to acidic
that these
resins
for
et ~. 222
Kennedy analogous
are for
phosphorous are
between
Np and Pu by elution acid
exchange
resin
polyvinyl
and 1, 4-his-
were
0.01 to O. 1 milliquivalents/
3.
of trivalent 45 with Am(III)
exon the
after
reduction
from
cation
to Pu(IU)
-
and
C.
and Gee. 172
ing from
A combination
the separation
of U(WO by 1 ~
at 90-10@
adsorbed
2.
report
ahead
with p-terphenyl The
sample
and
Fig. 45. Separation of Am from some common impurities by elution with HC1. The abcissa is drop number for a 0.3-cm diameter by 10-cm column. The 86 resin used was Dowex 50 X 4.
0.02 — M hydrofluoric
20 minutes
preparation
Easy
in Fig.
the ions from
16
of NP(V)
by Heimbuch
1.
shown
Pt(IV),
6 — M HC1.
with 3 ~ HN03. 435 separated and Sel’ chenkov
polymerized
activity.
are
Fe (III),
is then eluted
and KU--2)
scintillators.
except
No.
In the presence
Pu(IV)
with S02 for
was reported
the reductant,
purification
results
was to adsorb
and elute
and Nishanov
Zagrai
Np(IV)
1.5 — N and the Pu(HI) was
in the laboratory
10
Zolotov
resin
scheme
and Ce were procedure
I : 6MHCI , 1
DROP
change
general
Pm (see
of NH4 (I),
His
procedure
1 — M HC1,
5
resin.
procedure
the behavior
J-
products
was
2 — M HC1 wash
of the Pu.
in this
used the same
114
contaminants
His
with
fission
use an additional
elution
activities
mvestigated “
8’
common
actinide.
wash
HCI
were
product
the U02++
spectrometer
I,OM
0
workers before
HN03.
are
for
latter
products
and Dizdar
used to elute 8~
fission
Chetham-Strode Al(III),
The
in an HC1 system.
the U (VI)
beads
with
scintillating
toluene-divinylbe 2- (5-phenyloxyazolyl)
then surface-
sulfomted,
gram.
Sr90,
with
efficiencies
PU23’,
to give
30 to
50%
mixtures
-benzene capacities
and Pc1210 have
from
properties
nzene
as rang-
been
of the adsorbed
suggested:
adsorbable
radionuclides.
of ions from radionuclides prepared
and tested
compounds carboxylic
dilute
solution
in dilute
in solvent
and sulfonic 81
and sample
preparation.
solutions.
phosphorylated extraction resins
resins, systems.
in acidity.
which They
The
are
found
adsorption
affinity
of several
Co(II),
Ca(Jl)
ions
was Th(IV), Pu was
> Na+.
U{IV)
> U(VI),
not measured,
Fe(DI)
but Pu(IV)
> La(HI) would
> H+>
CU(II),
presumably
be with Th
known,
have been
and U. Inorganic
Ion Exchangers
Although largely
inorganic
superseded
capacities
by the synthetic
and more
exchangers. pounds.
tractable
However,
better
separations
from
to radiation
fission
by Kraus et al. 31,13r reported. The
fission
products
coefficients
for
concentration. column
has been
The
colurnm
After
washing
Pu and must be separated Ahrland and proposed for
et al.
47,
gel from
silica
gel to effect
Cvjet canin Pu from
long-lived
0.1 — N HN03, w~e Ru, and Cs activity Mn02
dried
fission
products. U(VI)
to Pu separations. Pu has been
sorption
of Pu(IV)
13 in Sect.
with only
of ZrJ
(see
Procedure
Pu(VI)
of several
acid onto a
through
the
8— M HN03. Cs follows
ions
similar
coefficients
The the
U,
are
plotted
PUJ and other
11 in Sect.
and U(VI)
on sflica
gel
to the one described
Pu by adsorption
113 The
used
as a function ions
by pH
of the former
on
VHI).
with hexone
a column
method
in the presence
composed 297 concentrated fluoride
of Mn02
is adsorb
through
on the columm
determined
on calcium
of
of Zr
The
environmental
from
a nitric
over
capacity
acid
for
U and
products
from
of the Zr,
99~0
zirconium
for
gram.
and Si oxyhydrates
from
the fission
the colurmz
to be 1 milliequivalent/
to separate
has been
water
samples
solution
352
prepared
and
by chemi (see
Procedure
V~). Ke nmedy
and Nb from
and
distribution
was loaded
studied,
products
from
and Pu(VI)
adsorbed
was
An exchanger applied
U,
nitric
and Ru pass
removed
has have
step.
Zr-Nb
and Cvjet canin
was
oxides
separation
passing
at 11 O“ C
agairmt
products
Sr,
the behavior
separation
solution
plotted
aqueous
of
quite
materisls
to separate Pu, 140 Equilibrium
46,
Ce,
distribution
extracted
a Zr-Nb
of hydrous
as ion exchange
Of the ions
U and fission The
also
properties
the Pu and Cs are
separated
a 6 — M HN03 112
U,
are
applications.
Pu and fission The
column
an easy
Cvjet canin
exchangers
com-
the finding
in process
phosphate
in Fig.
U,
by an additional 21, 22 studied
revealing
inorganic
phosphates
shown
containing
above.
and vale ncy adjustment. 341 Rydberg silica
The
by Gal and Ruvarac.
of Pu,
phosphate
of pH in Fig.
toward
Inorganic
on the
a separation
zti conium
primarily
of the ion exchange
the column,
in the synthetic
has proceeded
is an advantage
are
of the higher
obtainable
and synthetic
+ 0.02 — M NaN02.
and most. of the Nb stay
because
they
on natural
products.
of ions
long
has continued
use of zirconium
solution
at O. 5 — M HN03
work
reported
a number
principally
characteristics
which
discussion 242
given
been
Zr
this
damage,
A general been
field
have been
resins,
physical
experimentation
In the actinide
resistant
ion exchangers
et al.
223
carbonate
describe solutions
the absorption by hydrated
82
of Pu(IV),
titanium
oxide
U(VI), (HTO).
Ru,
Zr,
About
HN03
CONCENTRATION
(~)
Fig. 46. The dependence of the distribution coefficients of several ions on zirconium phosphate on the aqueous HN03 concentration. All adsorbates present in tracer amoumts. Solutions of Pu(~) were 0.005 ~ in sulphamic acid and 0.015 ~ in h drazine; solutions of Pu(IV) 0.02 ~ in NahT02 and solutions of Pu02~ 0.02 ~ in KBr03.1 &
1
I
1
,
1
,
,
1
1
â&#x20AC;&#x2DC;/
I
I
1
1 (2
-101
1
1
3
I
,4,
a
â&#x20AC;&#x2DC;7
1
1
1
1
I
9
PH
Fig. 47. mesh) .22
Log
D for
some
metal
ions
as a function
83
of pH on silica
gel
(KEBO,
50-100
95% of Pu(IV) volumes absorption tion
was removed
at a flow
rate
of Pu(IV)
of Pu(VI)
was
from
was not affected only
of this
system
processing
plants
is discussed.
Paper
Chromatography
and U(VI),
0.27 for
U(m)
valency
The
to have
paper
using
using
develop failed
paper
indicated acid
The
and Fink
carbonate
Rf values
The
column. The
conditions.
absorpA possible
wastes
for
mixtures
around
(1:1)
in
Pu(III),
Pu(IV)
ranging
from
6 — M HC1 and ranged
in between.
The
U and Pu by several
of solvent
also
reported
oxidation
states
and U(VI)
might
paper
The
ions
from
of lower
For
are
of the U and Pu were many
combinations
and Pu(VI).
cases
moved
be separated
cbromatographic
use of ion-exchange
w“orkers.
the Rf values
of both Pu(IV) but in a few
and acid.
by these
mve stigated
’31
or streaked,
Pu(VI)
ions from
ions falling
6 — M HC1 as a developer,
chromatograms
to move
the same
in HC1-butanol
the other
combinations
respectively. Fink
under
a matium
of 2000-bed
an HTO
of 5 mg/ 1 of U (VI).
chromatographic
Rf values. 47 separated et al.
U and Pu was
ET-20
and Pu,
U(VI),
different
to separate
Whatman
“reached
by passage
through
lower
Bildestein methods,
paper
and Am(lII)
Rf values
to 0.50 for
tended
volumes
Pu and other
determined
90
U(IV)J
solution
by tb.e pre aence
to recover
Clanet
1 to 10 — M HC1.
Na2C03
of the solution
20~0 in 1000-bed
application
and Pu(VI),
a 0.5 ~
of 1 ml/ cm2/min
example,
of solvent
and acid
In most
systems The
ethyl
U
not specified.
quantitatively.
in a methyl
with
0.56 and 0.98 for
ketone
to
PuOV) results
- dilute
nitric
system. Anion The
strong 29.
base
Strong
Exchange behavior
anion
exchange
adsorption
HC1 concentrations TABLE
of the actinide
(typically
of the actinides
above
IV- 29.
resin
6 ~
while
Absorption
elements
(a)Kd
resorption
states
1 or 2) in HC1. is shown ondation
occurs
and Resorption
oxidation
states
below
of Actinides
on a
in Table
IV-
occurs
at
(IV-VI)
2 — M HC1. on Strong
Base
Anion
in HC1 Solutions HC1 Concentration(~)
of Absorption(a)
for Resorption@)
m
Not absorbed
IV
6-8
2-4
v
6-8
2-4
VI
2-3
.
lo-10o
(b) Kd = 0.1-1.0
for
absorption.
for
resorption.
A convenient elements wash
Dowex
in the higher
Exchangers Oxidation State Actinide
in various
with
is to adsorb HC1,
way
Pu(IV)
and desorb
of separating or Pu(VI)
by reducing
0.1-1
Pu from
other
onto such a resin
actinides from
the Pu to the trivalent 84
and most
other
> 6 — M HC1 solution, with a suitable reducing
agent.
This
laboratory
by dilute from
method methods
for
Pu(IV)
may
acid
and effective
the separation be also
products
are
are
slower,
it has become
as well
one of the standard
as in larger
scale
process
from
than in the HC1 system,
resulttig
in some
Many
of the procedures
Wish
and Rowell
plants.
7 — M HN03 solutions and desorbed either distribution coefficients and separation factors
The
higher
that
of Pu,
adsorbed
or by reduction
fission
reactions
is so simple
loss
collected
but the room 325 of convenience.
temperature
in this
on anion
volume
are based
ex-
change.
coefficients
in HN03
Several
was
actinide
by these
by addition
Dowex - 1 is made
the 2 resins actinides
is quite
HF mixture separate
shows
the curves
e. g. for
the effect
for
HF
2 in HC1,
48-51.
equilibrium
completing
in Zr
tion
and in the resin
shown usual
in Fig.
Hardy
Fig.
for
The
53.
various
Pu(IV)
Data for and HN03
solutions
Many
results,
strong
The
base
exist
solutions.
which
The
of reduction elution
to Pu(DI)
of Pu(IV)
workers
amounts
oxidation
of U,
states
of
both in the solufrom
obtained
those
above
by multiplying
the actinides
resins.
These
cliff erences
from
for
7 — M HN03
elements
are the
by Fig.
The
shown
different
and in
resins
shown to be
1 from
great
in HN03
are
has been
on Dowex
54 and 55.
HC1 solutions
specificity
240
for
55.
exchange
resins
for
Pu separations,
Adsorption in 8 to 12 M HC1 and elution by reduction 108, 382, 447, 185, 383 ‘. 185, 293 with Hl in concentrated HC1,
has been
HC1 434 used
of the chloride
by HC1- HF mixtures
are
293’ 155
wash the column first with 7 — M HN03, HN03’ strip in 10 — M HC1 - 0.5 — M HI or NH41 solutiom of the somewhat greater selectivity and removal ease
The
data for anion
of the use of anion
with NH41 in 8 — M HC1, and NH41 in concentrated procedure
Dv,
significant
is shown
or with NH20H alternative
These
macro
somewhat
equilibrium
adsorbed
states
1.
in the HCl-
case.
quatermry
the adsorption of other 127 are shown in Figs.
examples
differ
coefficients, in this
show
species
valence
on Dowex-
data for
of the
11 — N HC1 - 0.06 — M HF,
spectrophotometrically
which
distribution
data in HN03
in the higher
both in HC1 and HN03 to Pu(III)
The
states
measured
bed density, 0.45, 162 has summarized
and different workers. = 337, 120 PU(N03)6 .
actinides
were
phase.
52 as volume
D by the resin
HC1 solutions
and hexavalent
experiments
polystyrene,
distribution
and Pu.
for
in these
no Pu data
comparison,
of the ions
and the Pu and Np together with 6.5 — N HC1 - 0.0004 — N HF. 266 Marcus measured distribution coefficients and Pu in the tetra-
for
so that the behavior
The behavior
by eluting
HN03,
Although
included
with
the ions
elements
distribution
to cbloromethylated
The 434, 240
Dowex-1.
of strong
and other
amine
U(VI)
Dowex-
are
175
with tr imethylamine.
valid
for
in Figs.
of dimethylethanol
is also
Zr
elements
equilibrium
the Zr
Np,
Pu from
determined
shown
results
workers,
similar,
in Dowex-2
and other
with
solution
obtained
2 is made
Dowexwhile
for
and HC1-HF
H2S04,
have
432’433’434
then with This
has been
procedures.
with
Pu(IV)
concentrated
method
of iron
system
85
common
is to adsorb
combines
of the nitrate resulting
mentioned
small before.
An
from
HC1,
7 — M and finally
the advantages system
with the
strip volume. 432, 433 These
d
I
I
I
I
1
I
I
,, , , x
I
Y
.
-.. ,
I
1
i I II !
2
1
1
[
[
. I
/
II In
I
,
,
r
1
11,
Iu
I
1
1
I
I
r
II
i
I
[#’ #
I
1.0 1 ,
02
Fig. 48. Equilibrium (Mo, Zr, and Nb curves
h
1
1
1
6 8 N Ha
1
1
10
di,stribution coefficients for furnished by L. R. Bunney
86
I
1
12
ll~~x,~ —.
1
I
IL
in HCl
solutions.432J
433
~
Fig.
49.
Absorption
of various
HN03
ions by Dowex
87
2 from
nitric
acid
solutionsf33
104
1
1
1
1 1
.— .-. I _-— , —
———
Ioa
.. . . —.
..—. ——
,
——
———
.-——
~q:YI .-
... ..- ——
I I
I 02
.— ,. {
“1
—-—
-
-——
——
- ..— —.
.——
— .—
/ –-+~.o&
( . #
X“
..—.
, i’1
-
-
“F’
,
I \
I
I 1
I
—
,—
I
t
1
P
.
ti
—
~—.
1.0 J
\
!
z-_
.—
1
4
$.
al
1 0
I 5
1 10
Is
20 ~
Fig.
50.
Absorption
of various
actinide
25
30
3s
H2S04
ions from
08
H2S04
solutions
by Dowex
2.433
a/~
9
/
4
/
/
‘~(VI~
I /
●,,
I
Pu(rv: ~
/ t \
f
i I I I
1! l., l.~
t
\ I I w
\
i I f I / [ /
\
\
%, ..
,
.. “-..,
\ I lFU n )
Ik...-.
[/ \
1 o
2
1Ur( IV T .-. -.’,...~ ~ i}.... ...
\\, 9 1 4
,, ~
/
I I 6
8
10
12
14
N HOl CCNTAINIXG 0.3N HP distribution
coefficients
89
of various
ions
on Dowex
2 in HC1 -
200 100 50
20 I
NPIX
-1
$
PUIIT
UISZ
O.10
~
I
H:l Fig. 52. Pu between
I
I
I
C: NCâ&#x20AC;&#x2122;i NT: AT~ON (~)
Volume distribution coefficients, Dv, for tetra Dowex 1 and hydrochloric acid solutions. 266
90
and hexavalent
U,
Np,
and
ANION
EXCHANGE
ANION
ANION
EXCHANQE
EXCHANGE
lo*~
‘oAc’D’m
FF
e)
!!!!$
Ion
DwEt
o lo~
AMBERLITE IRA 400 BFIEE CH
10
A BOOID 4LL
9,HNOS
f&HN03
P.l
246el MjHN03
0246610
0246010
I
I
01
0246610
0246a10
~,HCl
~,HCl
Fig. 53. Equilibr~um anion exchangers. 152 Individual a)
Pa;
distribution
coefficients
for
actinides
on various
references: Hardy
et al.
163
Th and U; Carswell b) C, d) e)
Kraus Ward
and Nelson and Welch
De-acidite Dowex
1; Aiken
Amberlite f)
Prevot
FF;
24T (unpublished
Phillips 23
data)
and Jenkins
1 RA 400 and French
319
A 300 D; Prevot
et al. 325
91
@@..
325
strong
base
Fig.
54.
Adsorption
of the elements
from
hydrochloric
acid
solution
by Dowex
1.
NO Ws.- MOutaGamONm 1-14â&#x20AC;? q m.us.-m.lar4D$owr10N
Fig. 55. Removal of elements anion- exchange resin. 127
from
solution
in 1 ~
nitric
acid
with
strongly
basic
240
methods
have been incorporated in sequential separation 108, 432, 433, 434 other elements. Np and Pu have been 204 Pu with NH41 before adsorption on the resin. The commonly
for
removal
done by anion
example
in 60~0 ethanol
separation which
with hydroxylamtie a pure
sorption
amounts either
HN03
Pu and many
by reduction
analysis
of the
of other elements is 280, 405, 319, 55
or HC1 solutions
of Pu from
U by adsorption
of U (VI)
is 2 — M in HC1 has been reported. and is not adsorbed in this form.
aqueous
one is low
sbxinkage
298 The
of the resin
on anion
exchange
Pu is reduced advantage
and rapid
resin
to Pu(III)
of this
system
adsorption
and de-
of the U(VI). In the nitrate
the distribution gradation
Pu,
a problem
above
at high
adsorbed
this
acid
8 — M HN03,
eluting with
in the separation
the Pu with
Ce(IV)
sulfate
scheme
from
from Am.
The
applications
are
either
Pu. Pu,
and Np by adsorbing
0.02 — M ferrous in O.25 — M HN03.
by adsorption
6 to 8 — M HN03 because and because resin de-
concentration
concentrations.
other materials 333 and Brauer separate
h~p by oxidation
included
Pu is usually
decreases
or to separate
Roberts and Np from
system
coefficient
becomes
to separate
eluting
separated
of Pu before
from
for
. The
over
of macro exchange
schemes
sulfamate, In another
of Th(IV),
Pu(IV)
the Pu
and finally method,
Th is
and Np from
8— M and of Np by
elution of the Th by 12 ~ HC1, of Pu by 12 ~ HC1 - 0.1 ~ NH41, ‘N03’ 4 ~ HC1. These authors report a clean separation with greater than 957. yields
by
both methods. Buchanan anion
exchange
methods
Other
syste”m
rapid with
separation about
in analysis
of Pu from
half
of the resin
containing
the other rapid
adsorbed.
separations
of Pu-”f
rate
These
half
of U,
issium”
Mo,
binary
Ce,
and Zr
aUioys for
Anion scale
used
a low
reaction.
an HC1-HF
exchange
processes
The
7 — M HN03
The
solution
from
these
Pu by
elements.
from
with
again
HN03
solutions
types.
of over
40 elements.
the of the The
the elutiom as a unit process are:
separation;
in a number
(1) the concentration 338, 339, 340, 325, 255
of Pu following
(2) the recovery
of Pu metal scrap; 336’331 and (3) the main separation step from 23, 57 The separation of Pu and Th in HC1 solutions has also been
products. 207
extraction
these
1 X 2) to speed
and purification
fission
a solvent
is used
the column
than 99.97” recovery
quantities to speed
Among
is slurried
in a column
of the Pu is already
(Dowex
greater
substantial
mixture,
most
resin
report
of the ions placing
can then be run through
because
cross-linked They
of different
solution
the bulk of the Pu before
Pu breakthrough,
when mixed
with
ions.
of the re sin.
without
authors
technique
Pu is desorbed
other
to adsorb
of the adsorption
of large
report
eluting
at a more
Pu by this
66
agents for Pu adsorbed on anion exchange resin in the nitrate 159, 419, 319, 189 and 0.36 — M HC1 - 0.01 — M HF. 243 hydroxylamine 243 Kressin and Waterbury used a “ slurry- column” technique for the
are
kinetics
et al.
described.
Anion determination
exchange
methais
of Pu in biological
have
material,
been used 33, 404
93
in several especially
procedures for the 205, 74, 254, 421
urine.
Toribara logical
403
et al. materials.
aqueous
solutions,
methods
but are
In very
work,
electrodeposition Pu,
varying
the pH.
stated
conditions.
density
acetate
and liquid
counting mixture
solutions
are
have
at pH 6-7.
been
bioin
used ~or radiochemical
However,
by electrolysis
shown
in Fig.
conditions
for
(2) plating
ma/ cmz,
Pu from of sample
scintillator.
on electrolysis
be separated
results
Optimum
750-1000
for
Methods
based
and Np could His
technique
not common because of the relative complexity 101 found that Pu could not be separated Cook
from
that U,
scintillation
was done by a single-phase
alcohol,
Separation
applications, early
a liquid
counting
absolute
Electrolytic Separation
used
The
from
the separation
time
of
~.
are
2 to 3 hours,
Np and U by
Samartseva nitric
56 as a plot
of the method. from
found
344
acid â&#x20AC;&#x2DC;solutions yield
stated
by
vs pH for
the
as (1) current
and (3) solution
volume
20 to
40 ml. Samartseva many Fe,
competing Al,
La,
also ions
Ba,
found
Cr,
Mn,
Ca,
separation
to an appreciable
to complex
the Fe.
On the other was could
strongly
dependent
deposition Pu metal
of these could
determined solvent
that
Bk,
dirnethyl those
acid
384
et al.
at any pH from
elements
Cr,
on a Hg cathode on a mercury
sulfoxide
only
successful
Fe
interfered
solutions
Co,
Ni,
rrom
and acetate
Fe,
Ph,
1 ~ HC1. from
saturated
were with the
was
added
of U and Pu
but that quantitative
acid
against
the ions tested
found that the deposition
cathode
solution 322
Among
at 0.002 â&#x20AC;&#x201D; M concentration
density,
nitric
Pu from
investigated.
of Pu was
Of these
and Na.
Oxalic
on pH and current
be deposited
among
Mg,
Sinitsyna
separation
up to O. 5 mg/ ml.
extent.
separated
Rein ~.329
best
hand,
not be achieved
that electrolytic
in concentrations
separations buffers.
Mn,
Sn, and Zn hy 321 found that Porter
an organic
with the metal
solution, chloride
and was the
NP
PH
Fig. 56. Relation of element yield to solution PH. The cathode was 100 mA/cm2 and the electrolysis time, 2 hr. acid.344
94
current density on the The solution was nitric
Clanet phoresis
e~.”
using
separated
10 ~
HN03
“electrophoretogram” U(VI)
would
mobilities
is shown
lie between in this
U(VI),
Pu(IV),
Pu(IV)
in Fig.
the experimental
in this
plot,
according
I 10
Support:
57.
conditions.
to the measured
1 8
6
4
I
Pu(lv)
1
1
I
2
2
DISTANCE Fig.
electro
scan of their
system.
~\ km75 >+ -z I-=so Uo a~25 -
by paper
gives
‘z < 100
POLE
and Cm(III) of a radioactivity
which
57,
and Am(IfI)
Am(III), A plot
as the electrolyte.
4
6
1
I e
I
1
POLE
+
10
(cm)
Separation of Pu(IV)-Am(III)-Cm( III).91 Electrolyte: 10 NHN03. “Millipore” HAWP paper. Development voltage: 25o volts. Time:
95
6 hours.
-
V.
DISSOLUTION
OF
PLUTON17JM
A. Plutonium concentrated renders
metal
dissolves Dilute
H2S04.
Pu soluble.428 Pu-A1
as well
H2S04
attacks
acid
can be dissolved
The
- NaN03.
or HC1 after
halogen
Pu slowly.
has been
in 6 ~
ANALYSIS
1
but not in IZN03
of Hl? to HN03 210 Pu metal. - 0.02 ~
is to dissolve
elements
or
addition
- 0.05 ~Hg(N03)2
method
actinide
acids, The
used to dissolve
HN03
An alternative
Pu and other 317,166
FOR
Plutonium
in HC1 and other
Sulfarnic
as HC1 and HC104.
of NaOH HN03
alloys
Metallic
SAMPLES
HF,317
the Al in a solution
can then be dissolved
in boiling
filtration.
B.
Other
Compounds
with
if ignited, dissolves only with great difficulty in the usual acids. Boiling P*2’ 445,328 with 85-100~0 H3P04 at 200° or concentrated nitric acid plus O.005 — M Hl~’,
with
5-6 — M
ammonium acid.107,62
H1451 have bifluoride, Ignited
potassium
been
Pu oxalates
The plutonium
the residue The
Pu-containing C.
Pu in these in excreted
and Beasley for
procedures
with HF or a basic VI.
Biological
for
counting.
foreign
Owing
material
counting
problem
fallout
without
serious
loss.
isotopes
an alpha
will
particle
and the resulting Most developed project
important
be degraded
pulse
height
used for
in the Manhattan
Project.
Source
in the case
of metabolized
of fallout
biological samples
the Pu soluble COUNTING
samples.
samples.
involve
treat-
in acids.
METHODS
is the preparation particles
is limited
requirements
in energy
will
of sources
in matter,
to approximately are
much
by energy
by interaction be smeared
suitable
the thickness
of
one mg/cm2
more
severe
analysis.
for
if the ratios
This
is so because
with the surrounding
medium,
out.
preparing
mounting
alpha counting sources in use today were 206 Jaffey and Hufford and Scott 189 summarize the techniques
on the one hand with thinness to be quantitative
soluble
Preparation
of alpha
distribution
with
Samples
environmental
AND
to be determined
of the methods
experience.
quantitativity
range sample The
are
of Withers
various
renders
with
or
Pu(OH) and finally 4534’ et al. has been
in the case
or other
is fusion nitrate
by fusion
dissolving
in Pu radiochemistry
to the short
dissolved
refractory for
Source
method
aluminum
to precipitate
readily
PREPARATION
on the counting
of alpha-emitting
from
step which
A. A universal
been
tube method 454
methods
fusion
SOURCE
have in water
to extremely
dissolving
Another
aqueous
and Environmental
ranges
samples, 303 describe
Most
sealed
samples.
samples
ment
with
and fluorides
” dissolving 263 the hydroxide.
used to dissolve
methods.
by treatment
bisulfate,
dissolving
Nielsen
recommended
followed
are,
in general,
on the other.
but not so important 96
to have
In assay a “thin”
a trade-off work sample.
of
it is very On the other
hand,
for
the separation
the source isotopic
dilution Table
reviews
mentioned
detail
suited
for
a discussion
Two
of the most counting
and (2) electrode adsorption
from
method
classic
“LaF3”
of LaF3-Pu,
method
great
source
general
of
and should
of alpha
evaporation
preparation.
reviews may 212,386,307
thin sources.
are
sources
for
produces
example
The
be con-
be con-
on a metal
of an aqueous
not so widely
filament
(See
or organic
of the sample
in
However,
used. very
the
satisfactory
Procedure
are
sources
4 in Sect.
VIII.)
only
principle
methods
a method
over
for
direct
alpha
to
an
is to be done.
evaporation reason
for
of even this
area
organic
failure
“thick”
is that the Pu and impurities
the entire
The
of a slurry
effectively
plate. in the
of the plate. solutions
thus confining of a circular plate, 426 to evaporate sulfuric used by Westrum
the edge
was
of
areas.
1 in Sect.
counting
The
produce
regard
evaporating
thick
evaporation
direct
analysis,
satisfactory.
effect
in this
evenly
total
energy
not be completely
local
the Pu 446 (Procedure
if only
on alpha
concentration
and the disadvantage
to produce
of Pu utilizes
to determine
is satisfactory
spread
describes
by heating
and simplicity
in the solution
counting
will
of other
to be plated
of speed
present
depend
mentioned
advantage
Tuck40’
which
solution
The
A.
of
in the case
such as volatilization
solution,
a tungsten
alpha
preparation
methods,
the determination
the method
free”
in the above
same
for
by alpha
in methods
lies
The
the thinness
at least
information
Other
for
laboratories.
any mass
followed
In general,
terials
Other
for
of this
arc (1) direct
has the advantage
to concentrate
solution
analysis
Evaporation
tending
a “carrier
methods
from
use in some
source
of mounting
an aqueous
“flashing”
and is in routine
However,
used
position.
method
references.
or spectroscopy
of vacuum
VIII).
the primary
widely
solution
This
are
of the problem
for
by energy
is not required,
of the project
and literature
backing
energies
methods.
above
more
A. 1 Direct
particle
quantitativity
is a summary
for
a vacuum,
while
analytical
VI-30
sulted
method
of alpha
is paramount,
of alpha-emitting the liquid acid
ma-
to the center.
solutions.
2 Electrodeposition This
analysis
method
apparatus
gives
He chose
formate
The
also
and Smith288 Mitche11452
gives
HC1- ammonium from
conditions solution
a rapid
a O. 1-0.2
of formic, for
method
for
g/ml
chloride
to produce
or sulfuric
occurs
precipitated
of ammonium
electroplating He gets solution
1 A/cm2. 97
oxalate trace
essentially
acid
quantities
1 using
energy
Th to
and ammonium of 100-300 reaction
(hydrated).
at the
Moore
to elect redeposit
quantitative
at pH about
from
densities
as a precipitation is PU(OH)4
for
complex
can be as much
of the actinides
perchloric
elements
suitable
a relatively
one sample
up to 100 ~g of Pu at current
solutio~
solutions.
plates
of requiring
electrodeposition
the compound
used an acid
chloride
for
of all these
of Pu,
thin uniform
The time
effort.
high yields
deposition
In the case
cathode.
minutes
a buffered
and achieved
mA/cm2.
greater
specific
of producing
and the disadvantage
particles,
and relatively
as two hours. ~0233 Cm.
has the advantage
of the alpha
Pu.
of actinides
from
deposition
in 15
a current
density
of
TABLE Method
1. Normal solution usually under a Solution tatively
m m
VI- 30.
Source
Preparation
and Principle
Methods
for Alpha
Applications
Evaporation - Placing on a suitable backing, Pt, and evaporation heat lamp, and igniting. may be pipetted quantiif desired.
1.
Preparation of sources for alpha counting from aqueous solution.
2.
Preparation of sources for alpha counting from organic solution.
Radioactivity
Measurements(a) Disadvantages
Advantages
1. Rapid,
convenient, quantitative.
2.
Easier to get uniform spreading. Organic may not have refractory impurities.
1.
Sample not uniformly spread if >25 pg of material. May cause error due to self adsorption.
2.
Same as 1 + more difficult to prevent loss over edge of plate. May require edge heating or stippling small volume at a time.
of Carrier 2. Slurry Transfer Salts - Co-precipitation with ~dle salt, transfer to plate, spread, evaporate and ignite.
Volume reduction for cases where solvent extraction or ion exchange methods are not applicable.
Relatively fast, easy method.
Co-precipitation and transfer may not be quantitative. Requires at least 0.3 mg of carrier. Self absorption losses may be serious.
- Electrolytic 3. Electrodeposition reduction of plutonium at a platinum cathode.
Preparation for energy
Very thin, uniform films arc attainable. Method can be made quantitative,
Requires special preparation of solution, requires relatively long time to prepare 1 sample.
Sublimation 4. Low Temperature in Vacuum - Prepare volatile compound, place in low temp erature oven in vacuum, cone ct vapor on suitable cold plate. The volatile compound is rendered non-volatile and the organic material destroyed by ignition.
Preparation of extremely thin sources for highest resolution alpha energy analysis.
ExceJlent sources any kind of backing may be used.
Orily a small fraction of sample cone cted. Volatile compounds are difficult to handle and constitute a health hazard. Not a routine method.
Sublimation 5. High Temperature in Vacuum - Place material in oven with suitable orifice, evacuate and volatilize at high temperature. Collect on a cold plale. The oven may be a dimpled W or Ta strip heated by rcsis~ance heating. In this case the plate need not be cooled.
Preparation of high quality thin samples for alpha energy measurements.
very good sources obtainable. Resistance heated strip method applicable to routine isotopic dilution analysis.
Not quantitative, however under favorable conditions - 90~0 yield can be obtained, Yield is usually about sf)~o The apparatus is relatively large and expensive.
of sources analysis.
â&#x20AC;&#x201D; (a)
Compiled
from
References
206 and 189.
.
Miller
and Brouns27’
1-2 — N KOH
solution.
that all elements A.
3 Other
which
precipitate
plates
from
The method
The
dilute
report
basis
( ‘0.01
~)
is not quantitative.
98% complete
for
solution
electrodepositon
This
method
interfere
of Pu(VI)
from
has the disadvantage
with the deposition.
of the method
method
is adsorption
HC1 solutions,
presumably reports
%rnartseva’”
for
preparation
of Pu(IV)
of ex-
onto glass
as the polymeric
that adsorption
or
form.
of Pu(IV)
is 97-
10-1 to 10-3 ~ HN03 solutions. 81 and Milstead made thin sources of U and Pu by electrostatically
a jet of the material
to be plated B.
The
an interesting
on Pt from
Car swell focussing
procedure with ozone.
in basic
122
and Sikkeland
thin Pu sources.
metal
a detailed
Pu was oxidized
Methods
El Guebely tremely
give “
The
which
was
dissolved
in a volatile
solvent.
Counting
of the determination of the amount of alpha radioactivity has been re213 206 and Hanna. 1’0 These accounts and recently by Johnson et al.. by Jaffey
viewed should
subject
be consulted
Table
VI-31
disadvantages The
pared
details
the major
of the various
types
detection
of counting
systems
systems
with
and literature
applications,
references.
advantages,
and
of each.
ratios
in the energies The
for
lists
of the isotopes of the alpha
of Pu can be determined
particles
Pu 236 is very
isotope
in alpha
useful
pulse
by making
use of the difference
analysis.
as a tracer
in this
method.
This
isotope
is pre-
by the reaction U235
using
highly
(d, n) Np
enriched
U
made “by any neutron isotonically occurring
pure. isotopes
236~
235
PU236,
to make
reaction
on U,
Since the alpha 239 (Pu , Pu240,
and PU238 ),
is not very
much
precaution
is that imperfections
result
in low-energy The
alpha
care
than the activity
particles
subtraction
as possible.
Since
Pu236
is not 236 is
an unspiked sample need not be run if the Pu 236 1s higher than that of the other commonly Pu
activity
the spectrum.
as pure
energy
for
this
greater
the PU236
must
of the other
in the sample which
of this
appear
tail
be taken
difficult
The
Pu isotopes.
and detecting
as a continuum
becomes
that the added
instrument or low
if higher
reason always
energy
energy
PU236
“tail”
isotope
in pre-
dominates. C. Another mass long
isotopic
spectrometer reactor
method
as the detecting 239 irradiations of Pu .
of a particular
a mass
spectrometer Schwendiman
Pu analysis.
of Pu in biological
sample
Methods
uses
the rare
Isotopic This
is needed.
isotope
Highly
instrument.
of the Pu 23g-Pu240
A determination activity
level
dilution
Other
ratio
Pu
enriched
must
determination
242
as the tracer and a 242 1s a product of
Pu
be made must
if the specific
be made
by means
of
since
the alpha particle energy of these 2 isotopes is the same. 360 have described a nuclear emulsion technique for lowand Healy 303 have reviewed the radiochemical determination Ifielsen and Beasley materials
and include
a critical 99
comparison
of various
counting
systems.
TAIIT.E
VI-31.
Method A,
Total
1, Air
Alpha ionization
Techniques
for
Measuring
Alpha
Application
Radioactivity.
Advantages
Disadvantages
Activity chamber
Total assay instruments.
- survey
Simple, easily repaired and cleaned, reliable, inexpensive.
Long decay time of pulse makes inherently wide pulses - limited to low counting rates. Low tolerance to ~ activity.
2.
Free-electron-gas ionization chamber (A, A-C02, He, N2, etc. )
Total
assay.
Sharp pulses permit high count rates and tolerance to ~ activity. Not microphonics. Reliable and stable. A known relatively unchanging geometry,
Signal-to-noise inferior to proportional counters, therefore more prone to spurious counts. Must be corrected for low-angle back scattering.
3.
Alpha
Total
assay.
High signal -to-noisd ratio, good j3 discrimination. Not at all microphonics.
Count rate sensitive to applied voltage. Requires pure gas for stability. Difficult to maintain stability for long periods.
4.
Scintillation
Total
assay.
Very
Lower tolerance to O radiation than ionization chamber or proportional counter. Greater sensitivity to sample size, and position.
5.
Low-geometry
Total
assay.
Can count sources of greater activity. Counting rate not so sensitive to sample thickness. Reproducible and reliable. No low-angle back scattering correction.
Not suitable for low activity. Sensitivity to sample position and area.
6.
Nuclear
Total
assay.
Great sensitivity and stability. Very simple apparatus.
Limited accuracy, considerable technique required in exposing and developing emulsions. Counting tracks is time consuming and tcdimls.
proportional
counter
o
0 alpha
counter
counters
Emulsions
low background.
TABLE
VI- 31,
Techniques
Method B,
Alpha
Energy
for
Measuring
Alpha
Application
Radioactivity
(Contl d)
A dvant ages
Disadvantages
Measurement
1.
Magnetic deflection spectrometer
alpha
Energy measurement mainly for determination of energy spectrum.
Very high precision and accuracy.
2.
Total ionization and pulse analysis. Frisch grid ionization chamber
Energy measurement determination of isotope ratios.
Convenient, easy to use. High geometry up to 5070. Tolerates large area sources. Resolution can be improved by collimation.
Semiconductor charged particle detector
Energy isotope
Very convenient capable of high resolution.
3.
measurement ratios.
-
-
Large, expensive equipment. Requires photographic technique for recording data. Counting tracks is tedious and time-consuming. Very low geometry. Thin sample required. -
Requires tion.
gas purifica-
Requires low gecmetrY. for high resolution. Detector may become irreversibly contaminated by volatile radioactivity.
Solvent eliminate
extraction
of Pu into a liquid
preparation in radiochemical 241 . of Pu n low-level biological
the @ activity The
incorporation
has been
reported
has been
of a scintillator
172 (see
Scintillation
page
counting
used to monitor
Hazards causes.
biological
criticality view,
half-life,
may
but some
The
occur. general
of personnel monitoring 32 and Dunster have written
Appleton
A. The are
prbnary
eaHily
isotopes
shielded
since
composition missible
and the gamma
“tie biological
of Pu varies concentrations
data are
be consulted
for
taken
to concentrate
(MPC) from
by NaI 123
VII-32.
detectors
radiation
activity,
surveying
inadvertent
the scope
of ingestion,
associated
of the activity
is done by the alpha VU-32
of Pu isotopes Bureau
lists for
since
Hazard
body
burdens
continuous
rather
soluble
occupational
Assuming
per-
exposure.
69, which
should
Isotopes.
Maximum Permissible Concentration for 40hour week (microcuries/cc)
0.04
Air
10-4
2 x
10-’2
3 x
10-”
10-3
9 x
10-’1
0.04 (=J
4
10’6
PU242 8 X 10-4
soluble
(b) Assuming
t.lmn
and the isotopic
and mtimum
Handbook
Plutonium
0.9
7 x
insoluble
(a)
particles
long-lived level
radioactivity
of Standards
Data for
insoluble ~241
by Morgan.
the alpha
Water
PU240,
re-
of Pu.
with the common
in terms
Mtimum Permissible Body Burden in Bone (microcuries)
Isotope
PU239,
of this
can be made.
has been treated handling
two
Safety
stated
the National
from
alpha
and techniques
on the safe
Radioactive
Table
Health
the gastro-intestinal
256
resin
detafls.
TABLE
PU238
of
reported.
prtiarfiy
Second,
is beyond
precautions
a manual
arise specific
in the bone.
and radiation
damage
239
streams.
of these hazards
is better
widely.
in Pu
of its high
is due to the possibility
The hazard
is alight.
the mass,
These
hazard
gamma-ray
because
concerning
subject
has been
of an ion-exchange
with Pu in the laboratory
discussion
comments
method
to
CONSIDEFUiTIONS
poisonous
and tendency A full
by this
of RI in process
SAFETY
who work
samples
0.4 MeV
the concentration
Pu is extremely
aa a method determination
details).
of the weak
to personnel
First,
has been proposed 135,403 The
procedures.
in the polymerization
61 for
VII.
long
scintillator
source
tract
the lung to be the critical
to be the critical organ
102
‘a)
organ.
x
~)
~)
291
The
most
common
alpha-emitting air
control
isotopes
pressure
by means
with respect
with remote
manipulators
ae
equipment
necessary 1.
This
monitoring
tories,
safety.
special
air,
of high
survey
done either
a variety
of
enclosure
of the actitity,
are:
release
“ spilling”
or
instruments,
and by personnel
are
to the enclosure.
laboratory,
these
of
at a negative
Operations
to the primary
Among
activities
is maintained
sealed
activity
of the accidental
of the laboratory
Protective
respirators
alpha
gloves
in addition
personnel
to the working
2.
length
or high-level
which
atmosphere.
can be done by hand-held
and monitoring at exits
arm
and practices
monitoring
containment
of an enclosure
or with
to insure
Adequate
is total
to the laboratory
In an intermediate auxiliary
practice
of radioactivity.
by continuous
monitoring
filtering
instruments
placed
area.
devices
clothing
and clothing.
is part
to prevent
In most
of the laboratory
inhalation
of airborne
high-level
radiochemical
practice.
The
labora-
availability
radioactivity
in the event
of the laboratory
as well
of
of a spill
is
essentisl. 3.
Procedures
procedures
especially The
out in advance
or the maintainance
kind, for
laboratory
amount,
normal
warning
and distribution
This
of large
beyond
work
and the skill the level
total
and care
care
limited.
“Good
space,
should
as well
as laboratory
chemical
be handled
be
is taken,
while
operation.
In any case,
This
hazard
is most
an “ always
which
will
not be a critical
While
the determination
the scope
of this
from for
review,
the U-SAEC
further
generally
safe”
amount mass
levels
Table
information
on this
is not very
subject.
103
is
well
can
be
done
become
becomes
At if
more
necessary
of the activity
defined.
of the operation
and for any
is essential.
Safety
amount
‘‘ Nuclear
as a
laboratory.
must be considered.
the operations
laboratory
or area.
in any configuration
Publication
radiochemical
in the radiochemistry
basic
mainly
materials
as the nature
which
of Pu in any room
32 gives
radioactive
procedures
monitoring
of the always-safe
from
of the handling
to serve
a necessity as well
containment
Criticality met
for
in an ordinary
factors
total
proper B.
permitting
are
at higher level
to the subject
is intended
becomes
laboratory
in detail
142
material,
of the operator, ordinary
considerably
of enclosures
containment
At the millicurie
activity
and Nielsen,
of the alpha- active
of one microcurie,
reasonable
subject
devices,
vary
introduction
of alpha
of course,
which
of protective
brief
by Garden
can,
concentration
very
The
in a review
activity
The limit
sulted
as emergency
by all personnel.
and orderly
operation,
amounts
to the uninitiated. fully
Low
tracted
and understood
of a clean
and emergency
to laboratory.
and manipulation
treated
operation
emphasized.
practices
more
normal
must be worked
housekeeping,”
The
for
or dispersed in a particular
data for Safety
This
by only
is an amount
in any medium. situation
is beyond
PU239. This table was ex444 Guide” which may be con-
TABLE
VII-33.
Basic
Data
for
Criticality
.LIass
Form
of Isotope
Hazard of Isotope
Recommended
for
for (kg)
Plutonium-239. which
is maximum
Safety
Minimum
Critical
Metal,
a phase(a)
2.6
5.6
Metal,
6 phase(a)
3.5
7.6
0.22
0,51
Solution
(a)
The
metal
is assumed
to be surrounded
104
by a thick
hydrogenous
layer,
VIII.
COLLECTION A.
The
literature
of Pu is replate
procedures.
A survey
enough
to do justice
detail
developed
criteria
26 survived
for
in detailed
arbitrary
criteria
equally The
The
for
target
Pu.
Two
analysis
fission
solutions
group
examples
are
impurities
included
in this
were
written
which
could
or more
collection.
be
complete.
(2) completeness
and (4) utility.
procedures
in
easily
The basic
in chemistry,
in application, between
separation
In some
which
cases
met these
procedures
concerned
sufficiently
analysis. ages
samples.
The
the purpose
starting
to fresh
There
with purifying for
are
materials
(2)
samples
Pu from
other
at hand,
usually
range
of nuclear
13 of these
with a specific
the separation
of Np and Pu and the removal
from
reactor
explosion
procedures
is concerned
category,
all purporting
step is, included
of course, were B.
Radiochemical
are
procedures,
procedures.
of procedures
is a separate
urinalysis
group products
of varying
radiochemical
and (3) urinalysis
debris
included.
separation
involving
of Pu before
in Pu metal.
in the literature, separation
Procedure No.
which
methods
quantitative
into (1) general
pulse
environmental
the initial
General
more
(1 ) distinctiveness
procedures,
or alpha
second
for
divided
in the first
and from
Urinalysis cedures
are
procedures
dilute
and are
had to be made
separation
counting
The
with procedures
the directions
fourfold:
and analytical
well.
dissolver
to very
radiochemical
and many
(3 ) generality
procedures
emitters
alpha
were
choice
purpose
alpha
by making
instructions,
a rather
with
54 papers
screening
screening
Introduction
to the name,
into procedures
Of the 54,
special
disclosed
OF PROCEDURES
primarily
similar
chosen Listing
because
to do the same
there
thing.
are The
to that in the other
primarily
for
so many chemistry categories.
distinctiveness
proafter The
of chemistry.
of Contents
Procedures
Author (principal)
Title
or method
m 108
1.
Welch
Determination of Pu when large of Fe and Cr are present (LaF3
2.
Moore
Separation and determimtion TTA extraction
3.
Maeck
Separation and determination of Pu in U-fission product mixtures (extraction of quaternar y alkylammonium - pluton yl nitrate complex into hexone - TTA extraction
114 ~
4.
Morrow
Plutonium
(anion
exchange
116
5.
Hoffman
Plutonimn
(anion
exchange)
105
amounts method)
of Pu by
)
112
118
Author (principal)
Procedure No.
Title
or method
6.
Hart
7.
(No
8.
Rider
U and Pu determination in highly irradiated fuel. (Hexone extraction, TTA extraction)
126
9a,
Lingjaerde
Pu from exchange
129
9b ,
Rydberg
Separation of Pu from U and fission products (BiP04 precipitation, TTA traction)
10.
Separation and determination of Pu from U and fission products in irradiated reactor targets (anion exchange â&#x20AC;&#x201D; TBP extraction) author )
Rydberg
124
irradiated )
U (cation
Geiger
U and Pu from soil, vegetation
12.
Sheidhauer
Pu from environmental water (chemisorption on CaF2, TTA
13.
Kooi
Pu from environmental (BiP04 precipitation, ferric cupferride)
14.
anion
131 ex-
Separation of Pu from U and fission products (adsorption of Zr-Nb on silica precipitation of CUSJ TTA extraction)
11.
Special
exchange,
132 gel,
environmental samples of and water (TBP extraction) samples extraction)
water samples co-extraction with
134
137
140
Procedures Larsen
Separation and spectrophotometeric determination of Pu from U-Pu-fission element alloys (TBP extraction from solution)
142 HC1
15,
Trowell
Separation of Pu before spectrographic analysis of impurities in Pu metal (anion exchange
144
16.
Trowell
Separation of Pu before spectrographic analysis of impurities in high purity Pu metal (extraction chromatography using TBP)
148
17.
Jackson
Separation
149
18.
Zagrai
Separation of Np and Pu by cation chromatography
Urimlysis
of Np and Pu by anion
exchange exchange
150
Procedures
19.
Brooks
Determination of Pu in urine cupferride extraction)
(ferric
20.
Perkins
Determination of Pu in urine cipitation, TTA extraction)
(PrF3
106
153
pre-
155
Procedure No.
Author (principal)
Title
or method
21.
Everett
Determination precipitation,
22.
Bokowski
Determimtion of Am in urine in the presence of Pu (BiP04 precipitation, LaF 3 precipitation extraction of Pu into di - (2- ethylhexyl) phosphoric acid
161
23.
Campbell
Determination of Pu in urine earth phosphate precipitation, exchange
164
24.
Weiss
Determination of Pu in urine (co-crystallization with potassium rhodizonate, LaFs precipitation, anion exchange)
25.
Bruenger
Determination of Pu in urine and bone ash (extraction by primary amines from H2S04 solution)
107
of Pu in urine TTA extraction)
(LaF3
(alkaline anion
166
Procedure Cr. —
1.
G. A.
Determination
Welch
Outline
~.
of Pu in solutions
(Ref.
Hydroxylamine
is added
carrier
Lanthanum
added.
amount
fluoride
of fluoride
counting against
amounts
of Fe and
446).
The acidity
state.
precipitate
large
of Method
to the trivalent
ammonium
containing
tray,
fluoride
and carries added
is separated
to reduce
the precipitation
measured
and mounted
with
a limited
By strictly
and chromium
washed
and chromium
and lanthanum
by adding
with it.
of iron
by centrifuging,
plutonium
is adjusted
is precipitated
the plutonium
and the a -activity
standard
to the sample
of the solution
nitrate
amount
controlling
of the
is prevented. on a flat
a scintillation
counter
The
stainless-steel calibrated
sources.
Reagents All
reagents
1.
Ammonium
are
2.
Nitric
3.
Hydroxylamine
4.
Lanthanum
5.
Ammonium
acid,
Dissolve
Store 6.
reagent
hydrockiloride, nitrate
available.
5!70 w/v
solution,
5 mg La/ml. hyxahydrate
solution,
in a polythene
12-57.
in 500 ml of distilled
water.
wfv
bottle.
lacquer. “ZAPON”
Standard Dilute
where
2~
fluoride
Cellulose
quality
9~
7. El g of lanthanum
Dilute 7.
analytical hydroxide,
lacquer
Pu solution,
a solution
tration
of known
of the diluted
constitution requiring
with
should
amyl
acetate.
0-5 ~g/ml. Pu concentration.
solution
need
be essentially
The
not be known, the same
exact
Pu concen-
but the isotopic
as that of the samples
analysis.
Equipment a - scintillation
1.
Type 2.
to dry
to cool
trays.
Stainless
steel,
for
and paint
and store
equipment. or B scintillation
Counting
Prepare Allow
1093A
flat,
mirror
use by heating a ring
the pr:epared
finish,
in a flame
of cellulose trays
unit with associated
lacquer
in a closed
equipment.
1-1/16 in, diameter. until the surface
is straw
round
Allow
the lacquer
@ass
centrifuge
the edge.
coloured.
container.
Procedure 1.
Transfer tube.
a suitable
Wash
to the tube.
portion
out the pipette [ Note
(a)].
I 08
of the sample with
2~
nitric
to a 3 ml acid
and add the washings
2.
3.
Add
O . 15 ml
(3 dr opfi) [Note
and stir
well.
Add
ammonia
9~
of hydroxylamine
hydrochloride
solution
(b)] .
solution
until
a faint
permanent
precipitate
is
formed. 4.
Add
2~
nitric
acid
until the precipitate
just
add O . 1 ml
(2 drops)
in excess.
5.
Add
(2 drops)
of lanthanum
6.
Add
O .15 (3 drops)
of 12 .5% ammonium
well
and centrifuge
for
O. 1 ml
dilute
7,
the solution
Remove [ Note
(d)]
and wash
fluoride
5 min before
removing
slurry
to enter
Wash
tray.
Spread
additional 10.
Dry
Measure tion Using ment
13.
Calculate
for
it to a
Do not allow
the
(e)].
of distilled
precipitate
water
and
to the counting
within
the cellulose
of solid
matter
with
necessary. heater
and ignite
heat to drive
“ZAPON’
the counting
off excess
ring.
Allow
tray
ammonium
to cool.
using
stable
a-scintilla-
(f)]
counting
[ Note
ml
centrifuge
[ Note
the tray
on the counting
[ Note
and correct
ground.
where
a radiant
off the
the activity
a clean
5-10 drops
over
and O .25
and transfer
pipette.
of the tube.
evenly
with a
acid
wash,
pipette
liquor.
up agglomerations
to a dull red
equipment
stir
a transfer
by stirring
of water
a transfer
part
of water
and burn
solution,
nitric
each
and the residual
beneath
in a flame
fluoride
12.
drops
After
tube with
and break
the slurry
tray
11.
the wider
the slurry
ring
with
twice
2 drops
with
the washings
lacquer
(c)]
the supernatant with
tray
the centrifuge
transfer
(~ mg La/ml),
well. fluoride
O .1 ml of 2~
solution.
the precipitate counting
[ Note
the precipitate
of ammonium
prepared
9.
liquor
of 1 ml of water,
Slurry
2 ml and stir
solution
then
10 min.
the super natant
mikture
.9.
to about
nitrate
redissolves,
tray,
measure
the counting
rate
the background
of the sample
of the equip-
source
for back-
(g)].
the concentration
relation
Pu (dpm/ml)
(a)
Usually
not more
(b)
After
of Pu in the sample
= 100 Cel/ EE2
V
[ Note
solution
from
the
(h)] .
h’otes
with (c)
(d)
each
addition
a platinum
About
0.1
after
each
A piece rubber
than 500 IJ1 should of reagent
the mixture
should
be well
stirred
wire.
ml of liquid
should
wash to ensure
of glass
be used.
tubing
be left
behind
at this
that the precipitate
drawn
teat.
109
out to a capillary
stage
and
is not disturbed. and attached
to a
The precipitate
(e)
tube, wider The
(f)
is easily
but it is difficult part
of the counter
plutonium
The background
(g) (h)
The
ratio
from
may be checked
source
should
(see
Appendix
not normally
El/ E2 may be replaced
of the plutonium the time
the narrow
portion
it if it is allowed
of the
to dry
on the
of the tube.
stab flity
standard
washed to remove
control
of sample
source
statistically
exceed
a
2 cpm.
by the ratio at the time
count provided
using
H).
of the counting
of standardizing
that the same
control
rates and at
source
is
used. Where
C
Counting
rate
. Volume
v E
Percentage
source E2
(para. I.
Using para. D,
7) obtain
paras.
background
as cpm.
equipment
for
the standard
equipment
for the Pu control
I).
of the counting of calibration
the Pu control
of the a-counting
500 IJl of the standard
a series
for
(Appendix source
I).
at the time
of sample
count
11).
Calibration
of standard
equipment.
Pu solution
sources
(O. 5 Hg Pu/ml)
by the procedures
(see
Section
described
B,
in Section
2 to 10. Measure
the counting
Determine counter
at the time for
corrected
of the coumting
(Appendix
efficiency
Percentage
=
APPENDIX
source
Percentage
â&#x20AC;&#x2DC;
source
in ml.
efficiency
plutonium
â&#x20AC;&#x2DC;1
of sample
of sample
of known
a low geometry
rate
of each
the disintegration
efficiency. counter.
Calculate
rate
(This
efficiency
case
the ratio
source
and correct
of each
source
is measured
for background.
using
an a -proportional
with a source
calibrated
in
)
in each
Corrected counting rate as cpm Disintegration rate as dpm and calculate
the counter
APPENDIX
II.
efficiency
Preparation
Prepare
a standard
approximate@
20 mg of this
tray,
that the liquid
ensuring
the liquid the tray
on the tray to cool
in acetone the counting a-proportional
solution forms
the spot
rate
of the control
counter
from
of known
a weight
by warming
source
Allow
pipette
gently
equipment.
110
10 pg/rnl
to a clean
beneath
to dry
Calculate
at room
of Pu.
heater.
10 ~g/ml
the efficiency
counting
Evaporate Allow
of collodion
temperature.
the disintegration
Transfer
prepared
of the tray.
a radiant
containing
and determine
efficiency.
about
spot in the center
of a solution
of activity.
source.
containing
a small
sufficient
to cover
ratio.
of the Pu control Pu solution
to dryness
and add just
E = 100 mean
Determine rate
using
of the counting
an
Efficiency NOTE: same
time
equipment disintegration
of Appendix
and E ~ , the efficiency
of calibration is measured
The procedures
100 Corrected counting rate (as cpm) Disintegration rate (as dpm)
=
of the equipment, with each
at the time
is obtained.
set of sample of sample
I and Appendix
of the equipment The
for
counting
determinations
count,
is calculated
rate.
111
II are
carried
the control rate
out at the
source
of the control
and E2 , the efficiency using
at the time
the previously
source of the
obtained
Procedure
2.
and J. E.
Separation
Hudgens,
Outline
LaF3
which
(Ref.
of Pu by TTA
extraction.
F. L.
Moore
287).
of Method The
ting
and determination
Jr.
sample
is pre-treated
and dissolving
in Al(No3)
may be present
Pu(IV)
is extracted
plate,
and counted.
and assures
from
2 ~
Yield
if necessary, 3 -HN03.
the proper
HN03
with either
HN03
The pre -treatment valence
and stripped
state
into
(IV)
10 ~
or by precipita-
destroys for
any polymer
the TTA
extraction.
HNâ&#x20AC;&#x2122;03 , evaporated
onto a
is quantitative.
Reagents Hydroxylamine of C.P.
grade
hydrochloride,
and diluting
Sodium
1 Ll,
is prepared
2 -Thenoyltrifluoroacetone
-xylene
diluting
nitrite,
1 ~,
is prepared
by dissolving
69.5 grams
it to 1 liter. by dissolving
69 grams
of C. P.
grade
and
it to 1 liter.
the ketone
and diluting
may
be obtained
from
St.,
Chicago
D1. )
51,
it to 1 liter Graham,
is prepared
O. 5~,
with
C. P.
Crowley,
xylene.
by dissolving
111 grams
(2 -Thenoyltrifluoro
and Associates,
Inc.,
of
acetone
5465 West
Division
Pr etr eatrnent acid
method.
into a 100-ml
Nitric
volumetric
flask
tion
carefully
is heated
under
boiling
water.
The
for
acid
~luoride pipetted
to a low boil
5 min.
nitric
A suitable
The
concentration
of this
cone.
aliquot
acid
and O. 1 ml of lanthanum
mixed
Then
0.3 ml of hydroxylamine
fluoric
acid
(27 ~)
are
a 5-rein
Next,
0.1 ml of lanthanum
stirred,
digestion
added
After
care
being
at room
temperature,
removed
with mild
1~
nitric
acid
lanthanum
fluoride
aluminum
nitrate
This removing tion.
suction.
precipitate
treatment
not only
the Pu from
for
precipitate
containing
several
aids
interferences, extraction years
for
is washed
acid,
and 1 ml of 2 â&#x20AC;&#x201D; M nitric
The liquid-liquid
successfully
The
with
is added
the precipitate.
centrifuging
ml)
( 5~)
the aoiution
is centrifuged
hydrofluoric
of the sample
solu-
just
with distilled
be approximately
(5 mg per
is stirred
ml)
The
is held
2~.
solution
is
of 0.4 ml of concentrated
hydrochloride
(5 mg per
not to disturb
the solution
â&#x20AC;&#x201D; 1~
carrier
temperature,
carrier
taken
( 1 ml)
addition
and the solution
at room
should
is pipetted
acid.
to a known volume
solution
After
hydrochloric well.
solution nitric
and the temperature
is then made
A suitable
centrifuge
of the sample
13 ml of concentrated
on a hot plate
solution
method.
into a 5-ml
a.liquot
containing
the solution
is
and 0.4 ml of hydro a platinum
stirrer.
is centrifuged
for
3 min.
and the supernatant After
another
is
5-rein
digestion
3 min and the supernatant twice
with
each time
0.5 -ml for
tbe Pu is then dissolved
is
portions
3 min.
of
The
in 0.3 ml of 2 ~
acid.
in depolymerizing as sulfuric technique
described
to the purification 112
Pu(IV) acid,
before in this
and isolation
but offers performing paper
a method
of
the extrac-
has been
of Pu isotopes.
applied
Procedure The centration
choice
solution.
The
the health
hazard
per
of the sample
of Pu activity
minute
presence
will
size
and of the beta of high levels
involved
by the magnitude ray
of radioactivity
and because
interfere
is governed
and gamma
a beta
with the alpha
ray
counting
emitters
of the con-
in the original
must be considered
counting
rate
because
of over
on the Simpson
of
109 counts
proportional
alpha
counter. One ml of the sample a 10-ml
beaker.
chloride
Three
solution
mately
80”C.
for
by the addition ‘
30-ml
The
until gas
solution
off and discarded.
of 1 ~
nitric
acid
for
The
3 min.
is discarded,
care
stripped
the organic
of 10 — M nitric alpha
being
acid.
readily
an equal
volume
in the aqueous
the last
by a 5-rein of 0.5 ~ phase.
in the organic strip
solution
phase
aliquot
is pipetted
to dryness
under
an infrared
in a suitable
tional
counter
is washed have
solution
oacetone
for
heat lamp.
plate
a Fisher
phase.
113
phase
wash
pu is then
into
strip
nitric
stainless
steel)
containing
barrier
may
solution
a red acid.
plate
for
organic
the methane
color)
The 1 min.
and evaporated
the evaporated
to destroy
be with
quantitatively
(produces
10 ~
volume
radioactivity
Pu remains
extracted
volume solution
an equal
and protactinium acid
-
is
an equal
The
2 min with
nitric
In this laboratory,
exclusively.
with
tube and centrifuged
(or
is used almost
of extrac-
2-tbenoyltri
the aqueous
-xylene.
of iron
onto a platinum
over
by mixing
of the 10 ~
The
of 0.5 ~
is too high in gamma
off into a centrifuge
counter.
and
at the time
the aqueous
settled,
when tbe Pu is stripped
alpha
to a
thoroughly
volume
of radiozirconiurn
percentage
to a dull red heat
and counted alpha
small
phase
disengaged,
thoroughly
re-extraction
is drawn
A suitable
is heated
traces
4 ml
is transferred
mixed
any of the organic
2 -thenoyltrifluor
The
aqueous
phases
by mixing strip
an equal
have
phase
not to lose
phase
If the aqueous
remains
aliquot
tie
to approximately
solution
aqueous
at approxi-
acid.
10 min with
organic After
taken
measurement,
removed
The
in nitric
for
The
into hydro-
and heated
is adjusted
nitrite,
is pipetted
hydroxylamine
thoroughly
acid. sodium
When the two phases
drawn
from
nitric
ceases.
1~
is extracted
fluoroacetone-xylene.
for
evolution
and 1 ml of 1 ~
is mixed
2 ml of 1 ~
be approximately
if necessary)
of the solution
of 1 ~
using
acid
solution
volume
drops
funnel
(pretreated
nitric
The
The
of several
to stand
should
ml of 2 ~
added.
5 min.
separator
allowed tion
are
solution
flow
sample matter propor
-
Procedure
3.
Separation
W. S. Maeck, Outline
M. E. Kussy
is oxidized
fission (Ref.
to Pu(VI)
as a tetraalkylammonium
deficient
of Pu in U â&#x20AC;&#x201C; and J. E. Rein
product
mixtures.
261).
of Method Plutonium
extracted
and determination
G. L. Booman,
aluminum
nitrate
reduced
to Pu(III)
with
nitrite,
then quantitatively
with
complex
salting
-iron(II)
extracted
into
and quantitatively
isobutyl
Pu is stripped
solution.
a hydroxylamine
permanganate
into methyl
ketone
from
mixture,
from
an acid-
the organic
oxidized
phase
to Pu(IW)
and
with
TTA.
Yield Overall
recovery
of Pu is 98.870.
Decontamination Overall carry-through
fission
is less
product
decontamination
is greater
than 1 X 104;
U
than 0.0570.
Reagents Reagent
grade
tetrapropylammonium Chemical
Research,
Inc.,
Aluminum in a 2 -liter
plate.
dissolution,
and stir 50â&#x20AC;?C.
for
several
Add
dissolution with
chemicals,
Eastman
and thenoyltrifluoroa
Gainesville,
nitrate
nonahydrate After
inorganic
hydrotide,
Fla.,
salting
beaker
were
until the hydroxide
Co.
1050 grams
Warm
(14.8 ~ ) ammonium
reagent
is complete.
volumetric
flask
nitrate on a hot
hydroxide
dissolves.
hydroxide
to a 1 -liter
Peninsular
of aluminum
of 800 ml.
precipitate
Label
from
purification.
50 ml of 10~0 tetrapropylammonium Transfer
White
obtained
without
to a volume
add 135 ml of concentrated
minutes
used
Place
solution.
and add water
Kodak
cetone
Cool
and stir
below
until
and dilute
to volume
water. The
pared
0.2 ~
fresh
permanganate ganate
Unless
purity
The
solutions
solution
100,000
ferrous
daily.
otherwise
Hanford
of the metal
are
is stored
disintegrations metal
was
sulfate 1.25 ~
and 0.22~
stable
for
in a dark stated, per
sodium
hydroxylamine
min
dissolved
95.QClqO PU239,
nitrite
solutions
hydrochloride
a month
should
and 0.05 ~
or longer.
be pre-
potassium
The potassium
permsn-
bottle.
the Pu levels The
(dpm). in 6 ~
in extractions stock
hydrochloric
4.31% Pu240,
were
solution acid.
approximately
was prepared The
0.28q0 PU241,
isotopic
from
high
composition
and 0.017. PU242.
Equipment The were
made
extraction centrifuge
methyl
isobutyl
ketone
in 15 X 125 mm test wheel cones
was used.
tubes
(4-methyl-2
Thenoyltrifluoroacetone
with a motor-driven
-pentanone)
with polyethylene
wire
stirrer.
114
stoppers.
extractions The
samples
extractions
and strips
An end-for-end were plates
made were
in 50 ml 1 -in.
stainless Frisch
An alpha
steel. grid
chamber,
scintillation
256-channel
counter analyzer
was used system,
for
for
gross
pulse
counting
height
and a
analysis.
Procedure. Add potassium
permanganate.
of methyl wheel.
6 ml of salting
2 ml of 1.25 ~ into another centrifuge.
to facilitate
Carefully
containing
ture
to stand for until
gas evolution
and stir
vigorously
planchet
under
for
Add
20 min.
Remove
Ignite
into the tube. for
Pipette
0.1 ml of 0.05 ~
3 ml of 3. 125~
the tube and strip
0.2 ~
strip ferrous
prepared
5 ml of 0.5 ~ an aliquot
and count.
115
Add
3 ml
5 min on the extraction
and 2 ml of the above
Stopper
3 ml of freshly
ceases.
a heat lamp.
separation.
prepared
containing
of sample
2 ml of the aqueous
0.1 ml of freshly Add
tube.
tube
and extract
hydrochloride,
transfer
5 min.
the tube,
phase
hydroxylamine
to a test
1 ml or less
stopper
15 X 125 mm test
tube
stand
pipette
is ob utyl ketone, Centrifuge
solution
for
phase
organic
centrifuge
nitrite
thenoyltrifluoroacetone of the organic
and then
and allow
sodium
phase
acid,
phase
10 rein,
to a 50-ml
sulfate
0.22 ~
nitric
the mixand let -xylene
and dry
on a
Procedure
4.
Plutonium
Outline
Pu is co-precipitated
precipitate
repeated
is washed
using
La(103)3
the Pu adsorbed successively a mixture
(Ref.
293)
of Metkod The
The
R. J. Morrow
from
with NaOH
with HN03
resin
column
and 2 portions
of HC1 and HI and mounted
solution
from
8~
of 10 ~ for
with La(OH)3
dissolved
precipitation
HN03
HC1.
with NH40H.
and the co-precipitation
The hydioxide
as the carrier.
on an anion
acid
solution,
.
The
Finally,
is repeated
column
and
is washed
the Pu is eluted
with
counting,
Purification This alpha- counted; emitters.
procedure it does
Samples
day old solutions and the beta
is designed
not yield
containing
primarily
for
separation
highly
purified
from
samples 1013
- 1014 atoms No foreign
of 5 X 1013 fissions.
content
was
of Pu have alpha
of Pu samples
betabeen
to be
and gammaisolated
activities
could
from
four-
be detected,
105 dpm or less.
Yield 60% if an electroplating vacuum
volatilization
technique
is used
for the final
step,
and 35% if
is used.
Procedure One operation
can do 12 samples
in 6 hours,
exclusive
of volatilization
or electroplating. 1.
To an acid
solution
add - 1 mg La+3
carrier
Pu alpha-emitting depending Add
2.
of mixed
five
minutes.
Add
enough
supernatant
the isotope
upon the isotope
2-3 drops
satâ&#x20AC;&#x2122;. NaN02
cone.
in a plastic
and an appropriate
tracer.
sought solution
bath for
centrifuge
amount
added
and heat
of activity
level
of activity.
in a hot-water
the solution
five
basic.
minutes.
cone
of standardized
and its level
and its estimated
\TH40H to make
at 60° C in a hot-water
3.
activities
bath for
Stir,
Centrifuge
and digest
and discard
solution.
To the precipitate
add 5 ml
min at 60â&#x20AC;?C in a hot-water
25~0
bath.
NaOH
solution,
Centrifi~ge
Stir
and digest
and discard
for
5
the supernatant
solution. 4.
The
precipitate
hydroxide
HC1 and a volume volume
The precipitate
6.
The
7.
The
of 0.5 ~
H103
is added
in a minimal of the order
volume
of 3 ~
of 4-5 times
the
of HC1 solution.
5.
after
is then dissolved
is then digested
sample
is centrifuged
which
the precipitate
sample
is again
for
10 min in a hot water
and the supernatant is washed
centrifuged
116
with O. 1 ~
solution
bath.
is decanted,
H103 .
and the supernatant
solution
decanted.
a.
9.
A minimal
amount
precipitate
with
After
of concentrated
HC1 is used to di6solve
the
stirring.
dissolution
the sample
is precipitated
with
sodium
hydroxide
and centrifuged. 10.
The
supernatant
with H20
solution
is discarded
and centrifuged
after
and the precipitate
which
the supernatant
is washed
solution
is again
discarded. 11.
To precipitate,
12.
Pipet
the solution
anion
exchange
-5-10
add enough
drop6)
HN03)
to di6solve.
HN03
Heat
resin
column effluent.
and twice
with
saturated
in hot-water
onto a 3 mm id.
and discard
each time,
8~
with H3B03
bath if necessary,
X 6 cm long
(previously Wa6h
Dowex
washed
column
A-1
(1 X 8)
thoroughly
twice
one ml portions
(usually
with
with 8 ~
2 ml 8 ~ HN03
of 10 ~ HC1.
Discard
all
washe6. 13.
To column
add 2 ml of a solution
ing eluate 14.
Either a.
of two alternatives
Boil
the solution
b.
Carefully
Evacuate
system disc
Evaporate three for
drops
2~
diameter
of cone.
solution point
of cone.
HC1.
With
1 to 2 ml, min.
plate
Before
off current, with
acetone.
1/4 in.
plates.
Rinse
a l-in.
at 5-6 volts
stopping remove Mild
solution flaming
117
acidity barely
as cathode,
with
the current,
to dryness
about
onto a
residue
adding
and wash
more
the rinses
to the
and a volume
the disc
suitable
with three
red
end
with two drops
for
add 1 ml cone.
of the plate
with cell
to the methyl acidic
2.5 amps
in
filament.
successively
of water
bell
filament.
to an electrolysis
adjust
Pt disc
solution
of the fflament
tube
then make
of vacuum
through
and redissolve
drops
Carefully
NH40H,
tube.
the remainder
filament
- 1/2 in. from
Transfer
HC1 and three
cone.
of current
to dryness HC1.
in the cell.
with
and pipet
the remaining
the contents
about
the solution
drops 1 -in.
boil
and flash
located
volume
of the tungsten
in air by application
platinum
collect-
or a 40 ml centrifuge
now be followed: small
depression
apparatus.
the filament
flask
may
to a very
onto the central jar
10 ~ in HC1 and 0.5 ~ in HI,
in a 50 ml Erlenmeyer
first
is desirable.
roughly
NH40H.
of
of roughly fifteen Shut
with water,
then
Procedure
5.
Plutonium
Outline
carrying
essentially
of Pu(IV)
cycles
in 12 ~
usually
gives
(notably
the resin
column.
After
adsorption
from
pg of U235 was background
which usually
The
Pu is collected a-counted,
very
clean
one of two ways.
analysis,
are
at least
five
expected
of the four times
as active
samples.
The The
simultaneously strength ditions
resulting
chemical
is constant
the yields
are
the lanthanum
can be performed
divided
to within
somewhat fluoride
on 2-in. The
with
a resolution
of yield.
+ 1%.
lower
to one-half
may
from
determined
(90-97yo), is less
of the
be determined
average
the average
which
probably
gives
aliquots
of very
because
efficient.
by is
of the number
in the two
a set of four of solutions
on
by pulse
of Pu activity
of cpm in the spike
and for
In analysis
step
also
in
aliquote.
is determine
The
are
of 1 - 1. 5Y0.
one-fourth
to be analyzed.
9â&#x20AC;&#x2122;77.
Pt plates plates
are
solution
by the number
)
and yields
Yields
15
tbe usual
column
of about
about
carrying
above
pulse-analyzed.
is subtracted
is usually
NTP is not
to one or two of the original
as the aliquot
value
yield
counts
Pu
containing
the resin
with a standardized
samples
acid;
(A solution
of PU236 in the sample
the calculation
the column.
be detected.
run in quadruplicate
samples
in 12 ~
of Fe and U
could
-analyzed
to the extent
precipitate
through
many of Pu on
= 10-6 mg)
from
may be added
products.
eliminates
with hydriodic
and no fission
of
resin.
and two
adsorption
and any traces
behind.
if necessary,
the fraction
of cpm in the two unspiked
yield.
directly
PU236 tracer
thus permitting two
to Pu(IH)
anion
out in the presence
and also
and Cm pass
quantitatively
(1 smidgin
usually
of the analysis,
spiking
Am
in ability A-1
fission
fluoride
Pu,
quantitative
a-emitters,
carried
step
of Np,
reduction
and may be a-pulse
Pu @ -activity
completion
column
and,
other
in the subsequent
the procedure,
flamed,
Samples
total
after
difference
~-emitting
of the lanthanum
resin
of 0.1 - 0.2 smidgins
are
interfere
and remains
run through
Pu from from
the almost
on a Dowex
precipitation,
the rare-earths
the column
to the +3 state
the great
volume-reducing
dissolution
while
and also
fluoride
may
on the anion
is effected,
is eluted
which
Pu utilizes
to be absorbed
decontamination
lanthanum
iron)
for
to separate
is an excellent
elements
reduced
fluoride
serves
complete
initial
of hydroxylamine,
present
185)
procedure
HC1 medium
of the procedure
The
HC1,
specific
on lanthanum
and Pu (IV)
One cycle
(Ref.
of Method The
Pu(III)
D. C, Hoffman
~der
Quadruplicate
spiked the analyzed
high ionic these
con-
analyses
in 3 h,
Reagents La carrier: PU236
5 mg La/ml
standardized
tracer
(added
as La(N03)3
solution
(in 3 ~
. 6H20
in H20)
HC1),
or Pu standardized HC1:
cone.
HC1:
3~
spike
solution
(12~)
118
(any mixture
of Pu isotopes
in 3 ~ HC1),
HF:
cone.
HF-HN03:
equal
H3B03:
volumes
saturated
NH20H.
HC1:
Solution
I: 0.1 ml cone.
Dowex
A-1
of 2 â&#x20AC;&#x201D; M solutions
solution by weight
35~o
in H20
HN03
per
(10% cross-link,
15 ml cone.
Nalcite
SBR)
HC1
anion
resin
slurry
in H20,
Preparation The portions
200-400
of water
the liquid stirred
and cone,
decanted
thoroughly
cylinder, rates:
<5
solution
disks
of 64-84%
is about 4.4 ~
in a large
successive
to settle resin
and
is then
graduated
of sedimentation The <10
cm/min
reagent
grade,
after
The
appears
to cause
usually
storage
under
by the addition
in H20)
HI cannot
unsuitable
preservative
Even
N2H4
analytical
the samples
is inhibited
tbe eluted for
pulse
contain
to
analysis. free
distilled
HI is
hydrazine
the HI solution.
with-
drops
enough
nitrogen,
of sufficient
to decolonize
be used
(up to
The final
in HI.
elutriant
.
1 ml of HI stock in HI.
by centrifugation
is permitted
the solution
The
on the basis
nitrogen.
preservative
and make
about 0.44 ~
is removed
solution
under
of HI witbout
Oxidation
a solution
present
since
the H3P02
unsuitable.
HI-HC1 to give
with
is allowed
and > 10 cm/min.
HI (Mallinckrodt
preservative)
preparations
207. by volume
times
pipet.
of water
withdrawn
cm/min
Distill
solution.
since
oxidized.
are
the resin
of a vacuum
its volume
<10
about three
in the procedure.
to mak,e them
slowly
fractions
cm/min,
the Pt collection
iodine
The
several
1.570 H3P02
Commercial
each wash
times
HI stock
out distillation,
After
is washed
with
and the following
in HI,
attack
HC1.
solid
or by means
is employed
5.5~
moist
by siphoning
< (1 cm/min,
fraction
mesh
to come
is readily
solution
The precipitate
is added which
and the supernate to equilibrium
oxidized,
fresh
is
at room
reagent
to 9 ml of cone.
results
from
saturated
with gaseous
temperature
is required
every
before few
HC1
the hydrazine HC1.
use and
days.
Equipment Centrifuge Block
for
Fisher Heat
holding
centrifuge
tubes
burner lamp
Pt disks: Pt wire Transfer Vacuum
2 in. diameter stirring
rods
pipets trap
10-cm
glass
40-ml
conical
and syringes
for
withdrawing
ion exchange
supernates
columns
(see
(optional) Note
4, Np procedure)
sample) centrifuges
tubes:
119
Pyrex
8140 (one per
sample)
(one per
Procedure Pipet
m. conical
centrifuge
large
tubes.
samples
(1 -ml
as 25 ml can be taken
the samples, identical
make
ml of solution.
reagent tion
(Note
of each
H3B03 solution
Note
The
and discard
Dissolve
washes
3).
may
wash
and remove
column
Wash
=.
through
these
remaining
transfer
column
helps
Dowex
with
1 drop
with
A-1
the addi-
~
HN03
of saturated of 1.5- 2.0 ml.
resin
1-2 column
tube with two
may be used
The
column
volumes
1 -mlâ&#x20AC;&#x2122; aliquots
air for
pressure the Am
(see
(Note
2) of
of Solution
I.
if so desired.
The
and Cm determinations;
discarded. of the centrifuge
rods,
may
migrating
a few
tube with
centrifuge
and pass
of ~20Hâ&#x20AC;?
HC1 direc~y
1.5 ml of cone.
the solution
HC1,
through
the
will
oxidation
) Wash
tube with
and permit
to run dry
while
air
into the column
to the top of the resin
of the HI solution
the centrifuge
to the column,
be forced
1-2 ml of tie
is applied
during
down the column.
to obtain
quantitative
is about
0.8 cm from
HI-HC1
elution. The
them
by any traces
1.5 ml of cone.
to pass
pressure
through.
is being
and channeling
yields,
drop
elutriant
The dark
activity
band and most
The
applied
and erratic
to it,
elution
collection
of
and those The
reaches which drops
are
expected
on a 2-in.
and collection
regarding
the end of the column are
is begun
to contain
not permitted
are most
is continued This
arranged
allows
However,
when the band for
for The
10-15
possible drops
on the periphery
of the activity
to run together. 120
about the lower peak.
Pt disk
its position.
and
may be seen
to be concentrated
off in a 6- to 8-drop
the end of the column.
in the band or misjudgements
the band
is put on the top of the col~n band of the elutriant
appears
of it comes
the end of the column,
the band has reached
irregularities
the center.
immediate
occur,
of the elutriant
after
cryst~s
to prevent
not be permitted
&I&
disk,
are
on the column.
air bubbles
no pressure
before
HF-2
HC1 to a volume
to a 5-cm
the column
washes
the sides
the washings
should
activity
drops
Wash
Add
of HN03
edge
5 min after
0.5 ml of 2 ~
by adding
cone.
washed
the centrifuge
the Pt stirring
(This
since
for
HC1
of cone.
with the use of pressure.
column.
HC1,
to stand
precipitate
has been
if not to be so used the washes Step 7.
of NH20Hâ&#x20AC;?
in HF by addition
the supernate.
the solution
which
from
~
strength
if necessary.
be driven
solutions
of acid
then 2-4 drops
2.5 ~
with about
and then adding
Transfer
I (Note
as
to 1 or 2 of
the supernate.
the LaF3
stirring,
4 of Np procedure)
effluent
and discard
the precipitate
may be warmed
Solution
aliquots
is added
with a solution
ad
and permit
centrifuge
=.
although
or spike
taper
Stir.
of La carrier
the solution
Centrifuge
solution,
long
reagents.
Wash
5.
into 40-ml
if possible.
volume
at least
Step 4.
Step
used If tracer
the solution
=.
Stir,
solution.
Agitate
of the above
are
or spike.
1-2 drops
Make
1).
aliquots
HC1 or HN03)
up to the same
to that of the tracer Add
(2~in
if necessary).
the others
=. per
tie
are
collected
taken of the Pt near
evaporate. original
Step
10.
Heat
the plate
aliquot
employed
Place
was
(Notes
the Pt disk to red heat
spiked,
under
a heat lamp
in an open flame
and pulse
analyze
and allow
and cool;
and a-count
the drops
a-count
to
if the
if PU236 tracer
was
4 and 5).
Notes 1, added
When
precipitate
The
tbe actual
measured
3.
decolonizing
directly
giving
too low.
following
The but the filament
as about The
enough
HF must be
the solution)
one-half
column
but also
HN03
resin
the volume
volwe
if the interfaces
may,
to
in Solution
be
seen.
I is necessary premature
calculated
of course,
can be clearly
and thus avoid
to fission
from
to destroy reduction
the
of Pu(IV)
is employed.
is evaporated
The
readily
in position
the filament
is heated
then flamed
and mounted
but are having
for
for
fission
usually
counting.
the sample
and checking
apparatus
rapidly
to
several
times
collector
(1/4 to 1/2- in. away) Pu-
vary,
control
The
between
O. 1~0 are
is
upon the
the filament
of the W filament
to within
and
Pt disk
depending
upon the distance
By careful
about 40q0.
a heat lamp,
diameter
to volatilize
The yields
and also
deposit
is heated
are
the
is evacuated
A 1 -in.
seconds
permitted
thickness,
under
by
results
evaporating
of the apparatus
above
a few
evaporated
no visible
W filament
in a vacuum
materisl.
are
counting
to sample
and the filament volatile
directly
to 2000°C
being
and the disk,
chamber
of Hg pressure
if any drops
on a 1 -roil
It is then pla’ced
may be prepared
the fission
preparation
Laboratory.
tures,
effect,”
for
or less
of the sample
“bathtub
attributable
plate
plates
However,
the column.
such effects
Pu activity
is then placed
count the Pu,
To avoid
1300”C to remove
plates
of cone.
is not flamed.
at this
5 X 10-4 mm
case
an extreme
procedure
constructed
in each
of the original
the activity
invariably
is defined
of the column.
If it is desired
to run together
size
of Fe is present,
(thus
state.
4.
to about
quantity
element
volume
The presence
properties
to the tripositive
plate
column
dimensions
experimentally
reducing
taking
this
La carrier. 2.
from
an appreciable
not only to complex
tempera-
ordinarily
obtained. 5. elution
The
Np activity
Step drops
of HN03
Discard bubbling,
per
1: By means
the effluent, etc.,
(During
to rebed
one elution
HC1 and cone.
this
run cone.
until the dark
process
the column
by means
Wash
the resin
Elute
the Np with
remains
with
on the column
after
manner:
of pressure,
the column
but can be resettled
may
has been
separate
several removed.
as a result
of
HC1 and pressure,
permitting
the
If the yield
low
of pressure.
cone.
HC1 containing color
)
itself. Step 3.
O~y
quantitatively
in the following
ml through
Step 2. column
whcih
of Pu may be removed
with
O. I ~
HC1 usually
HC1, give
0.1 ~ HC1.
about three yields
cycles
up to 8 5%.
121
of elution
is very
alternately
after
with
0.1 ~
Procedure
6.
Irradiated
Reactor
F. Girardi
Separation
(Ref.
Outline
of Plutonium
Targets
from
R. G. Hart,
Uranium
Pu is adsorbed
on anion
exti.ange
products
eluted
HN03
by reduction
solved
in HN03
NH20H
- HN03
1~
NH20H.
as Pu(III).
and extracted
spectrograph
analysis.
passing
Finally,
Corriveau,
are
and (2) isotopic are
described
Pu is then
extracted
into TBP
as the hydroxide,
in HN03
types
by
analysis.
to be done on 240 dilution by Pu followed 238 followed by a by Pu
dilution before
for
dis -
of analyses
(1) isotopic
analyses
The
are
7-11 ~
the Pu is back-extracted
two specific
These
1) from
through.
and dissolved
analysis,
These
(Dowex
Pu is then precipitated
describes
U targets.
resion
and impurities
as hydroxide,
procedure
irradiated,
The
into TBP.
, precipitated
This
pulse
with
the Pu remains
by mass
in
L. P. V.
of .Method
HN03 , the U and most of the fission
dissolved,
Products
C. B. Bigham,
167)
The
while
and Fission
M. Lounsbury,
the separation
procedure
is given.
Procedure Total
Pu,
isotopic
- 80C Hg of Pu and the other solution.
Only the second
is added aliquot
-400
dilution
of the heavier
measured The
the Separation
sample procedure.
Total
isotopic
#g of Pu and tie
other
Only the second
rate
carried
through
as described spiked
sample
and unspiked
calculation
lNo detailed reach isotopic See Footnote
section. the total
composition
of the total
238
.
are
removed
from
and a-counting
Pu content
in the unknown. one containing
equilibrium.
the ratios
disintegration
the isotopic Pu content
aliquots,
allowed
of unspiked
From
To the second measured
known.
Both
to stand for The two
z
discs
are
to
through
Two
be accurately
From
composi-
4 or 5 days
and the total
Pu concentration
accurately.
and are
isotopic
method
analysed.
must be accurately
must acid,
to reach
samples,
accurate
Pu
for
and are then carried
- 50 pg of Pu,
aliquot
nitric
in the following
and the isotopic
2
This
the Separation
solution,
with
containing
of the solution
to 15 ml with 7 ~ the spiked
dilution
need be measured
pg of PU238.
disintegration
allow
Pu,
the total
This
and isotopic
and the mixt~me,
to calculate
the dissolver
isotopes.
to stand
Pu is then mass
the unknown
it is possible
allowed
equilibrium
The purified
of the standard,
of the standard,
isotopic
are
from
To the secondâ&#x20AC;? aliquot
and the Pu concentration samples
one containing
removed
a high percentage
to reach
diluted
aliquots,
are
,ug of Pu containing
the spiked
-0.19
Two
accurately.
allow
added
.
pg of Pu,
need be measured
must be accurately
s oluti on.
240
aliquot
known.
-100
-400
containing
tion must be accurately
compositions
with Pu
the dissolver aliquot
is
and the PU238 samples
are
4 or 5 days samples
prepared
are
to now
from
each
of PU238 to PU239 in the rate
sample,
of the standard
PU238
it is possible
to make
an
of the solution.
study has been made to determine the length of time required to equilibrium, but it is known that some considerable time is necessary. 1. 122
Preparation was transferred used nitric tray
(4 drops
three
The
(1)
acid.
Two
The
take
to three
aliquot,
The
acid).
very are
The lamp
slowly
solution
micropipette
(TEG)
in dilute
on the source
and the disc
for
50 pg of U
The
glycol
to avoid
necessary
about
manner.
of tetraethylene
an infrared
hours
containing
in the usual
nitric
place
in 7-11 ~ Dowex
was ignited
decomposition
of
the drying.
and fission
with
20 ml of
with
1 ml of 1 .M nitric
An aliquot
The
nitric
acid,
was passed
1 in the nitrate
form
through
to absorb
a l-ml
tbe anionic
column Pu
complex.
uranium
isotopic (4)
tray
a solution
under
must
An aliquot
procedure
nitrate
(3)
source with
to dryness
of 250-mesh
(2)
plates.
in 10 ml of 1 ~
evaporation
by hot nitric Separation
steel times
of TEG
was then evaporated
to redness. TEG
to a stainless
was then washed acid
of a - counting
7.5
~
products
nitric
Pu was
-40
containing
and the remainder
eluted
washed
strong
through
acid
the column
was then displaced
acid.
of the effluent
analysis
were The
acid.
from
mg of U was retained
for
U
was discarded.
the column
with
4 ml of 1.0 ~
hydroxylamine
nitrate. (5)
The
PU solution
TBP-soltrol (6)
The
was
extracted
to remove
PU was precipitated
ammonium diluted
hydroxide,
to 0.5 rd
five
any U left from
times
with
the aqueous
dissolved
and extracted
2 ml portions
of 30%
with the Pu. phase
with
concentrated
in 100 k of concentrated with two O. 5-ml
nitric
portions
acid,
of 31)~0TBP-
soltrol.3 (7)
The 1~
RI
was then backwashes
hydroxylamine
xide,
washed
nitric
acid.
nitrate
once The
from
the organic
washes,
precipitated
with water,
solution
and dissolved
was then diluted
phase
with
3 half-volume
with ammonium
hydro-
in 20 h of concentrated
to 1001
with
1 ~
nitric
acid.
3
The TBP extraction sition products.
is necessary
to separate
123
the plutotium
from
resin
decompo-
Procedure
7.
Outline
Determination
from
(Ref.
447)
of Method This
of Pu(VI)
of Pu
procedure
into hexone,
concentrated
used
an oxidized
in addition
to two
HC1 and resorption
CeF4-reduced
cycles
LaF3
of adsorption
by reduction
cycle
and extraction
of Pu(IV)
on anion
resin
with NH41.
Procedure 1.
2.
Add
5 mg Fe+++
activity.
Boil
lusteroid
tube.
Make few
5.
containing
volume
of 15 ml (Note Stir
b).
Stir
with
2rnll 50-ml
Make
the solution
fuge.
Wash
Add
Dissolve
for
at a time, Add
supernate
a.
a few
10.
Add
NH40H
few
minutes.
in 3 drops
the precipitate
and wash
into a
stand
3 min and centri-
Discard
the supernate
bath.
Add
Heat
20 mg NaHS03
Continue
and heat for 2 ml
and
of HN03.
to 10 ml with water.
reduction.
with
to heat
a few
for
minutes.
1 ~ HC1 . I ~ HF.
the
a little 5 min. Cool
Discard
and the
to precipitate Centrifuge, 1 drop
H BO and heat on a 7 5°C water 33 1 ml HC1 and 1 ml water and continue
bath to obtain
La(OH)3.
Prepare
solution,
Transfer
Digest
Discard
in a hot water
the supernate
in 1 ml HC1 and 2 drops
with HC1 gas.
bath.
to a prepared a wash
124
Cool
Allow
solution
the
washes.
and wash the precipitate
3 min in a hot water
the solution
a clear
tube with water
NH40H.
the La(OH)3 for
Add
glass
and saturate
column.
Cool
in 1 ml saturated
to a 40-ml
Transfer
Wash
Let
10 ml water.
and dilute
complete
minutes.
on the water
solution
bath.
and wash.
solution
bath,
and wash.
with bichromate
the supernate
8 ~ NaOH.
with
the LaF3
to heat
Dissolve
HF treated
Decant
with stirring,
Wash
containing 9.
HF
the LaF3
bath for
with
the hydroxide
to insure
a
temperature.
immediately.
3 min on a 75°C water
cent rif uge.
Slurry
basic
1 mg of Zr
10 drops
for 5 ml
tube.
the Fe(OH)3
5 mg La,
with
5 min on a 75°C water
10 drops
1 ~ HF.
lusteroid
Digest
the supernate
room
and centrifuge
NHN03. —
clean
to a 50-ml
and dfiute with water to a +++ 3 mg Ce and 2 granules of
reaches
by adding
well
the Pu
HN03
and heat for
sample
Fe(OH)3.
the hydroxide
Discard
Add
containing
3 ml and transfer
Wash
NH40H.
a).
solution
to precipitate bath.
in 3 drops
well
until CeF4
(Note
solution
7.
1 drop
the Fe(OH)3
wash. 6.
ammoniacal
Dissolve
Precipitate
to the acid
down to about
on a 75°C water
‘a2cr207 . in tap water 4.
the solution
the solution
minutes
water 3.
and 1 ml HN03
Heat
the solution
AG
containing
bath for
a
5 ml water
and wash.
HN03.
to come
Dowex
with
to room
l-X8
the
in an ice temperature.
(100-200
mesh)
15 ml HC1 and l/2-ml
HN03
.
Rinse
Transfer remaining
solution Discard
Elute of
pressure
tape
to
50-ml
a
Add
10 drops
Cool
HF
in an ice
Xl~HF.
for
Repeat
15.
Evaporate
Steps
of HNO
a
the tape
portions
through.
and continue
6 ml of HC1 in 2-ml
and dflute
to
to
5 ml.
volume
a
of
portions.
approximately
to
Add
with a piece
of 10 ml.
time.
and Wow
to stand
a few
for
and wash the LaF3
with
minutes.
2 ml
1 ~ HC1
and wash.
in the 50-ml
beaker
off all iodine.
and precipitate
with
with 2-ml pass
to
11.
to drive
in a hot water
tb~ precipitate
tube
at
the supernate
3 tube.
5 mg Fe+++
portion
the solution
centrifuge,
the solution
addition
and 75 mg NH41,
beaker
Remove
through
stirring,
with
7 through
ml centrifuge
Digest
little
solution. with the
15 ml HC1 in Z-ml
20 ml HCl
2 -ml
5 min.
lusteroid
bath,
with
into a 50-ml
Pass
a
Discard
14.
Add
containing
2 mg of La and evaporate
20 mg NaHS03
Wash
of this
the column
and plug the top of the column
portions.
Add
portions
Wash
and washes.
the first
portion
-senfiitive
in 2-ml
Transfer
16.
solution
allowing
2-ml
1 -ml
portions.
the column
solution,
elute
Add
in 2-ml
an eluting
this
several the column.
to
the effluents
the Pu from
the second
13.
washes
portions.
11. Prepare
12.
the tube tith
these
bath for 5 ml water
approximately
Transfer
Fe(OH)3 few
a
to
the solution
by addition
minutes.
containing
5 rnls
1 drop
to a 40
of NH40H
Centrifuge,
with
.
and wash
NH40H.
Discard
the
supernate. 17.
Dissolve
the Fe(OH)3
solution.
Warm
solution
with
ketone)
and stir
transfer
pipet.
and more
19.
Record Am241
21.
of extraction
the hexone
phases
withdraw
the Pu from
O.1~
Centrifuge,
The
solution
Saturate
(methyl
for
3 min.
Centrifuge
to
(upper)
layer
a
to
a
dry
clean,
1 drop
40-ml
with
centrifuge
of saturated
NaBr03
as the
by stirring
â&#x20AC;&#x153; Final
with
the acid
(lower)
Separation
5 ml 6 ~ HN03 phase
241
of Pu
.
Stir
twice
the hexone
by stirring
and transfer and combine
is now ready
procedure
Do not continue
completely b.
and rapidly
Dissolve
and
for
and combine
for
for
the aqueous
the aqueous
3 min with
phase
2
with
step
3 unless
phases.
electroplating.
through
1 granule
step
there
time
to carry
the
5.
of Na2CR207 125
is enough
with
1/2 ml HF
5 ml
into a 50-ml
Notes a.
the
isobutyl
phase.
Back-extract
Repeat
minutes.
NaBr03
if necessary.
centrifuge,
beaker.
few
adding
twice,
saturated
the hexone
the hexone
Wash
HN03.
4 drops
stirrer
and withdraw
rein,
aqueous
a
Add
add 5 ml hexone
mechanical
a
.
bath for
crystals,
extraction
NH4N03
6 ~ HN03
hot water
Transfer the
the time ,,
original 20.
with
the phases,
Repeat
a
NTH4N03
separate
tube..
18.
on
in 5 ml
in a Pt dish.
Procedure
8.
Uranium
and Plutonium
Analysis
et al , (Ref. —.
B. F. Rider,
332)
of Method
Outline
Sample products.
For
described
here
this
of dissolved reason,
gives
irradiated
fuel
U and Pu are
a good
yield,
separated
together
highly
contain
with
before
a good
radioactive
analysis.
fission
The
decontamination
procedure factor.
Reagents
1. Distilled 2.
cone.
HN03
.
4.
2 ~ HN03 - distfiled cone. HN03 U233 solution, standardized. PU236 solution, standardized.
5.
KBr03
3.
6.
8~
- crystals,
NH4N03
ml double solution
until basic to mixing ml.
Hexone
8.
HC1 - C.P.
9.
1~
HN03
- Place
H20
Transfer to.400
grade.
in 2 ~
distilled
7.
reagent
Low
to pH paper.
density
distilled
natural
H20.
U blank.
200 ml distilled
in a large
cylinder,
Check
, double
beaker. Boil
16 ~
Bubble
off excess
NH3
add 50 ml of distflled
of solution
(1.31
HN03
+ 100
NH3 gas through (solution
neutral).
16 — -M HN03
, dilute
* 0.01 @20”C).
- distilled.
HNo
10.
307. H202
11.
0.2 ~
reagent.
3
Low
- distilled - meets
TTA
natural
cone.
HN03
U blank. , double
distiJled
A. C. S. specification,
in xylene
- 4.44 g=
low
TTA
dissolved
HN03
, double
H20.
natural
U blank.
in 100 ml dist~ed
x yl ene. 12.
Xylene
13.
Ether
- distilled.
14.
0.05 ~
15.
H20
- distilled. HN09
- double
- distilled
cone.
distilled
H20.
distilled.
Glassware All HN03 double
and rinsed distilled Separation 1.
glassware
used
with double water
before
is Pyrex
distiJled being
the aliquot
1 ml.
Add
acid,
and several
oxidation 2.
Add
3.
Prepare
until
soaked
are
rinsed
overnight with
in 50y0
50% HN03
and
Procedure
for
analysis in a 15-ml cone and evaporate 233 U one drop cone. and PU236 spike,
a suitable
KBr O
3+
Allow
crystals.
to stand for
to about nitric
1 hr to allow
of Pu to PU02.
1.5 ml 8 ~NH4N03
of 8 ~ about
has been Pipets
used.
and Decontamination Place
which
water.
two scrub NH4N03
in 2 ~
10 ml Hexone ready
for
in2
solutions Hh-03
with
~HN03,
and about
2 ml of 2 ~
use.
126
and evaporate
in separate
15-ml
10 mg KBr03
HN03
to about
cones,
and KBr03
2 ml.
containing .
1 ml
Preoxidize .
Keep
covered
4.
Extract
the U and Pu four
hexone
(methyl
original
with the two 5.
Strip
and HC1,
a gental
Prepare
aqueous
of pure HN03
from
1 drop
portions
of 16 ~ each
of
HN03
to the
extract
in turn
portions
of H20.
3.
with
five
portions
2-ml
to dryness,
Evaporate
nitrogen
add a few
to dryness
on a boiling
and 1 drop
step
2-ml
Scrub
in step
extracts
to dryness.
stream
3 ml of 1 ~
Pu and U residue
adding
prepared
take
5 min with
extraction.
hexone
the combined
of HN03 under
each
solutions
for
ketone),
after
the combined
Evaporate
6.
isobutyl
solution
times
drops
with HN03
water
bath.
of 30y0 H202 , add 1 ml to the
5 and two
1 -ml
portions
to separate
15
ml cones. 7.
Extract
immediately
0.2 ~ with
TTA
(thenoyltrifluor
solutions
Combine
the Pu two times oacetone)
prepared
the TTA
in step
extracts
for
20 min with
in xylene.
6.
Scrub
Save the aqueous
and add a few
crystals
2-ml
portions
of
e ach in turn
phase
for
U.
of trichloroacetic
acid. 8.
Mount
9.
After
the combined pulse
Cover
disk with HI? and evaporate
cone.
nitric,
Evaporate
with
aqua regia
dryness
with
cone.
mass
drop for
1/2 hour
Pipette
three
1 -ml
cones
2-ml
3
before solutions
the combined
Evaporate
sample
Treat
Evaporate
bath
several
to
times.
and submit
(step
Add
sample
7) with xylene.
for
ether
HN03
Evaporate
in 2 ~ Place
1
to
and dissolve
to dryness
portion.
Add
and reflux
the
on a water
bath.
, dissolve
the
HN03
the other
2 portions
solutions. portions
prepared
127
matter
of 8 â&#x20AC;&#x201D; M NH4N03
each extraction.
to dryness.
1~
present.
organic
and evaporate
in one 1 -ml
the U with four
scrub
cone.
portions
scrub
HNO
with a
to dryness.
to dryness.
the organic
of HN03
for
with two Evaporate
refluxes
U fraction
to destroy
1--fraction
of cone.
cone. Cover
times.
of HC1 to the washed
to destroy
2 drops
Extract
HN03
gently
with
15-ml
with
times.
and transfer
water
Again
analysis. 1~
residue
in two
disc
or four
or four
on a boiling
and 3 drops
flame
evaporated
HN03
analysis.
as follows:
a heat lamp.
Cover
seconds,
HhT03 to the evaporated
of HN03 about
cone.
under
three
three
and evaporate
HN03
spectrographic
dryness,
a few
Repeat
the combined
residue
11. Wash the original
14.
reflux
cone.
analysis
to dryness. Repeat
to dryness.
for a-pulse
mass
to dryness
and evaporate
50 ~ of 0.01 ~
13.
Evaporate
cover
to a 15-ml
on a Pt plate
the Pu for
HN03
pipette
12.
extracts
remove
disk with HF.
disk with
10.
TTA
analysis,
of diethyl Scrub
in step
extracts
ether, each
adding
extract
100 k
in turn
12.
over
1 ml of H20
in a 15-ml
15.
Add
3 drops
repeatedly
until the organic
ammonium on a water sample Plutonium
for
ratio
in a Frisch
of Pu23â&#x20AC;&#x2122;
salts. bath. mass
Then Add
Flame
in HN03
spectrographic
the amount
chamber
and Pu240
to dryness
gently
and evaporate
HN03
to the dry
to expel to dryness
cone
and submit
analysis.
of Pu in the original
the a spectrum
activity
obtained.
The
specific
isotopes.
The
PU239 plus
this
Uranium The
activity
activity
of the plate
analysis
activity
by the specific
prepared
is calcdated.
to Pu23â&#x20AC;&#x2122; activity 236 added, of Pu
of the mixture
Pu240
sample,
in step 8. ~ the
ratio
the original activity of Pu 239 to Pu240 atom ratio
a Pu
is calculated
from
can be converted activity
it is necessary
to Pu
to
The is 239
plus
is
that of the individual 239 240 plus Pu weight
of the mixture.
Calculation ratio
data is multiplied the amount
and evaporate
is destroyed.
dissolve
501 of 0.05 ~
multiplied by the original activity PU240 can be obtained. From the mass
by dividing
of HN03,
Calculation
To determine measure
of HC1 and 1 drop
of each
of the various
by the amount U isotope
U isotopes 233 spike of U
present
to U
originally
in the original
128
233
from
the mass
added
sample.
spectrometer
to the sample
to obtain
Procedure (Ref.
9a.
Separation
of Plutonium
from
Irradiated
Uranium
R. O. Lingjaerde
255) Outline
from
0.3-0.5
then eluted adsorbed
of Method The
Pu,
~
HN03
with
U and fission
2.0 ~
onto anion
products
and washed HC1,
are
with 0.5 ~
adsorbed
and the Pu is stripped
exchange
washed
resin,
on a cation
The
HN03.
with
with
8 ~
exchange
U and fission
8~
HC1.
HC1,
column
products
The
are
Pu is then
and finally
stripped
with
2 â&#x20AC;&#x201D; M HC1. Procedure 5 ml of stock and 5 ml of 1.0 ~ with
water.
of HN03 quently
coagulate
ing fission close
were
reduces
is not allowed
was washed
was
X02-
solution
NaN02
Pu(VI)
to fall
this
solution
with
0.5 ~
products,
was HN03.
to Pu(IV).
below
Care
O. 1 ~,
15 pg Pu),
and made
since
5 ml of 4.0 ~
up to a volume
has to be taken Pu then will
that
HN03
of 50 ml
concentration
hydrolyse
and conse-
The
adsorbed Then
washing
on Dowex 2.0 ~
with
50 (140-160
HC1 was
2.0 ~
applied
HC1 was
mesh)
and the column
to elute
continued
U and accompany-
until the ~-activity
to background.
of concentrated
fraction
which
about
in a flask,
on the column.
This
Pu and remaining amount
(containing
mixed
fission
HN03
was transferred
beforehand
had been
products
were
NaN02
added
+ some to another
washed
with
column
eluted
containing
concentrated
with
(to oxidize
8 ~
HC1,
Pu(LH)
Dowex
a small
to Pu(IV)),
and
1 (50- 100 mesh),
HC1 containing
a little
concentrated
HN03 . After little Finally
the sorption
concentrated
HN03)
the Pu was eluted
step,
the column
was washed
until the effluent with
2.8 ~
HC1.
129
with
was practically
8 ~
HC1 (containing
free
from
~ -activity.
a
Procedure
9b.
Outline
Separation
carry step
from
Uranium
Metal.
J. Rydberg
(Ref.
341)
of Method This
oxidation
of Plutonium
states
on BiP04, is provided
procedure
makes
use of the co-precipitation The
of Pu on BiP04. and then reduced by extraction
Pu is first
to Pu(IV)
into TTA.
oxidized
which
Yield
properties to Pu(VI)
carries.
of the different
which
An additional
is greater
does
not
purification
than 60~0.
Procedure 1.
The
U sample
rein,
giving
2.
The
solution
3.
The
oxidize
is dissolved a soItition is diluted
is made
precipitate fission
in HN03
in HN03
is clear)
is centrifuged
products,
and kept at 90â&#x20AC;?C for
30
and solid
NaBi03
is added
to
state.
0.1 ~
until the solution
HN03
and Pu(IV).
to 5 ~
Pu to the +6 valency
solution
added
in hot cone,
of U(VI)
(if it becomes
and 0.1 ~ This
off.
and especially
precipitate
those
turbid,
in phosphate.
with
carries
HN03
is
The BiP04 most
of the
a chemistry
similar
to
is made
in HN03
Pu(rv). 4.
The
supernatant
0.05 ~
in N2H4
reduced 5.
The
and 0.005 ~
is diluted
M then added
precipitate
contaminated
phosphates
treating drawn
Pu(VI)
In this
in FeH.
to 0.1 ~
(1 drop
, which
BiP04
is usually The
containing
1~
solution
,
Pu is rapidly
to Pu(III).
solution
Bi+H
6.
solution
carries
with
-10 ~
and made
KOH.
and the precipitate
for
each
all the Pu.
some
in the precipitate
with warm off,
in HN03
O. 1 M Bi+H
The
U is centrifuged are
converted
After
in phosphate. to
precipitate,
which
off and washed.
into hydroxides
centrifuging
is washed
0.1 ~
ml solution)
by
the solution
and dissolved
is
in hot cone.
HN03. 7.
After
some
LMHY03, â&#x20AC;&#x201D; acetone phase,
hours
at room
and extracted in benzene. leaving
with
This
the rest
temperature, an equal
gives
a pure
the solution volume Pu(IV)
of the U and the fission
is diluted
to 1
of 0.3 ~
thenoyltrifluoro-
solution
in the benzene
products
in the aqueous
phase. 8.
If desired, with phase
10 ~
the Pu(IV) HN03
can be back- etiracted
or HC104 after
with benzene.
130
a two-fold
in to the aqueous dilution
phase
of the organic
Procedure J.
Purification
10.
Rydberg
(Ref.
Outline
on silica
method
takes
gel from
fission
products
Pu(IV)
does
than 907’..
from
Uranium
and Fission
Products
of Method The
well
of Plutonium
341)
advantage
strong
is achieved
not carry.
nitric
and Nb are
Further
of CUS from
the Pu(IV)
is approximately
that Zr
solutions.
by precipitation
Finally
Purification
of the fact
acid
is extracted 106 from
a 0.5 ~
into
adsorbed
decontamination HN03
solution.
Yield
is greater
TTA.
~ -’y radiation
very from
of fission
products.
Procedure
1. The U03 sample 30 rein, 2.
The
giving
acidity
solution
of the cooled
is run through
of the Zr
3.
and Nb.
length
of 10 cm.
CUH,
La+++
are
added
products
with
The
solution
5.
The
gel.
a dimeter
0.1 ~
insoluble
This
for
, and the
removes
each
most
ml of solution)
to 0.5 ~
and carries
in 0.5 ~
in HN03
of 0.8 cm and a
carrier
CUS precipitates
M HN03. —
is diluted
of O. 3 ~
almost This
to 1 ~
thenoyltrifluor
practically
Th(UX1)
After
of Si02
have
at 90°C for
HN03.
in HN03
most
,
On
of the fission
The precipitate
to dryness
removes
and then kept for
H2S and restores
30
the Pu(IV)
state.
conditions
6.
columns
to 6 ~
and it is then diluted
is evaporated
solution
volume
U,
is adjusted
and kept
off.
min in hot -10 valency
solution
( 1 drop
sulfides
i’s centrifuged
HN03
and Pu(IV).
columns
and ZrOH
of H2S,
in hot cone.
of U(VI)
two
The
to the solution,
the addition
4.
is dissolved a solution
a two -fold
HC104 .
This
practice
it has
back provides
an additional
not proved
necessary
131
are
products
of the organic
into an aqueous
with
in benzene.
and Zr(IV)
of the fission
dilution
and extracted
oacetone
orily Pu(IV)
and the rest
can be etiracted
in HN03
phase phase
an equal
Under
extracted,
these leaving
in the aqueous with benzene,
with
purification to use this
10 ~ from step.
Pu(IV)
HN03 Zr.
phase.
or In
Procedure
11. Uranium
and Water
E. L. Geiger
Outline
(Ref.
from
Environmental
Samples
of Soil,
Vegetation
144)
of Method The
samples
A1(N03)
~ - HN03.
washed
with
and Pu.
and Plutonium
are
The
to bring
the Pu into solution
U and Pu is then extracted and back-extracted
4 ~ HNC)3,
Yield
pre-treated
is approximately
together
into water
as Pu(IV)
into 50% TBP
for
mountirig
in
in tetradecane,
and counting
as total
80 + 15 (S, D. of mean)%.
Procedure Preparation
of samples Cut oven-dried
Vegetation. into
a 150-ml
When
only
beaker.
white
Heat
Carefully
tion,
Cover
cool,
add 1 ml of 2 ~
tube.
Use
4 ~ HN03
into a 125-rnl with
acid normality
entire
sample
into a 50-ml
to cool
with a watch
glass
through
and repeat Proceed
and heat
Wash
combined a watch separator
1.5- liter solution
glass,
to the separator does
not exceed
1 liter
acid.
Add
this
40,
volume
~
in a 200°C
being Allow Cover
and decant
cylindrical
as possible Allow
step.
solution.
to cool
into a 125-ml
sand
treatment,
A1(N03)3
Allow
soil
the sample
to the next
treatment.
of the sample
beaker,
the residue
in the 100 -ml
graduated funnel,
The
and 10 ml of 4870
HN03-HF
proceeding
the
separator
in the crucible
to cool
and then filter.
being
careful
No.
40,
and if basic, to 30-40
with 4 ~ HN03.
to 5 ml.
20 ml of 4 ~ HN03,
Wash
Add
the sample the beaker
that the total
to the extraction 132
to a 125-ml
volume
beaker.
Evaporate cover
the with
cylindrical
with 4 ~ HN03
procedure.
ml.
into a 100-ml
and the filter
Transfer
at 30 ml.
beaker
and evaporate
such as Whatman
beaker
5 min.
Proceed
in a 1.5-liter
15 ml of 70~0 HN03
a filter,
29 ml.
funnel.
until the
Remove
the sample
of the residue
AI(N03)3
through
and heat for
funnel
~
centrifuge
the residue
and pestle
4 hr.
Heat
5 min.
No.
to
procedure.
Place
with nitric
the
as much
the hot 6 ~ HN03-0.25
the solution
dry before
Allow
1.0 g of the 200-mesh
for
Repeat
removed.
to
solu-
the supernate
Wash
3 ml of 707i HN03
in the sand bath for
Leave
5 min.
to the s eparatory
Weigh
2-3 min with a Pt rod. are
Al(N03)3
to a 100-ml
with a mortar
Add
furnace.
and allow
is 4-6 ~ and the total
at 600â&#x20AC;?C
to cool.
10.0 g
procedure.
sieve.
such as Whatman
at 30 ml..
Water.
Decant
sod
~
for
at 30 ml.
point
muffle
furnace
and decant
solution
and then add 15 ml of 6 ~ HN03-0.25
to the extraction
neutralize
at this
the sample
is completely
a filter,
graduated
the sample
graduated
a 200-mesh
of moisture
and weigh
a cold
the solution
to the extraction
and heat
for
with
the muffle
Centrifuge
the wash
solutions
and allow
the sample
all traces
funnel
5 g of oven-dried
furnace
that the sample
solution
and transfer
through
from
and boil
the transfer.
and decant
Pt crucible
then stir
funnel
solution
Proceed
Grind
can pass
the muffle
the sample
glass
separator
29 ml.
Soil.
careful
a watch
of the combined
not exceed
bath until
KN02
starting
the beaker
pieces
then add 10 ml of 8 ~ HN03-0.5
to complete
centrifuge,
should
HF.
with
cylindrical
4 ~ HN03,
from
remove
add 2 ml of water,
the beaker
into small
at 6000C,
the sample
ash remains,
cool.
vegetation
and transfer
in the separator
funnel
U
Extraction. Add funnel.
Dilute
30 ml of 5~o an air-driven
1 ml of 2 ~ to the 30-ml
TBP
KN02 mark
to the sample with
Agitate
in n-tetradecsne.
stirrer.
Discard
4 ~ HN03
the
in the 125-ml and stir
the solution
acid portion
(lower
cylindrical
separator
the solution
briefly.
vigorously
for
layer).
Wash
the TBP
with
4 â&#x20AC;&#x201D; N HI$03 and again discard the acid portion, Back extract with seven pw-tions of distiJled water, collecting the strip solution in a 150-ml beaker.
the combined a flamed
aqueous
stainless
to burn off organic if the a-count
portions
steel
planchet.
residue,
exceeds
to 10-15 Allow
ml,
then quantitatively
to dry
under
and count on an a-counter.
a specified
level.
133
transfer
a heat lamp, Retain
for
Add
4 min with
flame
portion
15-ml Evaporate
the solution
to
the planchet
pulse-height
analysis
Procedure L.
12.
Plutonium
Messanguiral, Outline
and A.
great,
is spearated
and further
has been
Environment
Meiraneisio
al Water
(Ref.
Samples
J. Scheidhauer,
352)
of Method Pu(IV)
step,
from M.
purified
shown
as low
by chemisorption
with two TTA
to be quantitative
and very
as 0.7 X 10-11 p Ci/ml
on solid
C aF2
cycles.
The
extraction efficient.
by taking
The
a large
as the concentration chemisorption
sensitivity
step
can be made
very
sample.
Reagents Concentrated
nitric
10 — N nitric
acid
2 — h’ nitric 1 — N nitric
acid acid
Concentrated
hydrofluoric
Concentrated
perchloric
Ferric
hydrochloride
hydroxylamine
Sodium
hydrochloride
nitrite
Ammonium 2 ~
acid acid
nitrate
Hydroxylamtie 1~
(d = 1.38)
acid
thiocyanate
A1(N03)3
- 0.5 & HN03
Calcium
fluoride
Solution
of 111 g/1 TTA
in xylene
Procedure 1.
Place
3 liters
of ferric 2.
Heat
3.
Let
ad
and agitate
Pour
with this
a glass
cool
down,
several
solution
add water
water
to be analyzed
~ydroxylamine
with
the solution
testing 4.
of filtered
nitrate
stirring making
crystals
rod to about sure
the Fe ‘++
of ammonium
in a plexiglass
to within
in a beaker
and add 5 g each
hydrochloride.
column
0.5 cm of the top.
60-7@C. is reduced
thiocyanate which
Start
from
is closed
agitation
by spot time
to time.
at one end and
with
a magnetic
stirrer. 5.
6.
Add
10 g sodium
HN03
( d = 1.38),
solved
the ferric
Then
After
(see
agitating
vessel.
8.
The
Fig.
minutes
for
1 hr,
filtration pump. cake
the tube under
which
fuloride
add 60 ml concentrated
HF when the HN03
has redis-
has formed.
powder
and place
the filtration
system
on
58).
Wash
the filter
several
then 45 ml concentrated hydroxide
of a laboratory
into
After
add 0.2 g calcium
the column 7.
nitrite.
invert may
the column
be speeded
two times pressure. 134
with
over
a 5-10 liter
by maintaining
250 ml of distilled
plastic
pressure
water
receitig
by means
introduced
Fig. 58. Cross sectional view of the agitation column. The material is â&#x20AC;&#x153;Altuglas MZDâ&#x20AC;? throughout except for the brass screws. The diffuser plate has a total of 213 holes drilled on 8 concentric circles. The inside dimensions of the column are 8.0 cm diameter by 60 cm high. The reader is referred to the original paper for a more detailed drawing.
135
9.
After
disassembly
in a 100-ml which 10.
Add
of the filtration
beaker.
is poured
The
is reduced
with water.
- HN03
Fe ‘~ Add
Continue
to evaporate
is completely 0.5 sodium
make
sure
nitrous 13.
Add
for
membrane
is placed
with distilled
water
to about
15 ml. and let (with
agitation.
Add
that the ferrous
to a boil.
When the
the filter
cool.
and wash
Make
ammonium 1.5 ml
sure
it
the
thiocyanate
).
10 ~ HNC)3 and Expel
ion is oxidized.
the
solution.
Agitate
so that the two phases
are
well
1/2 hr.
Permit
15.
Back-extract
the phases two times
to separate
with
phase
10 ~ HN03
and draw
off the aqueous
phase
with
a pipette.
5 ml 1 ~ HN03.
the Pu(IV)
the organic The
remove
by spot testing
and start
by spot testing
and brihg
20 ml,
hydrochloride
reduced
nitrite
15 ml TTA-xylene
14.
16.
briefly
vapors.
mixed
Wash
solution
to approximately
11. Add 4 ml 1 ~ hydroxylamine 12.
the filter
is washed
into the beaker.
4 ml of the Al(N03)3
volume
apparatus
apparatus
by agitation
two times
phases
are
with
with
5 ml 10 ~ HN03
for
1/2 hr.
Wash
3 ml 10 ~ HN03.
combined
in a 30-rnl
beaker
and evaporated
to
dryness, 17.
Take
18.
Stop heating
up with
perature 19.
Let
Add
Add
cool
thin glass
1 ml
beaker 21.
Stir
23.
Add
24.
Let
1 &J HN03
two times
The
26.
The
and 3 ml HC104 hydroxylarnine
and evaporate
hydrochloride
slowly
for
and transfer
for
Pu is next
and the organic combined
is reduced
to a 30-ml
to dryness. when the tem-
by spot testing
using
these
for
funnel,
washing
the
re-extracted
with
1 ml 2 ~ HN03
at maximum
the aqueous
speed.
phase.
Wash
two times
3 ml of 1 & HN03. by agitation
is washed phase
again
in the funnel.
vapors.
20 min
and eliminate
10 min with
the beaker washes
the nitrous
and stir
separate
phase
Wash
Combine
5 min to expel
aqueous
separator
1 ml of 1 ~ HN03.
to the funnel.
5 ml TTA-xylene the phases
that Fe ‘++
and verify
with
0.15 g NaN02
by agitation 25.
1~
rod.
and 0.5 ml 2~HN03. 22.
HN03
permits,
the solution
a very 20.
2 ml fuming and add 1 ml
two times
is evaporated
136
for
20 min with with
5 ml of 10 — N HN03,
2 ml of 10 — N HN03.
on a watch
glass
and counted.
Procedure (Ref.
13.
Piutonium
Outline
Environmental
Water
Samples
J. Kooi
and U. Hollstein
of Method BiP04
gas.
from
237).
The
solution
Pu is further
is used to concentrate
the Pu after
is heated
several
purified
nitric
acid,
HN03
and the Fe+++
to 100’C
by co-extraction
Finally,
the organic
99uj’ofrom
to Pu(IV)
to expel
cupferride
is destroyed
as the hydroxide,
Approximately
reduction
minutes
into ferric
matter
precipitated
Yield.
for
as Pu(IH)
by wet-ashing mounted
solutions
with S02
excess
S02. from
The
dilute
with H2S04
and
and counted.
containing
0.8 X 10-6 p CiPu/ ml.
Procedure 1.
Acidify
a 500 ml sample
of water
with
15 ml of 2 ~ nitric
acid
and add
10.4 mg of Bi3+. 2.
3.
Bubble
S02
gas,
technical,
wide
capillary.
Heat
the solution
to expel
to boiling
the excess
orthophosphoric
precipitate 4.
Filter
capillary.
h 5.
through
a filtering
Transfer little
rod
at least
Use
with
distilled
water
for
some
using
a
minutes
in total
resting
to a 250-rnl
the
has been to rtise
drawn
the beaker
on the funnel.
Suck the
narrow-necked
flask
on a ground-glass
beiker,
rinse
placed
plate.
the flask
prepared
15 min make
Allow
overnight.
of which
into a 50-ml
bottom,
After
stirring.
by preference the stem
and add 5 ml of freshly
solution,
20 rein,
at 10@C
the precipitate
directly
cut-off
solution
for
60 ml of a 1 — M solution of stirring with a glass rod and leave
25 ml of 6 — N HCL
the funnel
the Bi-Pu
hydrochloride
2 hr,
funnel,
and to dissolve
flask
it boiling
30 rnin with occasional
a fine-fritted
and the glass solution
for
the solution
Add slowly
umder continuous
to settle
into a wide
S02.
at 90”C for
through
through
and keep
of the
acid
the suspension
gently
with
a
10~. hydroxylarnine
up to about
100 ml with distilled
water. 6.
Using
a pH met-er,
ammonia. 7.
Transfer with
8.
Add
adjust
the solution
into
any kind of grease
described
in 14-16.
h water,
shake,
Add
Add
and let
30 ml of purified
into
by addition
a 250-rnl
a 1-1 s eparatory
funnel,
that can be completely 2 ml of a freshly stand
for
of 70-90
extract separator
lubricating
removed
ml of 2 ~
prepared
the stopcock
by the otidation
57. cup ferron
aa
solution
45 min. Shake the mixture
chloroform,
and run the chloroform paper
the pH to 0.7-0.8
0.1 rng of Fe+H.
through
a 4-5 cm No.
funnel,
using
repeatedly
for
41 Whatmsn
the same
1 min
filter
kind of grease
for
the stopcock. 9.
Shake taining a No. joint.
the chloroform
solution
1.5 g of cupferron 41 Whatman Transfer
ffiter the water
per
with liter,
paper layer
one. 137
20 ml of 0.3 ~ hydrochloric and run the chloroform
into a 250-rnl of the lower
roundbotiom sepsratory
acid layer
flask funnel
con-
through with
ground
into the upper
10.
Add to the solution cupferron
11.
Repeat
solution,
the whole
chloroform. from
12.
Transfer
the lower
after
Wash
down the sides
Add
15.
16.
Add
a 15-cm
Remove
nitrous
sucking
air through
until
or suction,
suJfuric
acid
in upper
(C. P.
iron-
and remove
and
with
cupferrate.
the remainder
in Fig.
grade)
for
flask
of red-brown
afi shown
(C. P.
Reflux
acid
vapors
and sulfur
59.
and attach
to the round-
30 min.
grade)
and heat until the solution
an attachable
bottom.
If the dry
repeat
14 and remove
residue
time
flask.
heating
slight
the dry
not appear
trioxide
by heating,
Two
before
be used,
to a red
snow-white
glow,
of the round-
after
cooling,
as above.
in 1 ml of concentrated
may be needed
by in the
should
in the neck
by heating
later
turbulence
burners residue
condensation
does
sulfur
first
creating
tube,
to prevent
residue
the white Some
trioxide
of the roundbottom
and the other
heating.
repetition
into the roundbottom traces
about 20 ml is left
one to keep the bulb hot, without
17. Dissolve
25 ml of purified
the first
yellow.
bulb and the neck
however;
from
both water-layers
papers
to remove
blowing
nitric
light
Discard
condenser.
2 ml of fuming
appe~s
(8 and 9) with
repetition.
of the two filter
1 ml of concentrated
and 2 ml of a 5%
45 min.
resulting
funnel.
as possible
by gentle
flast
for
twice
the water-layer
off the chloroform
bottom
0.1 mg Fe+++
procedure
the second
chloroform
Distill
funnel
and let stand
to the upper
funnel
of chloroform 14.
shake, extraction
lower
as little 13.
in the upper
HCL
the solid
while
gently
is completely
dis-
solved. 16.
The
final
sample
for
and 1/8 cm thick. counting
position.
drawn-off
HCL
of water. Enclose large
formation 20.
Place for
21.
Count
and two
upside
the tray
Rinse
to near
10-ml Let
beakers
in a porcelain
under
dish,
and satisfactory. Calculate c
where
Pu
Repeat
with
at least
it with
drops
ml of conwith
provided
off the high
10-15~0 ammonia
138
in a
the
to dryness. a second
counting with
voltage,
up to 47-50
in counts
of counter.
1 ml
of water.
5 min to ensure
A simple
the Pu concentration
of sample
a
dish,
and ignite
to oxides.
an a-counter.
Efficiencies
add a few
filled
using
according
device
a light
showed percent
trap
consisting for
to be very may
easily
to the formula
= 9.01 X 10-s ~pc/ml
A = activity
efficiency
onto the tray.
cover
switching
and,
in
onto the tray, a second
Evaporate
the hydroxides
and a ZnS screen,
without
heater
with
stand for
ing samples
tained.
the flask
of 35 mm diameter with the tray
solution
dryness,
of a photomultiplier
liable
a radiant
to be completed,
min to convert
the sample
under
the washing
down.
of Fe(OH)3
10-15
background
of the area.
evaporation
the tray
beaker
on a Pt tray
the counter
the green-yellow
and transfer
After
is deposited
the tray
transfer
about half
centrated
19.
Place
pipette,
covering
counting
Determine
per
minute
and E = percentage
insertrebe ob-
(b)
(a)
Roundbottom flask used for destruction of organic matter. (a) Set-up Fig. 59. (b) Set-up used for removing used for refluxing (----) and removal (â&#x20AC;&#x201D;) of nitric acidchloroform and sulfur -trioxide vapors.
139
Procedure Alloys
14.
Separation
by TBP
(Ref.
of Plutonium
Extraction
from
in Uranium-Plutonium
Chloride
Solutions
R.
P.
Fission
Larsen
Element
and C.
A.
Seils,
Jr.
249) Outline
of Method The
U and Pu are
in a 2 — M HC1 solution. Pu(IV)
with
NaN03
The
reduced
and extracted
Pu is then precipitated
to
U(IV)
and Pu(III)
U is then extracted into TBP
as the hydroxide
by contact
into TBP.
The
and back-extracted
and taken
with Mg turnings
Pu is then oxidized with
0.1 — M HC1.
to
The
up in HN03
for
spectrophotometric
materials
are
used.
determination. Reagents Unless
otherwise
stated,
reagent
grade
1. Tributyl
phosphate,
30-volume
~. in carbon
2. Tributyl
phosphate,
30 volume
~, in Amsco-140
3. Dilute liter
300 ml of tributyl with
carbon
of O,5 ~ sodium phate.
Scrub
filter
paper
phosphate
tetrachloride hydroxide
four
to remove
(a kerosine
(Commercial
(or
Amsco
to remove
times
tetrachloride.
traces
with distilled
Solvents
- 140).
Scrub
of mono-
water
distillate). Corp.
once
) to 1
with
200 ml
and dibutyl
and filer
through
phos-
a large
dry
cloudiness.
Procedure Dissolve this
type
the slloy
of material, Pipette
flask.
For
with
12~
Convert
minutes.
assembly,
phate transfer
funnel.
Treat
paragraph. and shake phase
Add
into a 60-ml
the stripping solutions
separator
funnel.
R.
P. , Anal.
Chem.
~,
Allow
phases
acid
and filtering
separator
Add
10 ml of O.2~ phase Add
phosphate
from
into 545 (1959). 140
assem-
outlined
in carbon separator in the next
organic
extracts
the stripped
organic
and combine
acid
the aqueous tetrachloride
the aqueous
phosand
funnel.
hydrochloric
5 ml of carbon
the
to separate
in the second
to the combined
of
chimney
and catch
the phases
and drain
acid
15 ml of 3070 tributyl
by the procedtire
to separate
its
(3X)
a period
in a filter
the flask Add
60-ml
organic
funnel.
tributyl
paper
over
10 ml of 30~0 tribut yl phosphate
phase
for
dryness
by filtration,
Rinse acid.
1 min.
the organic
the U solution
filter
elements
funnel.
hydrochloric
Discard
out dissolved
fiber
VIII
for
to near
to 10 ml and the hydrochloric
to a second
the phases
separator
Rinse
Group
aqueous
operation.
layer.
‘; Larsen,
Allow,
for
Erlemneyer
than enough
O. 1 g of Mg turnings
of glass
with
in the second
30 sec to wash organic
layer
phase
15 ml of 0.5~
1 min.
by evaporation
the volume
the U-bearing
the Pu-bearing
for
medium
and shake
the extraction
and combine
by Larsen*
10 to 20 mg of Pu into a 50-ml
separator
organic
described
be 35 to 70 mg of U, more
of 12M_ hydrochloric
tetrachloride
Repeat
the procedure
approximately
a double
portions
the U-bearing
tetrachloride
Adjust Add
cylindrical
5-ml
in carbon
will
the precipitated
in a 60-ml
bly with three
2 ~.
Using
separate
filtrate
containing
there
acid.
to about
using
to volume.
to a chloride
hydrochloric
concentration several
an aliquot
207” Pu alloys,
determination.
sample,
and dilute
phase.
and repeat strip and shake
Discard
the
a
50-ml
Erlenmeyer
of 2-ml
portions
Transfer
flask
of 16M — nitric
to a 50-rrd
spectrometrically.
smaller
volumes
O.2~
to otidize
-Amsco-140
a light
organic
phase
phase
transfer chloride wire,
2 ml.
pipette
of sodium
occur.
)
nitric boil~g
and stir
may be present
state
would flask
step
20 min.
and ensure
occur.
)
Allow
with water.
prepared
width from
Heat
treatment oxidation
to cool
Read the absorbance
a series
Calculate
of standards
only.
141
solutions,
the volume
centrifuge
mixing
cone
with
hydroxide
stand
for
with
will
the nitric
some
solution
any polymeric
and dilute
oxidation
blank
the Pu present
carried
through
in a Pu which state.
E
to the sexivalent
to volume
vs a reagent
the
would
2.0 ml of 16~
of the Pu to the quadrivalent acid,
With
state
the precipitate
Add acid
Add
(Evaporation
chloride.
Wash
destroy
a Pt stirring
5 min.
solution.
a
hydro-
precipitates.
not remove
supernate.
the wash
in hot 3M — nitric
of 0.02 mm,
While
and let
the clear
the precipitate.
the solution
to the
strip
of the Pu to the s exivalent
and discard
complete
dissolved
glass
plutonium
as it does
oxidation
(This
and trans-
of 0.2M — HCL
the aqueous
diluent
15 ml of
on a s and bath to reduce
mixing.
in excess
and discard
Add
to separate
10 d
from
as the inert
raffinate.
the phases
to a 15-ml
until
step,
step,
3 rein,
to dissolve
were
475 nq.I and a slit factor
5 min for
bath for
the precipitate
etric
for
centrifuge
water
dropwise
solution
in the next
Centrifuge
acid
hydroxide
raffinate
20 ml of tributyl
Add 0.5 ml of 207. hydroxylamine
15 min with occasional
volume-reduction
introduced
with water,
the solution
Add
Combine
and evaporate
the U.
Determine
use proportionately
is used
Add
operation.
to 7 ml with water.
hydroxide
is not a satisfactory nitrate
acid,
flask.
acid to dissolve
to the aqueous
aqueous
Allow
Erlenmeyer
Transfer
and let stand
the lower
addition
to 5 ml).
state.
(Amsco-140
1 min.
the stripping
and dilute
add 10M — sodium
10 drops
Discard
to a 50’-rnl
add 2 ml of 12M — hydrochloric to approximately
)
U,
(down
nitrite
after
up to volume.
less
flasks
100 mg of sodium
and equilibrate
and repeat
containing
1 min.
nitric
and make
the Pu to the quadrivalent
phase.
acid
fer the aqueous
samples
and equilibrate
organic
hydrochloric
(2X) “on a sand bath
5.0 ml of 16~
with water
and volumetric
approximately
the U separation
to give
acid
to dryness
Add
flask For
of nitric
Add
acid.
volumetric
U x-ray
phosphate
and evaporate
in a 10Tml in l-cm
from
cells
volumat
a calibration
the hydroxide
precipitation
Procedure
15.
Exchange
Method
Outline
Separation F.
with
in 6 — M HC1, Mg,
Mn,
Spectrographic
Analysis
of Impurities
Anion
405)
is dissolved
on an anion
is washed
(Ref.
of Method Pu metal
is adsorbed
of Pu before
Trowell
8 ~
in HC1 and an excess
exchange
HN’03.
column
The
solution
and spectrographically
Mo,
Ni,
Ti,
from
and wash
analyzed
of 8 — kl HN03
the resulting
for
is evaporated Al,
Be,
is added.
mixture
Ca,
to dryness, Cd,
Pu
and the column
Co,
Cr,
taken Cu,
up
Fe,
and U.
Reagents 1.
8 — M HN03
2.
6~
3.
Resin
(Note
HC1 (Note (Note
a). b).
c).
Procedure
1, Weigh into 2.
all traces
4.
Place
the resulting
50 ml sfiica
drain Add
of metal
silica
have
and dissolve
each by tipping
beakers. M Hh’03 add 5 ml 8 —
dissolved,
green
USing the minimum
the columns
5.
of 0.25 g of Pu metal
and mix well.
(d).
Transfer (e))
portions
1 ml 6 — M HC1 in 50-rnl
When Note
3.
duplicate
solutions
volume
beakers
to collect
to the ion exchange
of 8 ~
HN03
containing
the eluted
to rinse
1 ml of 100 ~g/ml
solutions.
Allow
colurnne
(Note
out the beakers. Sc solution
under
the Pu solutions
to
down to the top of the resin. 15 ml 8 ~
HN03
to the columns
and allow
this
eluting
acid to drain
through. 6.
Transfer
7.
Add
tions
Prepare
Note
draw
duplicate
cupboard
and evaporate
the solu-
(f). residues
into polythene
reagent
blanks
and warm
ampules. using
slightly
Note
to ensure
com-
(g)
the procedure
and reagents
above
the Pu.
Pass
0.3 ~
been
removed
HN03.
to the fume
HC1 to the dry
solution;
but omitting 9.
beakers
to dryness. 1 ml 6 ~
plete 8.
the silica
HN03
Note
through
(N&e
the columns
(h) ),
Recondition
until
all traces
the column
for
of green further
color
have
use with
8 ~
(i).
Not es (a)
Prepared
from
concentrated
HN03
(redistilled
from
silica)
and deionised
water. (b)
Prepared
from
(c)
Deacidite
FF
settle
10 min
for
gaseous (SRA
68).
HC1 and deionised Remove
and decant
off
142
fines
water.
by etirring
any resin
still
with water.
in suspension;
Allow repeat
to this
procedure bore for (d) (e)
untfi
silica
column
dimensions.
At this
stage
Condition HN03
all fines fitted
the
wool
3 ml wet plug.
resin
(See
in a 6-mm
Fig.
60).
solution
contains
(g)
This
solution
is ready
(h)
Collect
(i)
Add
the washings
Allow
immediately
blue to green.
before
use by allowing
for
free
analysis
HN03
to settle
Add fresh
for
the resin
with
and all air
funnel
bottle.
a pointed
l/8-in.
bubbles
and decant
off
any resin
the total
resin
volume
SORE
4cm
SORE
6mm
BORE
--
20 cm
QUARTZ
---
60.
have
10 tin
---
0 cm
method.
e residue
to bring
1.5cm
4cm
Pu.
by the polythene
and stir
resin
from
to the appropriate
it is in suspension
Fig.
10 ml 8 ~
--I:
the impurities
and transfer
10 ml 8 ~
rod until
from
them.
This
removed.
Use
a quartz
changes
the columns
suspension.
with
color
(f)
perspex
removed.
)
to run through
about
are
Ion exchange
143
column.
WOOL
PLUG
been
still
in
to 3 ml.
Procedure
16.
Impurities.
Separation
Extraction
Outline
HN03
solution
and the impurities
to the eluted graphite
solution
spark
eluted
which
Spectro~aphic
Method
Using
technique
concentration
for
may be restricted
Al,
This
range
is adsorbed
with 8 ~
Analysis
TBP
F.
of
Trowell
on a KelF/ TBP
HN03.
Sc is added
is then concentrated
Applicability. The
Before
(Ref.
405)
of Method Pu in 8 ~
column
of Plutonium
Chromatography
Co,
Cr,
method
covered
Ga,
Mn,
is intended
for
is from
by the reagent
by evaporation
Fe,
Ni,
chromatographic
as an internal
by the
and Ti.
the analysis
0.5 to 10 ppm.
standard
and analyzed
The
of high-purity
lower
limit
Pu.
of analysis
blank.
Equipment 1.
Column
(for
dimensions
and preparation
see Appendix).
Reagents
1. 6 ~ HC1. Note (a). 2.
16 ~
HN03.
8 ~
HN03.
Note
(b).
0,32 ~HN03. 3.
2 ~HF.
4.
CC14.
5.
Tri-n-butyl
phosphate.
6.
KelF.
(f).
7.
Grease
Note Note
(c).
(d).
Note
solution.
Note
Note
(e).
(g).
Procedure 1.
Weigh
2 g of Pu and dissolve
silica 2.
beaker.
When
all traces
clock
glass,
solution 3.
Cool
(Note
Redissolve complete
5.
Transfer volume
6.
Place solution
of the metal
rtise
into 5 ml
by tipping
with a clock have
down the sides
glass
6~
and warm.
dissolved,
rinse
of the beaker,
HC1 in a 50-ml Note
(h).
and remove
the
and evaporate
the
to dryness.
to ensure 4.
Cover
(i)),
add 5 ml
complete this
16 ~
solution.
residue
HN03,
warm
Evaporate
in 10 ml
8 ~
and add 5 drops
to a moist
HN03,
residue.
warming
2~
HF
Note
to ensure
solution. the solution of 8 â&#x20AC;&#x201D; M HN03
a 50-ml under
to the KelF to rinse
tall-form
silica
the column.
144
/ TBP
column
out the beaker. beaker
Note
(l).
using Note
containing
the minimum
(k).
1 ml 20 pg/ ml Sc
(j).
7.
Allow
the solution
from
chromatographic
column
0.5 ml/min. column 8.
a flow
rate
and allow
of approximately
to drain
through
the
to a 100-ml repeat
CC14,
separating
the wash
funnel
and wash
with two further
CC14.
in a fume
Redissolve
HN03
solution
the washed
dryness 10.
8~
rate.
conditioned
of 10-ml
Transfer
down to the top of the
maintaining
40 ml
the eluted
10 ml
portions 9.
Add
at the same
Transfer with
(5) to drain
solution
to the 50-ml
cupboard.
the residue
Note
beaker
and evaporate
to
(m).
in 1 ml 6 â&#x20AC;&#x201D; M HC1 while
the beaker
is still
warm. 11.
Duplicate agents
12.
reagent
above,
Prepare from
are
the electrodes
dividing
the aliquot
standard Remove HN03
equally
(o))
Note
HN03.
using
the procedure
by pipetting
and re-
between
and reagent
blank
Pu from
and then wash
0.1 ml of the solution
of waterproofed
duplicate
the adsorbed (Note
sparking
of a pair
Prepare
lamp. sample
prepared
the Pu.
for
(10) on to the tops
an infrared
13.
blanks
but omitting
graphite
the two electrodes, pairs
and dry under
of electrodes
solution.
Note
the column
by eluting
the column
with
electrodes,
for
each
(n). with
water
O.32 y
to remove
the
(p).
Notes (a)
Prepared
from
(b)
HN03
redistilled
AR
gaseous
HC1 and deionized
from
silica
water,
apparatus.
Diluted
with
deionized
water. (c)
Prepared
(d)
CC14 AR 8~
from
HF AR
conditioned
and deionized
before
water.
use by shaking
with
an equal
volume
of
HN03 .
(e)
Commercial (see
Appendix).
(f)
Low
density
TBP
purified
by steam
KelF
modding
powder,
distillation
less
and alkaline
than 100 mesh
washing
(see
Appendix).
(!3)
0.1%
Apiezon
(h)
Each
sample
(i)
A vigorous
~
in CC14.
should reaction
be done in duplicate. occurs
if addition
of concentrated
HN03
is made
to hot residue.
(j)
H the residue
is allowed
to go to dryness
it will
be difficult
to re-
dissolve. (k)
See Appendix
(1)
Vitrosil
tall-form
volume
of about
for
column beaker
preparation. nominally
75 ml.
145
50 ml capacity
in fact
has a
(m)
The
activity
of the solution
of the Pu metal. of solution
this
to be evaporated
the tolerance
limit
(n)
Each
and reagent
(o)
Transfer
(P)
The
column
The
effect
sample
each
is due almost
In general
the solution life
blank
is limited
of this
will
without
four
residue
TBP
is that the adsorbed
becomes
content a number exceeding
cupboard. thus have
as some
to the Am low to allow
at one time
in a fume
to the appropriate
run and the column
break-through
to dryness
allowed
entirely
is sufficiently
exposures.
bottle.
is washed
Pu layer
must be replaced
off with
becomes
each run.
longer
when the danger
with
of Pu
apparent.
Appendix Purification 1.
of TBP 250 ml
Place flask
fitted
commercial
with
to 80â&#x20AC;?C,
but take
2.
Remove
the source
3.
Pour
distillate.
care
Note
of hot
Filter
steam
not to heat
NaOH
distillation.
above
this
in a l-litre
Heat
temperature.
distil
for
3 hr,
the mixture Note
rejecting
(a). the
(b).
aqueous
deionized
deionized
and 100 ml 0.5 ~
head for
of heat and steam
the hot TBP/NaOH
the (lower)
4.
TBP
a splash
mixture
phase.
water
water.
Wash
the TBP
and then with two
Note
(Whatrnan
into a separating
funnel
with two 100-ml
and reject
100-ml
portions
portions of cold
(c).
541 paper)
the washed
TBP
into a clean
with
solid
dry reagent
bottle. Preparation 1.
of KelF Chill
Powder
KelF
low
density
microhammer 2.
Sieve
3.
Wet
mill,
the milled
(BSS).
Note
powder
powder
C02
and grind
in a
(d).
and collect
the material
passing
100 mesh
(e).
the powder
excess
molding Note
of 6 ~
transfer
with acetone, HC1 mote
(f)).
Allow
to a 1- liter the KelF/HCl
beaker
and add
suspension
to stand
over night. 4.
Pour
the KelF/HCl
plug and allow by pouring 5.
Finally,
deionized
and then spreading
1.
into a ftmnel
to drain water
dry the washed
the acetone Preparation
suspension
the acid
away.
through
KelF
Wash
with a cotton
the KelF
free
wool
from
acid
the funnel.
by pouring
the powder
fitted
acetone
out onto a polythene
through sheet
the funnel and allowing
to evaporate.
of Column Mix ml
12 g KelF deionized
powder water
and 12 g TBP and mix
to a smooth
to a slurry.
146
paste,
add about
10
2.
Transfer
about
with water glass
plunger
Note 3.
Repeat
Keep with
of this
press
slurry
small
so that an evenly
to the column
quantities
packed
of this
column
(Note slurry
(g))
filled
down with a
of the KelF/
TBP
is formed.
(h). this
column 4.
a quarter
and gently
procedure
with further
portions
of the slurry
until the
is complete.
the column 40 ml
8~
filled
with water
HN03
until
required
for
use and condition
when required.
Notes (a)
TBP/NaOH
(b)
This
(c)
mixtures
removes
most
bump
violently.
of the free
n-butyl
remainder
is removed
by washing.
The initial
separation
and washings
alcohol
must
from
the TBP;
the
be done hot to avoid
emtisification. (d) (e)
Chilling Making
assists
the grinding
the powder
process.
just moist
with
acetone
will
prevent
to
it sticking
the sieve. (f)
To remove
(g)
28 cm X 1.2 cm Pyrex
(h)
Care
must
may
result
quartz
a very
wool
slow
any metallic
impurities. column,
2-mm
bore
tap and fitted
with a
plug. be taken
in the preparation
in Pu breakthrough flow
rate.
147
during
of the column, elution;
tight
loose packing
packing will
give
Procedure Short
17.
(Ref.
Separation
procedure
that
Pu(III)
adsorbed
adsorption
N.
Jackson
and J. F.
of Method This
strongly
Exchange
204)
Outline
on the fact
of Np and Pu by Anion
has been
HC1.
The
for
is not adsorbed
macro
on anion
by dissolving
saturated
separation
with
amotmts
exchange
the hydroxides
is quantitative
while
from
It is based
Np(lY)
adjustment
is
is done before
in a concentrated
The Np is removed
NH41.
of Pu and Np.
resin,
The valence
at high HC1 concentrations.
on the column
which
is described
HC1 solution
the column
with
2 â&#x20AC;&#x201D; M
and complete.
Procedure The
purification
then undertaken. dissolved for
The hâ&#x20AC;&#x2122;p and Pu were
in 210 ml of cone.
30 min
and poured
2.5 cm diameter effluent
were
HC1 and the wash
HC1 sat.
precipitated
a flow
blue
rate
[ Pu(III)
collected
FF
anion
of 1 ml/min
].
The
approtimately50
column
Pu
239
centrifuged, was
allowed
was and
to stand
20 cm 10ng and The first
was then washed
No activity
separately.
solution
was maintained.
column
mgof
as hydroxides, The
with NH41.
onto a Deacidite
while
pale
from
of 2.3 g of NP237
was found
with
200 ml of
100 ml cone.
in a drop
collected
at
to follow
the dark
green
the end of the washing. The
Np was finally
eluted
band of the Np down the column cone.
HC1 wash.
activity
was found
the glass
wool
daughter
of Np
The whole
with
2~
of tbe Np was
in any eluate
after
at the top of the resin 237 .
this
It was
HC1.
and the first
possible
40 ml of eluate collected
stage.
column
148
with the
in the next 50 ml of eluate.
Some
and was
was included
~ -y
activity
assumed
was detected
to be Pa 233,
the
No on
Procedure Zagrai
18.
Separation
and L. I, Sel!chenkov Outline
HC1 solution
with
(Ref.
Exchange
Chromatography
V.
D.
435).
of Method Np(IV)
~
of Np and Pu by Cation
and Pu(III)
after
reduction
are
adsorbed
with
on the cation
S02 at boiling
0.02 ~ HF and the Pu stripped
with
water
resin
KU1 or KU2
temperatures.
from
0.25
Np is eluted
0.5 ~ HF.
Procedure 1.
To 6-8 ml of 0.25 ~ HC1 containing about half
2.
glasfi
column
Pass
S02 gas through
heating 3.
of the resin
Allow
( 1 mm
on a boiling the solution
to the column and pass
pg amounts
in the hydrogen diameter
to cool
vigorously
to room Plug
solution
Wash
the resin
Elute
the Np into a Pt dish or a Teflon
10 ml
of
0.25
the Pu with
min while
4-5 ml of 0.5 â&#x20AC;&#x201D; N HF.
149
and transfer
the resin
with cotton
the column,
~ HC1,
HF. Elute
15-20
the top of the column
through
4.
6.
add
the pleti-
and 1-2 ml of water. for
temperature
5.
with
to fill
bath.
with a pipette.
the remaining
of Np and Pu,
required
X 90 mm high)
the solution
water
form
followed
beaker
with
by 10 ml of H20. 40-60
ml of 0.02 ~
Procedure
19.
Outline
Determination
sample
HC1 and adjusted
hydrochloride
extracted
chloroform,
with
precipitated
ammonium
procedures
R.
are
iron
carrying
O.
R.
Brooks
(Ref.
and the residue
56)
is distilled
the Pu is finally
hydroxide,
dried
at the end of this
on iron off,
et al.
state
in
with
cupferride.
This
and the cupferrides
mounted
again,
by Smales
dissolved
to the trivalent
and co-precipitated
on that described
given
and ashed
Pu is reduced
the chloroform
The
with
is dried The
solution
is wet oxidized.
is based
of urine
to a pH of 1.
hydroxylamine
procedure
in Urine
of Method A 24-hr
dil.
of Plutonium
with cone.
is
residue
HC1,
dried,
and flamed off to Fe203. This 233 Differences in the two
procedure.
Reagents Ferric
chloride
145 mg of FeC13/liter
solution.
Hydroxylamine
hydrochloride 5 ~. aqueous
Cup ferron.
solution,
(i. e.
50 mg Fe/liter).
50 g of NH20H-
solution. renewed
HC1/liter
.
weekly.
Procedure
1. 2.
Evaporate
a 24-hr
basin
under
When
dry,
200-ml
3.
scrape
silica
infrared
sample
infrared
of urine
overnight
in a 2-liter
porcelain
lamps. out and quantitatively
dish with washings
transfer
of 4 ~ HC1,
the residue
and re-dry
to a
it under
lamps.
Place
the sample
by periodic
in a muffle
additions
furnace
of 3-ml
lots
at 5 OO”C, and hasten
of cone.
HN03
oxidation
to the dish when it
is cool. 4.
Dissolve beaker
the white and make
about
100 ml to a final
silica
residue
NH20H” 5.
Adjust
burette
with constant forms,
as this
solution.
3/4 hr to allow
41 filter
chloroform
paper
reduce
and shake
to settle
with
of Pu(VI)
150
from
a
Allow
the solution
to Pu(III). fmmel
thoroughly
of iron
separating
dropwise
that no phosphate
recoveries.
20 ml of distilled
indicator.
until the operator
added
the funnel
to
an insoluble and 10 ml of
and add 2 ml of and let
stand
cupferride. thoroughly.
and then run it off through
into a 100-ml
by shaking
a pH meter
Shake the contents
to a 250-ml
washings
of cresol-red
separating
formation
only
solution
drops
It is essential
reduction
complete
WItil
2 — N NH40H
to a 500-ml
30 ml of chloroform layer
by a few
may
1 hr to ensure
Stir
5 ml of FeC13
with
transfer
4 ~ HC1 and water
of 2 ~.
stirring.
the solution
chloroform
ml of 4 ~ HC1,
to 1 (with
do it visually)
5 ~. cup ferron
No.
Add
solution
Transfer
Add
remains.
the pH of the
to stand for
7.
acidity
followed
precipitate
for
in ’30
HC1 solution
can correctly
6.
residue
up with alternate
funnel. water
Allow
a 7-cm Wash
the
Whatman the
and run the
chloroform h-o.
into a 250-ml
41 filter
solution
paper
round-bottomed
and add a further
a scavenge.
Return
as before.
After
flask
leave
a 7 cm
to the original
aqueous
and 2 ml of 5 % cupferron
5 ml of FeC13
shaking,
through
the water
the solution
to stand
for
as
another
3/4 hr. 8.
Extract until
the cupf errides
the chloroform
into the 100-ml a pipette
9.
and collect
Add
20 ml of distilled they
Evaporate
flask
11.
3 ml of cone.
H2S04
heat.
Evaporate
the final
ness
is not white,
to a pt
further
3-ml
using Dry
this
rod
the tray,
of the acids
in air.
and If the
and take
to ensure
HC1 and transfer for
to dry-
evenly
with a fine
over
drops
transfer.
of water
precipitation
of a
Use two
a quantitative
up in a few
complete
by means
background.
HC1 to obtain
then take
and finally
before
the tray
Maximum
Maximum rate
and add
of ferric
hydroxide.
the tray
(15 cmz
effective
a bunsen
to form
the red
surface)
tip.
heat it over
oxide
counting.
and sample
“background”
With
Maximum
level
Level
level
is 0.01%
a method
permissive
Permissive
permissive
assumed
Corresponding
maximum
in air.
to the residue
each
for
one period
of 8 hr in an
counter.
Calculating
Excretion
an
Procedure
Count a- scintillation
using
by blowing
aliquots
counted
of cone.
precipitation
a glass
Fe203 Counting
cupboard
by blowing
of cone.
previously
solution,
2— N NH40H
Spread
in 3 ml
tray
aliquots
the final
enough
14.
the residue
pipette
Dry
the
chloroform.
6 of H2S04
add further
and shake
into the 250-ml
drops
HN03
the
funnel.
with
the fiml
from
around
extracts,
paper
and 1 ml of cone. trace
forms
the extracts
in a fume
Remove
lot separately
again.
Dissolve
13.
the filter
chloroform
mantle.
Add
residue
12.
and wash
filter
– or
chloroform
separating
to the chloroform out,
each
with
which
in the 100-ml
settled
off the excess
“Electro-Thermal”
of chloroform
paper
of cupferrides
water
have
lots
— and filter
the filter
the washings
After
15-ml
colorless
Wash
the ring
top,
round-bottomed 10.
three
remains
fumel.
to remove
funnel.
with
per
in the body
in urine
is 0.04 EC for
Pu
239
(solution).
day.
Permissive
recovery
in Urine
Level
in Urine
of 90% and a counter z 2.8 cpm above
151
is :, 4 p~c efficiency
“background,
of (say) ”
ss~o,
the
Reporting
Results
Results
< <1
are
reported
in p~c/24-hr
sample
in the following
ranges:
0.1 ppc
> 0,1 p~c > 1
PWC
(exact
figure
reported
with
standard
deviation).
NOTE: Deviations of economy. affect in step
from
this
report
in steps
The use of smaller
the overall 11 above,
recovery. a more
4, 7, and 8 above
quantities
By using rapid
oxidation
152
of reagents
the amounts
were were
of H2S04
was achieved.
made
for
reasons
found not to and HN03
quoted
Procedure
20.
Procedure)
Determination
R. W.
Outline
Perkins
procedure
smaller)
on an 8-mm2 85.2 percent
(Ref.
in Urine
(Small
Area
Electrodeposition
316)
of Method This
200 ml (or
239
of Pu
area
describes
urine
samples,
of a stainless
?3. 6 percent
a method
for
the rapid
and the subsequent
steel
standard
disk.
The
separation
electrodeposition
yield
for
239
of Pu
from 239
of the Pu
a set of five
samples
was
deviation.
Procedure 1.
Place
the urine
sample
(200 ml or less)
add 50 ml of concentrated evaporate
to about
20 ml.
then transfer
water, about
20-30
HN03, Add
water)
Erlenmeyer
carrier
(Note
20 ml of H20
and cool
under
to a 100-ml
Lusteroid
test
the solution
ml of wash
in a l-liter
40 mg of Pr
containing
flask,
(a))
and
running tube (using
5 ml concentrated
HF
and
stir. 2.
Allow
the sample
to stand
nate and dissolve concentrated
HF
centrifuge
3.
Transfer (or
clear).
5.
TTA
(100 g/liter)
the aqueous
of 0.5 ~ HN03,
phase
5 min.
Collect
Combine
Add
Wash
the residue
policeman
evaporate 7.
Add
the
8.
Electrodeposit
9.
The
Add
20 min.
with two
Collect
the aqueous phase
add 5 ml of concentrated KN03
10-ml
layer
in
and shake
to make
sure
adding
water,
HN03,
and evaporate
3 ml of
to dryness.
) (Note
2).
all of the residue washings
Rub sides
of
is in solution.
to the sample,
then
to 3-4 ml. (O. 25 ~ cell
(NH4)2
with
C 204),
an 8-mm2
overnight
electrodeposited
transferring
stainless
steel
the solution cathode
area
a counter, under
at 110 d.
sample or exposed
a microscope*
may
be counted
to a nuclear to provide
* Schwendiman
phase
for
3).
counted C.
5 min
15 min.
and shake
the organic
15 min.
evaporation.
4 ml of electrolyte
ground
L.
and shake
each.
1 ml of 0.1 ~
to an electrodeposition (Note
funnel
in 7 ml of 0.5 ~ HN03
with
5 rein,
phase.
layers,
solution
5 ml of
the precipitate
and shake
5 ml of 8 ~ HC1 to the orgsnic
with policeman
the super-
Add
~ HN03.
NaN02
and wash
5 min
the aqueous
the aqueous
Dissolve beaker
to stand
in benzene
10 ml of 8 ~ HC1 and shake beaker.
discard
and dissolve
separator
0.25 ml of 2 ~
concentrated â&#x20AC;&#x2DC;c 104â&#x20AC;&#x2122; (Use low heat for final 6.
the sample
the supernate
to a 120-ml
Add
Discard
a 50-ml
2 rein,
and 20 ml of 2 ~Al(N03)3-0.5
portions Add
centrifuge
in 50 ml of 2 ~ HN03.
Allow
discard
the solution
until
10 ml of 0.45 ~
4.
and stir.
2 rein,
in 5 ml of H20
30 rein,
the precipitate
and J. W.
Healy, 153
Nucleonics
@
directly track
a greater No.
film
on a low backand the a tracks
sensitivity.
6, 78,
80-82
(1958)
June.
Notes 1.
The
element
Division Chicago, ground;
praseodymium
as purchased
of the American Illinois) whereas,
could
Potash be used
the use of
(from
the Lindsey
and Chemical directly
without
lanthanw
Chemical
Corporation,
West
causing
a high back-
as a carrier
resulted
in a
high background. 2.
At this direct
3.
The
point,
the sample
counting
if small
electrolytic
cells
at one end for cathode
and cylinder
deposition
consist
of lucite
stainless
plating
can be evaporated area
steel
surfaces.
and â&#x20AC;&#x153;defines
cylindegs
which
,., .,
154
which
contact
lucite
the electrodeposition
,.
..
caps
A beveled
on a counting
dish for
is not required.
disk
are
threaded
the stainless fits
area.
between
steel the cap
Procedure
21, Determination
Outline
in Urine
R.
125
J. Everett
et
al.
of Method Micro
amounts
thenoyltrifluoroacetone measured
of Plutonium
of Pu are
(TTA)
by proportional
Evaporation
isolated
extraction,
counting
by lanthanum
fluoride
and electrodeposition.
coprecipitation, The a activity
is
or by autoradiography.
and Electrodeposition
Reagents
and equipment.
Electrodeposition Stainless less
apparatus
steel
disks,
and cells,
0.5-in.
diam
Aluminum
nitrate
solution
distilled
water;
add 23 ml cone.
distilled
water.
Cone.
X 0.005-in.
thick,
polished
stain-
steel.
ammonium
Ammonium
hydroxide
hydroxide,
100 ml with
– Dissolve
HN03
distilled
acid,
36% HC1.
Cone.
hydrofluoric
acid,
487’. HF.
nitric
phosphoric
acid,
in 800 ml
to 1 liter
with
Dilute
10 ml cone.
NH4CH
to
water.
hydrochloric
Cone.
and dilute
9H20
– hTH40H(3 O% NH3).
10~. solution–
Cone.
Cone.
378 g A1(N03)3-
HN03.
TO~o
acid,
85% H3P04.
1— N nitric water.
acid – Dilute
63 ml cone.
2 — N nitric
acid – Dilute
125 ml cone.
HN03
to 1 liter
HN03
to 1 liter
with
distilled
with distilled
water. 8 ~ hydrochloric tilled
acid – Dilute
667 ml cone.
HC1 to 1 liter
with
dis-
water.
8 ~ potassium
hydroxide
– Dissolve
112 g KOH
2— N potassium
hydroxide
– Dissolve
28 g KOH
Sodium
hypochlorite
Sodium
nitrite
water.
– 5 ~. solution
solution
Prepare
Hydroxyl~mine Lanthanum
solution
– NH20H.
1 ml
= 20 mg La. solution
(TTA)
before
– Dissolve
Thenoyltrifluoroacetone
1 ~ HN03.
1.2 g NaN02
immediately
hydrochloride nitrate
distilled
water. water.
NaOC1.
– Dissolve
fresh
in 250 ml
in 250 ml distilled
in 10 ml distilled use.
HC1. 6.2 g La(N03
– Dissolve
)3. 6H20
in 100 ml
5 g thenoyltrifluoroacetone
in 100 ml benzene.
Procedure 1.
2.
To
1 liter
urine
cone.
H3P04,
While
stirring,
10 ml excess
in a 2-liter
beaker,
add 20 ml cone.
HN03,
5 ml
occurs.
Add
and heat to 850C. add cone. and continue 155
NH40H
until precipitation
heat and stirring
for
1 hr.
the beaker
3.
Cover
4.
Decant
5.
Filter
Place
7.
Cool
filter
9000C for
overnight.
careful
not to disturb
onto Whatman
with 10% NH40H. and precipitate
No.
Discard
in 50-ml
the precipitate.
50 filter
paper.
Wash
the filtrate.
Vycor
crucible
and ignite
at
1 hr.
residue
Transfer
8.
settle
being
the precipitate
the precipitate 6.
and let
the supernate,
and add 25 ml 2~ HN03.
to centrifuge
less
than 50 ml.
Cool
to room
Warm
tube with 2N — HN03
temperature
to dissolve
wash,
and add 1 g NH20H.
residue.
and keep
HC1.
volume
Stir
until it
dissolves. 9.
Add
1 ml La(N03)3
solution
and adjust
volume
to 75 ml with
2N —
HN03. 10.
Stir
and add 7 ml cone.
stirring 11.
Let
stand
3 min more,
supernate. 12. 13.
Break
stand for
Stir
Transfer
Add
10 ml
Note:
Add
TTA
For
HC1 layer
Carefully
analysis,
water
color
Cool
appears.
Evaporate
electrodeposition
5 ml
the TTA
cell,
solution
and three cell
to electroplate
times
22.
Remove
cell
without
23.
Remove
disk from
5 min.
Add
10 ml
20 min. beaker.
2~ KOH
phases
with
disk
156
to step Let
distilled Let
separate
separate
until
a pale
volume. once
or let
reddish-brofi solution.
Transfer with
to
1 ml NaOCl
water,
current. with
and
Do not boil
and 2 ml 57. NaOCl
distilled
separate
and repeat.
extraction.
and electrolyte
and wash
phases
to 1 ml.
the beaker
on a
17.
water
phases
Repeat
original
interrupting cell
The
)3
NaN02
can be evaporated
and extract
washing
Connect
lightly.
9,
)3.
5 drops
Let
proceed
to one-half
21.
flame
Add
20 min.
and add 83 KOH by drops
carefully
A1(N03
funnel.
the two HC1 extracts
Add
as in step the supernate.
and add 2 ml A1(N03
Otherwise,
layer.
into 50-ml
evaporate
rod
and extract
counting.
aqueous
HF
is 75 ml.
15 min.
Add 10 ml 8~ HC1 and extract
go dry.
20.
stand
volume
and discard
the
vigorously.
layer.
a rapid
for
until
and add 38 ml more
solution
20 ml distilled
drain 19.
stirring
discard
and stir
7 ml cone.
to a separator
Let
aqueous
and discard 18.
then remove
2~ HN03
stirring,
by adding
with
the solution
planchet 17.
2 rein,
and carefully
ml
Centrifuge,
vigorously
and mix.
and discard
while
3 min.
up precipitate
solution 16.
add a few
2N — HN03 in portions, Repeat LaF3 precipitation
solution. 15.
stand
then centrifuge
To residue,
Add
then let 14,
Let
HF.
rods.
5 hr at 80 rd. Discard
distilled
can now be a-counted
water.
solution. Let
dry and
or autoradiographed.
Autoradiography Reagents
and equipment.
Developer, Fixer,
Kodak
Kodak
D- 19.
F-5
Nuclear-track
alpha
(NTA)
plates
– l-in.
X 3-in.
glass
slide
with
25-P
emulsion. NTA
exposure
camera.
Microprojector Chromic Plate
acid
– arc
illuminated,
solution
– Dissolve
with 21X objective 0.2 g Cr03
and 20X ocular.
in 1 liter
distilled
water.
preparation 1.
Fill
2.
In darkroom
staining
in staining-
dish rack. Let
4 min.
Remove
rack
In darkroom
Lmmerse
drain
of Cr03
solution.
remove
slides
rack
Turn
5 sec.
from
with
disks
from
and slides
off red
tank and let
Series
face-
Fit
top securely
for
1 week.
After
wash
safe
Rinse
develop
Wash
5.
Count the a tracks
plates
an area
for
box and place
in C r03 light
solution
and wash
in
dry.
spiked
load
NTA
plate
in slide
over
NTA
plates,
of positioner. camera
10 min in D-19
and fix
20 min
Expose
in dark box.
developer
in F-5
at
fixer.
1 hr and let dry. with the microprojector. which
h’TA
plate
compared
with known
is called
is 38.82 mm2
coumted on a predetermined are
plates
water
of O. 1409 mmz,
the exposed
filter,
and place
NTA
in distilled
4.
found
slides
disk positioner
down into holes
on camera,
exposwre,
68”F.
AO light Place
of camera.
and drop
3.
full light,
procedure
depression
2.
safe
tank 20 min.
Autoradiographic 1.
red
for
rinse 3.
dish two-thirds with
number
with a standard amounts
Each one field.
or 277 fields. of fields curve
projection The
total
Tracks
are
on each plate.
prepared
from
covers area
Tracks urine
of Pu.
Calculation Since from
standard
1 liter
urine
sample
was used,
dpm Pu/liter
urine
= dpm
curve.
References S. LM. Sanders. L.
C.
Determination
Schwendiman
Plutonium
in Urine,
of Plutonium
and J. W.
Healy,
” Nucleonics
@
in Urine,
“Nuclear78 (1958).
157
Track
DP- 146,
March
Technique
for
1956. Low-
Level
of
Procedure D.
L.
22.
Determination
Bowkowski Outline
(Ref.
wet-ashed
solution. KOH.
Pu is co-precipitated
with
The
in the Presence
extract
is repeated
is mounted is included
ants.
for
of Plutonium
acidified with
The
procedure in urine,
urine, LaF3
and the fluoride acid
the BiP04
from
an HC1
is metathesized
from
a 2 ~
HN03
with
solution,
counting.
to illustrate
of Pu and Am
or a reducing
from
into di(2- ethylhexyl)phosphoric
phase
procedure
determination
with BiP04
and the Pu is co-precipitated
co-precipitation
Pu is extracted
phosphate
acid
HN03,
LaF3
and the aqueous This
in Urine
of Method The
is
of Americium
53).
the extraction
could
presumably
of Pu(IV) be used for
by back-extraction
into acidic a simultaneous
of the Pu either
into
strong
solution.
Reagents Bromthymol indicator
blue
indicator
in 500 ml of distilled
Bismuth
nitrate
solution
solution
water
made
– Dissolve
HNO and dilute 3 O. 1 g of Bi per ml.
contains
4 ~ HC1 – Add a volumetric
flask
one g of reagent one pellet
to one liter
with
distilled
[ Bi(N03
distilled
HC1 to approximately
up to 1 liter
nitrate
with
grade
of sodium
water.
500 ml of distilled
510 ml of cone.
HC1 to 1 liter
in a volumetric
flask.
688 ml of cone.
HC1 to 1 liter
in a volmnetric
flask.
Company, Dowex nitrate La++/
West
solution
Chicago,
Illinois,
50X12
cation
stock
solution
ml.
Only
exchange
is freed
resin
obtained
solutions
– La(N03
)3,
as received
from
column
from
actinum
by the method
is used to prepare
containing
working
0.05 d/rein
water
or less
the Lindsey
Chemical
a-emitting
impurities
of Farabee.
*
solutions
containing
of a activity
per
on a
The lanthanum 25 mg of
mg of La+++
used. 2— M Hydroxylamine
hydrochloride
distilled
water
Prepare
fresh
nitrite
to one liter. solution
in a 100-ml before
O. 1 — M D2EHPA Chemical
hydrochloride
and dilute
2 ~ Sodium
Company)
– Dissolve Store
– Dissolve
volumetric
flask
139.0 g of C. P.
in brown
grade
hydroxylamine
bottle.
13.8 g of sodium and make
nitrite
to volume
(NaN02-AR)
with distilled
in water.
use. – Add
32.3 g of di(2-ethylhexyl)
to chloroform-AR
in a 1-liter
phosphoric volumetric
acid flask
(Union
Carbide
and make
to volume
with chloroform. 8 ~ KOH – Dissolve water
in
water.
6 ~ HCl – Dilute
nitrate
hydroxide. )3. 5H20-AR] This
8 ~ HC1 – Dilute Lanthanum
are
344 ml of cone.
and make
with
231.2 g of bismuth
in 660 ml of concentrated solution
– Dissolve
alkaline
and dilute All
other
65.3 g of potassium
hydroxide
(KOH
86% -AR)
in distilled
to 1 liter. chemicals
are
either
of reagent
or C. P.
*
L. B. Farabee, 5th Ann. Meeting-Bioassay 1,959 (USAEC Report TID-7591 Nov. 1960 p.
158
quality.
and Analyt. 78).
Chem.
Grp. , Oct.
1-2,
Sample
Pretreatment The volume
evening
voidings)
volume
and the liquid
or marking nitric
asbestos
is measured
pen.
acid
are
of a “ 24-hr
level
Several added.
BiPOa
are
added
in HN03
the solution
1 ml of octyl
aicohol
is added
The
of bismuth
dropwise
followed
sample
by gentle
is digested
nitrate
and rapid
of concentrated
an
boiling
nitric
acid
in a steam
solution,
to the heated,
stirred
for
additional The
Urine volume (ml)
Cone. HN03 for 0.15 M (ml) —
500 600 700 800 900
4.8 5.9 6.8 7.5 8.7
3.0 3.6 4.2 4.8 5.4
3.0 3.6 4.2 4.8 5.4
9.6 10.5 11.6 12.45 13.50
6.0 6.6 7.2 7.8 8.4
6.0 6.6 7.2 7.8 8.4
14.4 15.0 16.4 17.3 18.5 19.2
Wet-aahing Several it is placed The
Bi(N03)3
(ml)
soln,
9.0 9.6 10.2 10.8 11.4 12,0
of Bismuth drops
to
per
(Table
VIIf - 1).
100 ml,
ia
is digested
of stirrin”g
beaker
is removed
bath and allowed
disturbed
for
supernatant aspirated
off
(avoid
water
rinse.
supernate
carefully
rinse
transferred volume
mately
to a 90a distilled is cenand the
discarded.
walls
with 4 ~ HC1 from
final
tube with
5 min at 2000 rpm
beaker
The
precipitate
transferred
The precipitate
for
samPle
of 3 hr.
disturbing
centrifuge
trifuged
the
is carefully
and the precipitate ml Pyrex
from
to stand W-
a minimum solution
by an
at 80 + 50C.
are
The
then rinsed
a wash bottle to the 90-ml
in the tube
should
down
and the tube.
The
be approxi-
50 ml.
Phosphate
of octyl
sample
added
Concentrated
0.09 ~
precipitate hour
sample
water
(ml)
9.0 9.6 10.2 10.8 11.4 12.0
in an aluminum dried
are
solution.
Requirements
H3P04
the solution
to 80 +5”C.
to 60 mg bismuth
to the
to its original
to make
of approximately
equivalent
solution.
hydroxide
hydrochloride
bath heated
to a concentration
indicator
is readjusted
is added
initiated
ammonium
blue
ammonium
volume
The
to dryness.
over
stirring
130 ml of concentrated
500 mg of hydroxylamine
placed
is then added
solution
the sample
Concentrated
VIII-1).
TABLE VIII-1. Solution BiP04 Precipitation.
tube;
pencil
and 200 ml of concentrated
by 1 ml of bromthyrnol
by addition
and the beaker
An amount
1500 1600 1700 1800 1900 2000
The
beaker.
a china-marking
and placed
to the cooled
If necessary,
water.
(Table
acid
1000 1100 1200 1300 1400
and two
with a Speede-Vap
Approximately
cautiously,
phosphoric
added
beads,
motor.
endpoint.
with distilled
0.15 ~
with
at high heat.
is completed
green
value
bar
stirring
Neutralization yellow-
tb a 2-liter
on the beaker
is covered
morning
Coprecipitation
a magnetic
hydroxide
transferred
(two
appearance.
A stirring over
glass
sample
denoted
The beaker
a clear
urine
and the sample
are
pad on a hot plate
until it attains
equivalent”
alcohol block
are
added
to the HC1 solution
at approximately
is then repeatedly
159
100”C,
wet-ashed
with
in the 90-ml
and the solution several
taken
ctrops of
)
concentrated
nitric
whiteness,
acid
in a block
it is evaporated
Lanthanum
twice
Fluoride
rinsed After Two
addition
2 ml
solved
for
addition
The
of 2 ml of 27 ~
heated
supernatant
D2EHPA
Following
70”C for
5 min.
acid
thrice
chloroform
The
min with a 5-ml stem
are
tube are
mixed
cone.
thoroughly.
and the solution
5 min and then centrifuged and the precipitate
LaF3
is reprecipitated
and centrifugation
added
dis-
for
by
steps
to the precipitate
is centrifuged
of the precipitate
the precipitate
with
are
and care-
three
minutes
and
of toluene.
with for
Aspirate
conical KF.
D2EHPA
portion
ml of 1:100 hydrofluoric
aqueous
layer
is allowed
acid
layer
for
Lanthanum
drawn
with
is
for
3
through
fluoride
is pre-
to stand 5 min
off and discarded.
wash
is 3 ml
5-rein
is shaken
is then withdrawn
tube.
solution
once
in chloroform
and the aqueous
centrifuge The
The
sodium
the solution
tube is rinsed
furmel,
3 min and the aupernatant
solution
Shake
and centrifuge
ing the supernatant
Drain steel
lamp
removed
ceases,
5 min.
Planchett
tissue.
25 -ml
evolution
centrifuge
The aqueous
of 2 ml of 27 ~
10-15
The
of 0.1 ~
are
one ml of 2 — M bath at
in a water
the “water bath and 2 ml of 2 ~
to the separator
portions
extracts
for
from
is heated
When bubble
funnel. added
in 6 ml of 2 ~ HN03,
and the sample
swirling.
5-ml
into another
at 2000 rpm
Sample
are
aspirated
water,
the mixture
is added,
with
portion
by addition
an infrared
off.
and the rinse
then extracted
sorbent
cooling
separator
periods.
to a stainless
After
added
of 2~ nitric
at 2000 rpm
of the 90-ml
to the centrifuge
then added,
digestion
The tube is then removed are
to a 30-ml
cipitated
walls added
to stand for
hydroxide
drawn
solution
transferred
centrifuged
are
is carefully
The preceding
hydrochloride
solution
the funnel
to
Extraction
hydroxylamine
nitrite
The
the tube contents
(273)
of 2 ml of distilled
HF.
carefully
has ashed
HC1.
ml of 8 ~ potassium
to boiling.
the supernate
acid
The tube is allowed
the addition
Five
)3 solution,
hydrofluoric
3 min.
Following
the sample
in 8 ml of 8 ~ HC1 and the solution
tube.
of 4 ~ HC1 and the rinse
in 2 ml of concentrated
repeated.
centrifuge
of 0.1 ml of La(N03
with a Pt stirrer.
at 2000 rpm
ash is dissolved
conical
an additional
ml of concentrated
stirred
fully
chloride
to a 25-ml
with
After
to 350”C.
8 ~ HC1.
Coprecipitation
The bismuth is transferred
heated
with
15 min.
planchet
and flame
with a low-background
with
Slurry
the centrifuge
the precipitate
a disposable
the dried
proportional
and invert
planchet counter
160
with
capillary
150 min.
distilled
pipette.
to red heat. for
cone
quickly water
over
ab-
and transfer
Dry the disk under
The a activity
is then counted
Procedure
23.
Campbell
Determination
and W.
Outline
D. Moss
of Plutonium (Ref.
Pu is concentrated
that
sorbed with
The
are
prepared
Exchange
by co-precipitation in 7.5 ~ nitric
1 X 2 anion
removed
with
hydrochloric
planchetting
counting
urine
is dissolved
onto Dowex
on the column
specially
from
precipitate
solution
by direct
by Anion
E.
D.
of Method
phosphates. from
in Urine
74)
exchange
resin.
12 ~ HC1.
earth
and the Pu absorbed
Interfering
anions
The Pu is eluted
and hydriodic
or by electrodeposition
with alkaline
acid
from
ab-
the column
and the a activity
acids,
of the eluate,
followed
determined
by standard
Q-
techniques.
Equipment Ion exchange reservoir,
glass
graphic
column.
2-5/8
column
in.
tube 3 in.
The ion exchange
long by 1-3/32
in,
long by 5/16 in.
column
i. d.,
container
capacity
40 ml,
i. d. , constricted
consists
of a
on a chromato-
at the tip.
Solutions Hydriodic (analytical
reagent
servative
) under
nitrogen.
electrodeposition Oxidation
acid grade,
acid
solution. in hydriodic
acid,
The hypophosphoroua
step and also
of the prepaced
(up to 20% by volume
Prepared
stock 5.5 ~
by distilling
acid
with the preparation
hydriodic
acid
solution
of 647. to 847. hydrazine
hydriodic
acid
1.5 ~. hypophosphorous preservative
interferes
of satisfactory is inhibited
in water)
acid
pre-
with the
planchetted
by adding
to decolonize
samples.
enough
hydrazine
the hydriodic
solution. Hydrochloric
hydriodic cipitate
acid
stock
formed
saturated
with
by hydrazine
with
days because
acid-hydriodic
solution
gaseous
is removed
hydrogen
it decomposes
acid
Prepared
by mixing
hydrochloric
acid.
elutriant.
9 ml of concentrated by centrifuging;
chloride.
The
the super natant
reagent
must
1 ml of The pre-
then is
be prepared
every
few
easily.
Reagents All grade
other
reagents
used
in the procedure
are
prepared
from
analytical
chemicals. Preparation
of Ion Exchange
A glass with from
50 to 80 mesh, Richmond., washing solution.
wool
2-1/ 2 to 3 in. anion
Calif.
).
with at least The
pledget
in the tube
of a distilled
exchange The
Column
resin
resin
column
(Bio-Rad
in the column
two 5 ml portions
resulting
water
flow
supports slurry
the resin. of Dowex
Laboratories, is converted
of 7.5 ~ nitric rate
161
is 1 ml/ min.
acid
The tube is filled
AG1-X2.
chloride
form,
32nd and Griffin, to the nitrate before
adding
form
by
the sample
Preparation
of Sample
The cylinder
with
in a steam
24-hr
nitric
bath at 75 to 80”C,
ml of phosphoric hydroxide
acid
to form
stirring,
for
allowed
or equivalent
concentrated
to settle
After
for
precipitate,
several
form,
of ammonium
30 min.
stirring
bar from
at room
temperature.
The
tube with
distilled
is washed cipitate
with
water
dilute
heating
centrated
nitric
The
acid
Isolation
The
but will
acid
solution
and allowed
residue
each
next is added.
The
column
acid,
which
trated
is allowed
hydrochloric
the resin,
dilution
acid
to drain
hydrochloric steps
are
at room
The being
into the centrifuge
from
the column
NOTE: immediate
to dryness
is whitened
in an
with con-
overnight
(preferred
ion exchange with three
through
the column
doivn with
completely.
acid
Three
from
column 5-ml
portions
before
the
ml of concen-
without
to a minimum,
effluents
method).
5 ml of 7.5 — N nitric
to the top of the resin
the 7.5 ~ nitric
is dis-
with heat if
of a prepared
the column
All
precipitate
tube is rinsed
to drain
carefully
completely.
tube.
Finally,
disturbing
and allowing
the absorption
to the top of the column, retained
the
and washing
the first
centrifuge
of 0.5 ~ HC1 and allowed crystals
several
in a 15-ml
of hydroxylamine
and 2 ml of hydriodic-hydro
chloric
.-
acid
several
tube.
to drain
The completely
hydrochloride solution
are
drained
and collected.
The hydroxylamine oxidation
added eluate
with two 5 ml portions
to the top of the resin
through
allowed
through
added
and the remaining
then is eluted
added
with the pre-
discarded.
discarded,
column
centrifuge
the cylinder
combined
be dissolved
temperature
then is washed
One to two ml of 0.5 ~ HC1 are drops
and dis-
to a 90-ml
phosphat,p
may
centrifuge
reservoir
are
earth
residue
to the reservoir
rinse
keeping
The
easily
to drain
acid
the alkaline
acid.
completely.
acid,
overnight
the precipitate
is discarded,
finally
for
bath and the
undisturbed
from
are
several precipitate
is continued
the water
supernattmt
with
Should more
300”C.
from
is transferred
of 7.5 ~ nitric
is treated
is
of the Pu
dissolve
to drain
with continuous
is transferred
and the residue
One
ammonium
the precipitate
to remain
is aspirated
30 min.
is stopped,
from
is allowed
is heated
is digested,
and the stirring
is removed
The
for
in the tube then is evaporated
at 85 to 90”C,
in 25 ml of 7.5 — N nitric
necessary,
is added,
and the washings
at approximately
The ashed solved
the stirrer
precipitate
acid,
material
stirrer,
graduated
cylinder
concentrated
supernatant
and centrifuged.
block
Ion Exchange
phosphate
The
is complete.
the sample
{20~0 ) nitric
in the tube.
aluminum
a magnetic then enough
the supernatant
earth
to a 2-liter
liter).
and the clear
hydroxide
morning
alkaline
per
precipitation
the cylinder
the cylinder,
The following carded.
to be sure
After
is transferred
and the sample
minutes,
hydrofide
an excess
with
to the sample,
30 min of digestion
ml of ammonium
the remaining
sample
(50 ml of acid
and stirred
is added
a copious
1 hr.
urine
acid
hydrochloride
of the hydriodic
acid.
162
is added
An excess
to the column
to prevent
of hydriodic-hydrochloric
acid
solution
should
step.
The
heating
not be used because
eluate
block
of possible
interference
in the tube then is evaporated
in the electrodeposition
to approximately
1 ml in an aluminum
at 75°C.
Electrodeposition The residue hydroxide sodium
using
(The
final
polished ..
the vaporation
phenolphthalein
hypochlorite
the contents
from
as indicator.
concentration stainless
the electrodeposition
disks
Determination
of Alpha
The a activity
counting
method.
The background
cell
with distilled
Pu is electrodeposited
5 hr.
The
2 ml of
to the tube,
apparatus
and
water.
on 1/2 in.
and techniques
for
et al.*
Alpha)
steel
emulsion
of choice
of the NTA for
plates
method
more
method
rapid
can be determined
or by the standard is 0.007 dpm,
evaluation
either
by”
electronic with an accuracy
of results
is the electronic
of the a activity by the phosphor-coated mylar method described by *Xc The phosphor method uses a 1-in. photomultiplier tube and an
of the Los
described
amplifier Alamos
by Grave
adjusted factory
is neutral,
added
and Harley.
all-transistorized Group
are
by Schwendiman
on the stainless
Track
determination
8 ~ potassium
Activity
(Nuclear
Hallden
The
for
described
the NTA
A method
is 1 ~.)
at 200 mA
of Pu are
hydroxide
to an electrodeposition
of the alkali
steel
with
When the solution
and 5 ml of 2 — N potassium
of the tube transferred
of 1.6 dpm.
is neutralized
son
to an optimum for
*L. C. (1951).
and counter Scientific *3
system
Laboratory!s
designed Physics
et al.
The background
efficiency
of 45 ~..
of this
The precision
by P-1
(the Electronics
Division), system of this
similar
to that
is 0.015 cpm when counting
is satis -
0.1 dpm.
Schwendiman,
J. W.
Healy,
D.
L.
Reid,
and G. E.
Hanford,
1861 (1960). **N. A. Hallden and J. H. Harley, Analy-t. Chem. ~, *3 Office, Rpt. NYO R. T. Grave son et al. , AEC New York Operations (TID ORE, Oak Ridge, Term, )
163
HW-22680
1523
(1950).
Procedure
24.
Potassium
Rhodizonate
Outline
Determination
of Plutonium
W.
H.
Shipman
of ethyl
purified
by Co-crystallization Weiss
(Ref.
with
374)
of Method Pu is co-crystallized
volume
in Urine
and H. V.
alcohol
by co-precipitation
The Pu is eluted
with
with potassium
to a pH 9 solution with
LaF3
rhodizonate
of the reagent
and adsorption
6 ~ HC1 - 0.2 ~ HF,
by adding
in urine. on an anion
electrodeposited
and
an equal
The Pu is further exchange
resin.
a-counted.
Reagents Potassium Dowex
anion
Lanthanum purified after
from
was
All
exchange carrier
resin
dissolved
Richmond,
was dissolve
through
the anion
HC1 was
grade
Calif.
d in water
exchange
removed
concentration
of reagent
Ohio).
Laboratories,
nitrate
Excess
to a final
either
Co. , Bryan,
(Bio-Rad
be passage
to 10 ~.
were
Elder
Lanthanum
in 2 ~ HN03
chemicals
B.
AG1 -X8
a activity
the HC1 content
other
(Paul
solution.
interfering
adjusting
the salt
rhodizonate
column
by evaporation
of 5 mg of La++
or C. P.
).
and
and
per
ml.
quality.
Procedure Based was
evolved:
ferent
volume, Add
upon the experimental
The procedure reagents
are
1 g of potassium
for
rhodizonate
of the sample
with HC 1 to pH 2 to 3 effects
for
several
minutes
Dissolve mg of La ‘++ separating
and isolate
the crystals per
ml)
Add
from
with
solution.
Add
Without
separating
stirring
to the supernatant
acidification
to pH 9 with
ethyl
alcohol.
5 — NT
Let
stand
and make
the precipitate
(5
Without
carrier
with
the supernatant
liquid.
and 5 ml of concentrated
alkaline
from
liquid.
carrier
Centrifuge.
add 0.5 ml of lanthanum
H3B03
water
is not fresh,
1 ml of lanthanum
Discard
carrier
) Adjust
30 ml of 27 ~ HF.
and centrifuge.
Centrifuge. with
(Lf the urine
in 5 ml of saturated
10 ml of distilled
a dif-
by centrifugation.
the liquid,
liquid
For
such circumstances
500 ml of absclute
the crystals
and precipitate
the precipitate
about
Under rapid
with
procedure
volume.
amounts.
in 50 ml of 2 ~ HN03.
to the supernatant Dissolve
HC1.
the rhodizonate
the precipitate
stirring
may be difficult.
analytical
sample
to the sample.
of the reagent
and crystallize
a 500-ml
used in proportionate
solubilization
NaOH
the following
results,
is described
with concentrated
the liquid,
Centrifuge.
NH40H.
add O.5 ml of lanthanum
Discard
the supernatant
liquid. Dissolve ml of water, separating stirring
make
in a small
and reprecipitate the precipitate
with
from
to the supernatant Dissolve
H2S04
the precipitate
concentrated
the liquid,
liquid.
the precipitate
volume
of concentrated NH40H.
HN03,
Centrifuge.
add 0.5 ml of lanthanum
Centrifuge.
in concentrated
Discard HN03.
with liquid.
about 3 ml of concentrated
and heat to dryness. Dissolve
the salts
9— N with
concentrated
in 10 to 15 ml of 6 — N HC1. HC1. Let stand 5 min. 164
Add
15
Without carrier
the supernalant Add
add about
0.5 ml of 0.4 “N — NaN02
and
Pour AG
l-x8
the flow
the solution
(Cl-: rate
Wash Collect
the column
with
in a Teflon
Dissolve
Dissolve fitted
0.297 to 0.144 mm)
column,
previously
4 X 0.62 cm anion
waahed
the salt
with a tantalum
15 ml of 9 ~ HC1. beaker
which
the salt in concentrated
2 ml of H2S04J
HC104,
a Teflon
with
exchange
10 ml of 9 — N HC1.
resin Adjust
to 2 ml/ min.
the eluate
drynese,
through
Elute
contains HN03
with 30 ml of 6 — N HC1-O.2 15 mg of NaC1.
and transfer
Evaporate
to glass.
Add
N HF. — to 3 ml of
and heat to dryness. in 1 ml of water
disk.
Add
and transfer
4 ml of 6 — N NH4C1
to the electrodeposition solution
and 2 drops
cell of concentrated
HC1. Electrodeposit centrated tantalum
NH40H. disk
Alpha
at 2.5 to 3.0 A for Wash
the solution
20 min.
from
on a hot plate.
count.
165
Quench
the cell
with
the cell
with
distilled
water
1 ml of conand dry the
Procedure
25.
Primary
Determination
Amines
Outline
F.
W.
of Plutonium
Bruenger,
Concentrated
urine,
by a mixture
back-extracted
with
Reagents
8 ~
Ash
R.
by Extraction
Atherton
(Ref.
with
61)
of bone
branched
ash is made
primary
alkyl
1— M in H2S04
amines.
and
The Pu is then
HC1 and counted.
with a U308
purchased
from
with half
2-in.
standard
J.M - T,
is a 27r proportional
instrument
of accepting
Prirnene
washed
or a solution
of highly
The a-detection
was
and Bone and D.
and Equipment
capable
checked
in Urine
J. Stover,
of Method
Pu is extracted
design
B.
stainless
supplied
a mixture
Rohm
steel
by the National
of tert-alkyl
and Haas,
its volume
of 1 ~
analysis.
Urine
of conventional
counter
Bureau
primary
performance
5 ~. by volume
The
Prirnene
in polyethylene
bottles
Pa.
before
is
of Standards.
amines,
Philadelphia, H2S04
counter
planchettes;
in xylene,
solution
is
use.
Procedure Urine concentrated
formic
the specimen
basic
tainer.
to attain
boiled
without
extracted. The following
cool
washed
twice
with
are
of 8 y
destroyed
is dissolved planchette
by heating
dried
over
Bone
from
under
aliquot
analysis.
Bone
HN03
of this
is ashed
as possible
solution
is taken
every
75-ml
evaporated
to dryness
under
a heat lamp
in solution
with
to a separator Any
CaS04
to
the organic
phase
phase
with
is
with
20 ml of
20 ml of 8 — M HC1.
-diameter
is
of the two
organic
at 5000C.
to a Z-in.
is
in xylene
and then the organic
or in a furnace
4 ml of concentrated
solution funnel.
that forms
is heated Transfer does
for
4 hr at 600°C
and diluted
250 mg for
This
JM-T
extracted
with
been
sample
separation The
from
the Prirnene
and transferred
The
After
is again
a heat lamp
an open flame HN03
phase
is
and is allowed
extraction.
Pu is removed
5~
solution
proportionally.
of Primene
15 min.
second
a
aqueous
not exceed
added.
funnel
for
of the con-
enough
The
contaminants The Pu residue stainless
steel
a counting,
in as little
suitable
are
in concentrated for
dissolved
The
increased
aliquots.
for
The
render
up to 500 ml have
are
100-rnl
is shaken
and Pu is back-extracted
HC1 fractions
volumes
into a separator
H2S04.
HCL
containing
sample.
ml of a 57’. solution
is put aside
25 ml of 1 g
portions
5 ~. Primene, combined
Twenty
far,
of reagents
used for
wool
and the mixture phase
Thus
10 ml of
would
on the wall
flask
in the final
over
which
of Pu by adsorption
of 2 ~
are
of urea,
to a Kjeldahl
1 hr.
glass
temperature.
the aqueous
two 20-ml
in loss
amounts
of reagents
borosilicate
to the sample
phases,
about
volumes,
amounts
to room
result
hydrolysis
is transferred
for
larger
through
excessive
concentration
charring
For
filtered
of urine
an acid
is collected
to avoid
and could
An aliquot
H2S04
added
acid
for
analysis,
volume
HCOOH,
is completed
not interfere.
with a 10-ml
volume.
of bone
of HN03
portion
it is clear,
cooling,
is and a
ash should
The aliquots
the amount
Pu is extracted 166
after
to a known
phase.
and a 6 O-ml
bath until
and,
The. amount
of the aqueous to minimize
in a water
with H20
are
and then put
of 2.5 ~
H2S04
and then transferred
rinse
of distilled
as described
above.
water.
is
Glossary A/coNF.8/
1-17
Vols.
ful Uses New
York,
A&CONF.
Energy,
September
Ed.
in Geneva,
Energy
1-33
Vols.
Conference
Conference
August
– Proceedings
on Peaceful
1958 (United
– Atomic AEC
of the International
held
on Peace-
1955 (United
Nations,
1958).
15/1 English
International
AEC
– Proceedings
of Atomic
Nations,
Uses
of the Second
of Atomic
Geneva,
Energy,
United held
Nations
in Geneva,
1958).
Commission
– Manhattan
District
and later
Washington,
D. C.
AEC
declassified
reports. MDDS -.Manhattan TID AECL
District,
- Technical
– Atomic (ilso
CEI-
ANL
- Argonne
CEA
- France. CEA-TR
Oak Ridge,
Information
Energy
Division,
of Canada,
and CRDCNational
DP
- E,
I.
du Pent
EUR4EC
– United
Hw
- General
Aiken,
So.
Chalk
followed
Laboratory,
assigned
Oak Ridge,
Ltd.,
prefixes
Comrnissariat – Series
Term. Term.
River,
Ontario.
by number.
)
Illinois.
a 1’ Energie
Atomique,
by the AEC
to translations
de Nemours
Paris. received
and Co. , Savannah
River
from
CEA.
Laboratory,
Carolina.
States
- Euratom
Electric
Joint Hanford
Co.,
Research Atomic
and Development Products
Program.
Operation,
Richland,
Wash. JENER
- Joint
KAPL
- Knolls
LASL
- Los (LA -,
Establishment Atomic
Alamos
LAMS-,
- Oak Ridge
USNRDL
- U. S. Naval
UKAEA
- United
AERE
- Atomic
Atomic
Group, Energy
– Health
New
followed
Energy
and Safety
by number.
)
San Francisco,
Calif.
Authority. Establishment,
Establishment,
Branch,
Norway.
York.
Mexico.
Laboratory,
Energy
Research
Kj eller,
New
Tennessee.
Defense
Atomic
Research,
Schenectady.
Laboratory,
Radiological
Kingdom
- Research
Energy
Laboratory,
- prefixes
National
AEEW
Nuclear
Laboratory,
Scientific
and LADC
ORNL
AHSB(RP)
for
Power
Winfrith,
Harwell,
Dorset.
Berks.
Ra~~ogical
Protection
Research
Establishment,
Div. , Harwell.
Berks. AWRE
–“ Great
Britain
Atomic
Weapons
Aldermaston,
Berks. DEG-INF-SER IGO & IGR PG
– Industrial
- Production
Books “The
- Development Group
Group,
and Engineering Hdqtrs.
Risley,
, Risley,
Warrington,
Group,
Risley,
Warrington,
Warrington,
Lanes.
Lanes.
Lanes.
Referenced: Transuranium
G.
T.
Seaborg,
Elements”
(McGraw-Hill
J. J.
and W.
Katz
M.
Book Manning,
167
Co. , Inc. , h’ew York, Eds.
1949).
“The
Actinide G.
“Progress co. “Progress
T.
Elements”
Seaborg in Nuclear
, Inc. , New in Nuclear
Ltd. , London,
(McGraw-HiJl
and J. J. Katz, Energy York,
Series
Book
Co. , Inc. , New
York,
1954).
Eds. III.
Process
Chemistry”
(McGraw-Hill
Book
1956-61).
Energy
Series
V.
Metallurgy
1956-61).
168
and Fuels”
(Pergamon
Press,
References NOTE:
The
first
19 references
ning
of this
monograph.
20.
A.
Adamson,
W.
Clinton
are
Labs.
contained
in Sections
, Oak Ridge,
Term.
I and II at the begin-
CN-2224,
Jan.
1945.
21.
S. Ahrland,
I.
Grenthe,
and B.
Noren,
Acts
Chem.
Stand.
@
1077 (1960).
22.
S. Ahrland,
I.
Grenthe,
and B.
Noren,
Acts
Chem.
Stand.
~
1059 (1960).
23.
A,
M.
Aiken,
Chem.
24.
A.
M.
Aiken,
M.
25.
K.
Alcock,
Nucl. 26.
K.
Alcock,
Chem. 27.
I. V.
F.
Chem.
F. V.
~,
C. ~,
and T.
Bedford,
W.
~,
82 (1957).
Bruce, H.
AECL-1786,
Hardwick,
1951.
and H. A.
C.
McKay,
J. Inorg.
100 (1957).
G.
F.
Form-in, transl.
28.
H. W.
Alter,
H. W.
Alter
Best,
E.
Hesford,
and H. A.
C.
McKay,
J. Inorg.
Nucl.
L.
L.
Zaitseva,
and N.
T.
Chebotared,
L.
V.
Lipis,
~
N.
S. Nikolayev,
Neorgan.
Khim.
~,
951 (1 958).
AEC-tr-3505. W.
D.
and
30.
F.
Anselin,
31.
C.
B. Amphlett,
32.
G. J. Appleton
33.
M.
E.
34.
R.
J.
F.
Baroncelli,
D,
Progg,
328 (1958).
29.
35.
Moss,
Alendrikova,
English
Engr.
P.
Haas,
and
E. Zebroski, Faugeras,
and
H. J.
Zebroski,
Vol.
Compt.
28, p.
UKAEA,
Dunster,
‘AEEW-R-292,
Anal.
Chem.
~
KAPL-442,
1950.
1950.
Grison,
15/1,
UK.AEA,
Bsltisberger,
I.
and E.
A/CONF.
Bains,
E.
KAPL-314,
Rend.
~,
17, Paper
1996 (1956).
271.
AHSB(RP)
R.
6,
1961.
1963. 2369 (1964).
G.
ScibonaJ
and M.
Zifferero,
G.
Scibona,
and M.
Zifferero,
J. Inorg.
Nucl.
Chem.
~,
205 (1963) 36.
l?. Baroncelli,
37.
L.
J.
Beaufait, Vol.
Analysis,
II.
Inc. , Richmond, 38.
M.
Beran
(1963).
and
Jr.
H.
R.
Lukens,
Radiochemical Calif.
Acts
” NP-5056
Procedures,
~, 75 (1963).
of Radiochemical (del. ),
Tracerlab,
, 1952.
Havelka,
and S.
Radiochim.
Jr. , “Handbook
Collection
Czech.
Chem,
Commun.
~,
2510
In German.
39.
K.
S. Bergstresser
40.
M.
G.
41.
B.
Bernstrom
42.
U.
Bertocci.
43.
G.
F.
Berkman
Best,
and G.
R.
and L Kaplan, and J.
Rydborg,
UKAEA,
Waterbury,
LASL,
ANL-4573,
Jan.
Acts
Chem.
AERE-R-2933,
E. Hesford,
May
and H. A.
C.
LA-3091,
1964.
1951.
Stand.
Q,
1173 (1957).
1959.
McKay,
J.
Inor,g.
Nucl.
Chem.
~,
136 (1959). 44.
G.
F.
Best,
H. A.
~,
315 (1957).
45.
T,
K.
Bierlein,
46.
R.
E.
Biggers
4’7.
H.
Bildestein
Fuels”
L.
C.
F.
McKay,
Kendall,
and D. A. ~.,
Osterreichische
and P.
and H.
Costanzo,
“Destructive
R.
Woodgate,
H. van Tuyl,
ORNL-TM-580, Analysis
Studiengesellschaft
SGAE-CH-8/1964. 169
J.
Inorg.
HW-25074,
Chem.
1952.
1963.
of Lnirradiated fuer
Nuc1.
Atomenergie,
and Irradiated Vienna,
48.
D.
49.
hr. A , Bonner
H. Boase,
Wiley
J. K.
Foreman,
and M,
and Sons,
New
50.
M.
Bonnevie-Svendsen,
51.
Z.
Borkowska,
and J. L.
Kahn, York,
y Applied
1951) Chap.
Millcarski,
Talanta
~
53 (1962).
to Chemistry”
(John
6.
“Reprocessing
M.
Drummond,
‘‘ Radioactitit
Analysis”,
and M.
Taube,
JENER-59, J. Inorg.
1959.
h’ucl.
Chem.
~,
359 (1964). 52.
D.
F.
53.
D.
Bowkowski,
Bowersox,
54.
M.
Branica
55.
J. K.
LASL, Am.
and E.
Brody,
J.
LAMS-2884,
Indust. Bona,
P.
Feb.
Hygiene
A/ CONF.
Faria,
and R.
1963.
Assoc.
J. , ~,
15/1 Vol. F.
59 (1964).
17, p 172,
Buchanm,
Anal.
Paper
2412.
Chem.
~,
1909
(1958). 56.
R.
O.
R.
Brooks,
UKAEA,
AERE-AM-60,
(see
slso,
Smalea
~.
,
AERE-c/R-533). 57.
R.
E.
Brooksbank
58,
K.
B.
Brown,
Progr.
59.
K.
B.
Brown,
K.
A.
T.
Gresky,
60.
F.
R.
Bruce,
F.
W.
Bruengerr
A.
C.
A.
J.
Bruenger,
p 58.
E.
Bruns
W.
Nilsen,
A.
Brunstad,
HW-51655,
July
64.
A.
Brunstad,
HW-54203,
1957.
65.
A,
Brunstad
66.
R.
F.
and C.
and R.
Buchanan,
Div.
of Tech.
Infer.
67.
J.
S. Buckingham,
68.
L.
R.
May
Bunney,
HW-52796,
Faris,
K.
A.
, Oak Ridge,
N.
E.
Coleman, -119,
Vol.
2, Chapt. Anal.
AEC
June
IV,
p 557.
D, J. Crouse,
1960.
Atherton,
HW-70084,
Smith,
A.
2, Appendix
8-3,
p 363.
Chem.
Chicago
~.
Opns,
1671
Office.
1961.
1957.
P.
C.
F.
III, R.
C.
J.
C.
CCC1226,
~.,
(1962)
63.
Blake,
and D.
1964.
I-H, Vol.
Energ y Ser.
Stover,
L.
62.
ORNL-3566,
0RNL-CF-60-1
Weaver, Nucl.
B.
also
McDuffee, Ener gy Ser.
Allen,
Progr.
(See
T.
Nucl.
and B.
61.
(1963).
and W.
1957. and J.
Term. , TID-7560,
Cavin,
Ballou,
Sept.
Orlandini,
and C.
J.
A.
Pascual,
P.
Hughes,
June 1958,
Goodall,
HW-59283,
and S. Foti,
AEC
pp 179-88. Feb
1959.
USNRDL-TR-228,
1958.
69.
L.
L.
Burger,
HW-44888,
70.
L.
L.
Burger,
J.
Phys.
.71.
L.
L.
Burger,
I.
M.
72.
J.
P.
Butler
73.
F.
A.
Cafasso,
H. M.
74.
E.
E.
Campbell
and W.
75.
M.
H. Campbell,
76.
G.
Carleson,
A/ CONF.
77.
G.
Carleson,
Svensk
78.
S. C.
79.
W.
80.
D. J.. Carswell,
N.
and J.
Carniglia, Carson,
1957. Chem.
Rehn
~,
and C.
S. Merritt,
D.
Jan.
8/17,
Clinton
p 111,
Labs.
Nucl.
J.
1952,
1956. Phys.
LADC-5922,
Chem.
@
1944 (1964).
1963.
1961. Paper/137.
Tidskrift
Jr. , H. S. Gile, J. Inor g.
LASL,
HW-19949,
Aug.
and 1. Johnson,
Moss,
Kemish
Slansky,
AECL-353,
Feder,
HW-68003,
590 (1958). M.
~
55 (1958),
, Oak Ridge,
Term.,
CN-3339,
and”J.
W.
Vandewater,
Chem.
~,
384 (1957).
170
Aug.
HW-3911O,
1945. Sept.
1955.
81.
D. J.
82.
M.
Cefola
Carswell
83.
R.
B.
and J.
and W.
Chenley,
Milstead,
J.
S. Andrus,
G.
J.
Nucl.
Energy
KAPL-M-MC-2,
Hunter, and T.
~,
51 (1957).
Sept.
J. Webber,
1949.
UKAEA,
AERE-C/M-327,
1958. 84.
A.
Chesnk,
~
85,
A.
Chesn6,
86.
A.
Chetham-Strode,
No.
66, pp 58-64,
NOV.
1962.
In French.
Calif. 87.
M.
88.
89.
Chmutova,
L.
O.
Christenson,
M.
C.
and Physical
Publishers,
New
G.
Nucl.
Radiation
Sci.
Eng.
~,
Laboratory,
557 (1963).
Berkeley,
Petrukhin,
and Yu.
A.
Zolotov,
Zh.
Analit.
Khim.
In Russian.
“ Extractive
E.
Bathellier,
1956.
588 (1983).
E.
and A.
Jr. , Lawrence
UCRL-3322,
K.
~,
G. Koehly,
W.
York,
Chudinov
Kellrey,
A.
Metallurgy 1960) W.
and G.
N.
J.
Bearmint,
and J.
of Pu and its Alloys”
D. Wtiliams,
Yakovlev,
Ed.
R.
Humphrey,
(Inter science
pp 75-88.
Radiokhimiya
~
506 (1962).
In
Russian. 90. 91,
F.
Clanet,
J.
Chromatog.
F.
Clanet,
J.
Clarence,
~,
85 (July
and M.
1961).
Verry,
J.
In French. Chromatog.
@
440 (1964).
In French. 92,
J. W.
93.
J. W.
Nov.
94.
Codding,
W.
O.
Haas,
Jr. , and F.
K.
Heumann,
KAPL-602,
W.
O.
Haas,
Jr. , and F.
K.
Heumann,
Ind.
1951. Codding,
~,
145 (1958).
A.
S. Coffinberry
and M.
B.
Wsldron,
Pro13r.
Nucl.
Enp.
Energ y Ser.
Chem.
V,
Vol.
1,
pp 354-410. 95.
C.
F.
Coleman,
Chem.
~,
A/ CONF.
K.
B.
Brown,
1756 (1958). 15/1,
Vol.
(See
C.
A,
Colvin,
97.
A.
E.
Comyns,
Chem.
98.
W.
V.
Conner,
Dow Chemical
99.
R.
E.
Connick,
100.
R.
E.
Connick
Feb.
101.
0.
A.
Cook,
102.
G.
P.
Cook
103.
J.
Corpel
(English
HW-79354,
Oct. Rev.
in “The
and F.
D. A.
Costanzo
105.
H. W.
Crandall,
106.
L
107.
H. W.
H. Crocker, Crocker,
Moore,
Ind,
and K.
Eng.
A.
Allen,
510.)
1963.
~
115 (1960). Co. , Rocky
Chem. H.
Sot.
McVey,
Transuranium
and O. Jones
104.
and D. J. Crouse, Brown,
Flats
Div. , Golden,
Colo.
1964. J. Am. and W.
transl.
Moore,
Coleman,
28, p 278 Paper/
96.
RFP-356,
J. G. also
Regnaud,
UKAEA Anal.
HW-TR-45.
)
and R.
Biggers,
J.
R.
AECL,
E.
Thomas, CRDC-697,
HW-68655,
Feb.
~,
J. Am,
1528 (1949). Chem.
Vol.
Elements”, IGO-AM/W-68, Chim.
Acts
~,
ORNL-TM-585, and E. May 1961. 171
Sot.
Zebroski,
7fi, 14B,
474 (1953). p 147,
Jan,
1957.
36-9
(1962).
July
In French.
1963.
AEC-TID-1OO22,
1957 (AECL-488).
Paper/3.5.
Aug.
1947.
108.
109.
E. A. F.
C.
L.
Crouch
Culler,
and G.
Progr.
5-4,
110.
J.
G.
Cuninghame
and G.
111.
J.
G.
Cuninghame
and G.
112.
113,
also
(See
of Silica
D. Cvjetcanin
and N.
H. W.
115.
C.
Deptula
and S. Mine,
116.
M.
deTrentinian
Rappt.
No.
1426,
R.
Diamond,
M.
~,
G. A.
Dupetit
119.
R.
Durham
W.
July R.
Pu(VI),
~,
” JENER-45, NukleonikS
France.
~,
~,
) 54 (1956).
72 (1957).
from
Zr
of U and Pu from
and Nb
Zr,
Nb,
1958.
the Isolation
of Pu by a Solvent
1956.
~
197 (1961).
“Extraction
Chesn6,
p 172;
54 (1956 ).]
April
“On Oct.
Chem.
(1956).
1958.
“Separation
1. Dizdar,
5-2,
Paper/822.
and Pu(IV)
Aug.
223-8
and Purification
Comrnissariat
A l’lihergie
of Pu with
Atomique,
Paris,
1960. K.
Jr. , and G.
Street,
T.
Seaborg,
J. Am.
Chem.
Sot.
1461 (1954).
118.
120.
Chem.
Chem.
~,
1, Chap. 560,
J. Appl. Nucl.
of Mn02,’’JENER-54,
and A.
Amine,’1
Vol.
Nucl.
of U(VI),
and Z.
a Tertiary
Miles,
Inorg.
Cvjetcanin,
Procedure,
III,
Chem.
J. Inorg.
Gel, ” JENER-57,
den Boer
Nucl.
P 464, Miles,
L. J.
Extraction
117.
L.
and Cs on a Column
D.
Inorp.
~
“Separation
on a Columr.
J.
Ener .gy Ser.
also
authors,
D. Cvjetcanin,
Ru, 114.
same
Cook,
Nucl.
Chap.
[See
P201.
B.
and A.
H. W.
Jr. , Radiochim.
Aten
and A.
M,
Aiken,
AECL,
and R.
Mills,
AECL,
Oct.
1961.
Acts
CEI-55,
~,
Feb.
48 (1962).
1953.
(Reprinted
1960. ) W.
Durham
reprinted,
AECL-1399,
121.
Ph.
and G.
122.
M.
A.
123.
F.
Elliott
124.
H,
Eschrich,
125.
R.
J.
R.
O.
Mills,
126.
L.
B.
Farabee,
127.
J.
P.
Faris,
Dreze
Duyckaetis,
El Guebely
and T.
and G. W.
Everett,
L.
Liege
for
W.
Sandia
Atomenergi,
Corp.
Clinton
~
and Faris
and R.
and
EUR-436.f.
~,
1963.
473 (1957).
78 (1963).
N.
, Oak Ridge,
Revised
Stand.
Norway,
Edwards,
, Albuquerque,
),
Brussels,
Chem.
Kj eller,
G. W.
Labs.
ANL-6275;
Acts
Nucleonics
Brewer,
(Rev.
University,
Sikkeland,
Pearson,
Institutt
CEI-62,
A.
Mex.
Term. F.
KR - 11 —J
J. Jack, SC-4783
T.
1961. A.
(RR),
, MON-H-218,
Buchanan,
Linn, Feb.
Jr. , and 1964.
1947.
ANL-6811,
1964. 128.
P.
129.
C.
Ferradini
130.
J.
R.
Faugeras
(Masson
~ 131.
R.
et tie,
1962) Vol. Corpel,
W.
Mason,
F.
Fink,
XV,
cle Chemie
hlinerslej”
p 661.
CEA-791, and D.
Traite
1958. F.
Peppard,
J. Inorg.
of California,
Los
Nucl.
Chem.
291 (1961).
Fink
UCLA-30,
G.
ll~Touveau
Heuberger,
Paris,
and J.
Ferraro,
285, M.
and M.
and K.
University
Angeles,
1949.
132.
J.
R.
Flanary,
133.
J.
M.
Fletcher,
A/ CONF. Progr.
8/9, Nucl.
pp 528-31,
Paper/539.
Ener PY Ser. III,
172
Vol.
1, Chap.
4-1,
p 105.
134.
V.
135.
A.
136.
S. C.
V.
Fomin,
R.
E.
Kartushova,
and T.
I.
Rudenko,
J.
Nucl.
Energy
~,
247 (1957). Fontaine, Foti
Talsnta
L.
Baude-Mslfosse,
and E.
n_,
C.
and M.
Freiling,
Cunz,
CEA-1977,
USNRDL-TR-444,
July
1961.
1960.
[See
also
385 (1964 ).]
137.
E.
L.
Francis,
UKAEA,
138.
N.
H.
Furman,
W.
IGR-161
B.
Mason,
(Rd/R),
and J.
1959.
S. Pekola,
Anal.
Chem.
~
1325
(1949). 139.
I. J.
140.
I.
Gal and O.
S. Gal,
Gal and Aleksandar
(Belgrade), ~;
~,
No.
1, 1-17
M.
Ganivet,
142.
H.
B.
~
Garden
(Annual
(Apr.
June and E.
Reviews,
Vol. Inst.
1962).
N.
R.
Geary,
UKAEA,
144.
E.
L.
Geiger,
Health
145.
A.
S. Ghosh
Radiation Tranal. E.
1960.
Nielsen,
28, p 24, Nucl.
Sci.
Paper/468. “Boris
In English.
[See
Kidrich”
also
J.
Chromatog.
In French.
in “Annual
Inc. , Palo
143.
J.
Bull.
549 (1964 ).]
141.
146.
A/ CONF/15/1,
Ruvarac,
Alto,
RISLEY-8142, Phys.
Mazumder,
~,
P.
Laboratory,
V.
Vijnana
Gindler,
J.
Parishad
of Nuclear
1957) Vol.
“Science,
”
7, p 47.
1955,
405 (1959).
Belakrishnan,
and R.
California,
Livermore,
from
Review
California,
Anusandhan
Gray,
Jr. , and J.
Glendenin,
K.
Flynn.
Chem.
59 (1955).
R.
N.
Singh,
Lawrence
UCRL-trans-938(L).
Patrika Huizenga,
~,
149 (1961).
Phys.
Rev.
11~,
1271
(1959), 147.
L.
E.
Anal. 148.
B.
~,
Golds chmidt,
F.
P.
R.
F.
and I.
Regnaut,
Buchanan,
PrevotJ
and E.
A/ CONF.
P.
Steinberg,
8/9,
pp 492-7,
Paper/349. 149.
P.
D. Goulden,
(also 150.
D. W.
151.
V.
R.
AECL-348) Grant,
I.
J.
W.
Durham,
March
1955.
Inorg.
Nucl.
Grebenshchikova
and V.
Chem.
Corriveau,
~,
AECL,
CRDC-640,
69 (1958).
and V.
N.
Bobrova,
Radiokhimiya
and N.
B.
Chernyavskaya,
and C.
M.
~,
544 (1961).
In Russian. 152.
V.
I.
Grebenshchikova
(1962). 153.
C.
Groot,
154.
D.
M.
Vol.
1. M.
Gruen,
155.
J.
E.
156.
R.
Gwozdz
Guthrie
Rehn,
S. Fried,
28, p 112,
Nuclear
Radiokhimiya
~
232
In Russian.
E.
Haeffner
158.
G.
R.
Hall
Slansky,
Graf,
HW-19303,
and R.
L.
Dec.
McBeth,
1950.
A/ CONF.
15/1,
Paper/940.
and W.
E.
Grummitt,
and S. Siekierski,
Research,
157.
P.
and A. and R.
168/V,
1960.
Hdtgren, Hurst,
AECL,
Polish Also
Nucl.
UKAEA,
AECL-1745,
Academy
Nukleonika
Sci. AERE
173
and Eng. C/M
May
of Sciences,
1963.
Inst.
~
671 (1960).
~
471 (1958).
88 (Rev),
1950.
of
,
159.
J. W.
Handshuh,
160.
G.
Hanna,
C.
New
York,
~
1960.
in “Experimental
1959),
E.
161.
W.
162.
C.
J.
Hardy,
Progr.
163.
C.
J.
Hardy,
D. Scargill
H.
Hardwick
Nuclear
Segr6,
and F.
Ed.
Physics”
Vol.
Bedford,
III,
UKAEA,
and J.
M.
and Sons,
AERE-C/M-112,
Ener gy Ser.
Nucl.
(John Wiley
p 54.
UI,
Vol.
Fletcher,
J.
1961.
2, Chap. Inorg.
8-2,
Nucl.
p 357. Chem.
~,
257 (1958). 164.
K,
M.
Harmon
and W.
H. Reas,
Chap.
4-8,
165.
R.
G.
Hart,
AECL,
CRDC-630,
1957.
166.
R.
G.
Hart,
AECL,
CRDC-822,
1959.
R.
G.
Hart,
F.
Girardi,
167.
168.
p 184. (Also
Progr.
M.
S. Havelka
HW-49597
Lounsbury,
C.
AECL.
CRP-761,
and M.
Beran,
1603 (1963).
III,
Vol.
2,
A. )
B.
Bigham,
1959.
[See
Collection
L,
V.
also
Czech.
P.
Corriveau,
Talanta Chem.
~
and
94 (1960 ).]
Common.
, Z&J,
In German. 413
Sci.- Eng. , ~,
169.
T.
V.
Healy,
170.
T.
V.
Healy
and H. A.
C.
171.
T.
V.
Healy
and A.
Gardner,
172.
A.
Nucl.
(See also UKAEA, H.
Ener FY Ser.
Nucl.
W.
McKay, J.
AERE-C/R-800.
Heimbuch
and H. Y.
(1963).
Trans. Inorg.
UKAEA,
(Also
Faraday Nucl.
Sot.
~
Chem.
~
AERE-R-4191. 633 (1956). 245 (1958).
)
Gee,
AEC
ISew York
Opns.
Office,
NYO-9138,
1962. 173.
D. L,
174.
D.
Calif. L.
Calif. 175.
F.
177.
E.
E.
, GCRL-1169Z Heisig
Hicks,
Lawrence
Radiation
Laboratory,
Berkeley,
Lawrence
Radiation
Laboratory,
Berkeley,
1952.
and T.
E.
, UCRL-1664,
Hicks,
Feb.
“Ion
1952.
Exchange”
(McGraw-Hill
Book
Co. , Inc. . New
1952).
A. HeUer, Tel
and T.
Helfferich,
York, 176.
Heisig
Aviv,
R.
Elson
and Y.
Marcus,
Israel
Atomic
Energy
Comm.
,
IA-736.
Hesford,
E. Jackson
and H. A.
C.
McKay,
J.
Inorg.
Nucl.
Chem.
~,
279 (1959). 178.
E.
Hesford
179.
E.
Hesford,
180.
T.
and H. A. H, A.
C.
C.
McKay,
McKay,
Faraday
Trans.
and D.
Scargill,
Sot.
~
J. Inorg.
573 (1958). Nucl.
Chem.
~
321 (1957). E.
Calif. 181.
Hicks
and H. W.
, UCRL-912, Higgins,
Crandall,
Sept.
W.
Lawrence
Radiation
Laboratory,
Berkeley,
1950.
C.
E.
H. Baldwin,
182.
0.
F.
Hill
and F.
J.
Leitz,
HW-21663,
1951.
183.
0.
F,
Hill
and F.
J.
Leitz,
HW-23160,
pp 24-5.
184.
J.
C.
Hindman,
A/ CONF.
185.
D.
C,
Hoffman,
LASL,
LA
15/1,
and J.
Vol.
M.
Ruth,
28, p 349,
1721 (Rev),
174
1954,
~
Paper/941.
pp 271-279.
Aug.
1952.
)
186.
D.
E.
Homer
and C.
F.
Coleman,
ORNL-2830,
Nov.
187.
D.
E.
Homer
and C.
F.
Coleman,
ORNL-3051,
March
188.
G.
R,
Howells,
Ser.
III,
Vol.
p 3, Paper/ 189.
D. L.
T,
3, Chap.
and B.
Paper/
3-2,
and K.
P 151.
Saddin@on,
(See
also
1961.
Progr.
A/ CONF.
Nucl. 15/1,
Enerpy
Vol.
17,
F.
Scott,
in “The
Transuranium
Elements,ll
16.l.
190.
A.
Hultgren
191.
G.
J.
Hunter
and R.
E.
K.
Hyde,
“The
192.
Hughes,
307.)
Hufford
p 1149,
G.
1959.
and E.
Radioactivity
Haeffner, B.
A/ CONF.
Chenley,
Nuclear
Properties
Properties”
Vol.
15/1,
UK-AIM,
17, p 324,
AERE-AM-19,
of the Heavy
(Prentice
Hall,
Paper/
Elements.
Inc. , New
144.
1959. II.
Jersey,
Detailed
1964) pp 804-838.
193.
C.
194.
M. G. Inghram, D. ~u240 as Determined
C.
195.
E.
H.
April
1957.
196.
H. Irving
and D. N.
Edgington,
J.
Inorg.
Nucl.
Chem.
~,
158 (1960).
197.
H. Irving
and D. N.
Edgington,
J.
Inorg.
Nucl.
Chem.
~,
321 (1961).
198.
H. Irving
and D. N.
Edgington,
J. Inorg.
Nucl.
Chem.
~,
314 (1961),
197. Edgington,
J. Inor g . Nucl,
H. Ice,
R.
Irish
199.
See
200.
H. Irving
201.
N. ~,
Ref.
M.
HW-10277,
and D. N.
Isaac,
P.
~
507 (1961).
T.
Ishimori
204.
N.
Jackson
205.
W.
R.
R.
K.
Rease,
Fields,
Watanabe,
and J.
Jacobsen,
National
and T.
M.
Chem.
Gruen,
F.
Short,
1962,
and Analytical
J.
USA EC,
A.
H. Jaffey,
D.
B.
James
208.
E.
N.
Jenkins
and G.
W.
Jenkins
and R.
J. W.
“The
209.
E.
N.
W.
J. Jenkins,
211.
E.
R.
212.
N.
R. Johnson,
Jette,
(Inters
J.
21,
Inorg.
of
169 (1961).
h’ucl.
Chem.
M.
E. Pubs.
214.
M.
215.
M.
Kasha
216.
R.
E.
E. Pubs.
Jones,
24 (1958).
, New
and G.
E.
In Russian.
I.
1959.
Annual
12-13,
” pp 596-732.
Streeton,
1961.
Meeting Argonne
~
1963.
hTov.
AERE-R-3158,
Dec.
1954. 1959.
463 (1963).
D. OIKelley,
1963) Vol.
York,
in “Inorganic
2, Chap,
D. O’Kelley,
1963) Vol
Chemistry”
VII.
in “Inorganic
2, Chaps.
Chemistry”
III and VI.
1953.
in “The
Rudenko, English
March
AERE-C-R-1399,
365 (1955).
and G.
Dec.
~
,
LADC-5424,
UKAEA.
Chem.
York,
Sheline, T.
Oct.
UKAEA,
and G.
Eidiler,
July
Seventh
LASL,
Sneddon,
Phys.
, New
Japan
1962.
Nucl.
HW-30384,
Kartushova,
AERE-M-444,
Elements,
Eidiler,
Ener gy Sot.
At.
~, 11 (1962).
pp33-42.
Christensen,
Chem.
Johnson, cience
L.
J. Inorg.
(Interscience R.
Actinide
and E.
J,
Acts
Chemistry,
206.
210.
UKAEA,
ANL-6637,
Laboratory.
Fujino,
Radiochim.
207.
N.
HW-49483,
and D.
and J. Akatsu,
on Bio-assay
213.
P. R. Fields, and G. L. Pyle, “Half-life 236 Daughter, ” briefly noted in ANL-4653.
152 (1960). Ishimori,
203.
Hess,
by its U
and W.
T.
202.
June 1948.
Transuranium
and V. trans.
175
V.
Elements,
Fomin,
Soviet
J. At.
Atomnaya Energy
” Paper/3. Energ. ~,
14. ~,
831 (1958).
217.
W.
E. Keder,
J.
Inorg.
218.
W.
E.
J.
C.
Ryan,
219.
W.
J.
C.
Sheppard,
Keder,
Nucl.
Chem.
and A.
~,
561 (1962).
S. Wilson,
J.
Inor~.
Nucl.
Chem.
~,
131 (1961). E.
Keder,
and A.
S. Wilson,
J. Inorg.
Nucl.
Chem.
~,
327 (1960). 220.
D.
M.
Kemp,
UKAEA,
221.
J.
Kennedy,
UKAEA,
222.
J.
Kennedy,
R.
V.
Davies,
223.
J.
Kennedy,
J.
W.
Peckett,
224.
V.
A.
P.
N.
Khalkin,
AERE-R-4119,
July
~
Aug. and B.
K.
and R.
Palei,
and A.
A.
225.
K.
Kimura,
Chem.
Sot.
Japan
J.
K.
Kimura,
Chem.
Sot.
Japan
J. ~,
227.
E.
L.
ANL-JJK-14B-45,
Term.
CN-2726,
228.
E.
L.
King
229.
P.
Kirk
Dec.
and W.
and C.
Manhattan
Dist;
Reas,
Redden,
230.
J. Kleinberg,
231.
W.
Knoch
232.
W.
Knoch,
233.
R.
Ko,’ ~
Jan.
234.
R.
Ko,
1963.
235.
R.
J. Kofoed,
236.
J. Kooi,
237.
238.
LASL,
Z.
J.
Kooi
A.
H.
V. N. Kosyakov,
nl. , May
Chem.
1947,
(Supp.
Health
1),
Phys.
Kooi,
S. Gureyev,
N,
Nelson,
A/CONF.
241,
K.
A.
Kraus
and F.
Nelson,
Ann.
K.
A.
Kraus,
245.
L.
Kressin
Ku~a,
8/7,
Phillips,
p 245,
in Alkyl Argonne
of
Phosphoric
National
Acids,
Laboratory,
T.
Paper/731. 8/7,
Rev. A.
p 113,
Nucl.
Carlson,
R.
Waterbury,
Analyt.
et al J Radiokhimiya —-
Collection
U. Hollstein,
Paper/837.
Sci.
~,
31 (1957).
and J.
S. Johnson,
26, p 3, Paper/1832.
and G.
E. Krevinskaya
1962);
not published.)
and F.
K.
Czech.
Chem.
~
Chem.
~,
1598 (1962).
545 (1959).
Commun.
27,
2372 (Oct.
1962).
In German. 246.
L.
Ku~a,
247.
V.
I.
248.
W.
also
Jaderna
Kuznetsov Sotiet
J. At.
H. Langham,
1947.
(~”SO
Energie and T.
~
286 (1962).
G. Akimow,
Ener HS, Manhattan
LAMS-603.
”
1954.
In German.
8, 49 (1 962). — Yakolev, “Separation
Symposium,
Kraus,
I.
Nov.
1021 (1960).
41 (Feb.
Extraction
Kraus
M.
A/ CONF.
Q,
and G.
by Solution
A,
243.
Chemistry,
TID-5002;
1963.
Phys,
A.
Vol.
1804 (1951). Analytical
Report
U,
Health
K.
H. O.
~,
525 (1961).
K.
244.
Oak Ridge,
1956.
(Proceedings
15/1,
Labs.,
1954.
239.
A/CONF.
Sot.
Elektrochem.
240.
242.
Clinton
AEC
at Transplutonium
1963.
215 (1963).
1956.
~ements
given
also
Term.
~,
and J.
E.
(See
Elements:
Z.
Hollstein,
Hoogma,
~,
1038 (1960).
J. Am.
Jr. , HW-53368
and U.
1956.
1964.
63 (1961).
1721 (Rev),
JENER-Pub-11,
M.
~,
AERE-C/R-1896,
AERE-R-4516, Radiokhimiya
“Transuranic
Naturforsch.
Transuranium Paper
LA
Lindner,
HW-79738,
Nemodruk,
1946.
Oak Ridge,
and R.
UKAEAJ
UKAEA,
1944).
H.
J.
1962.
Robinson,
Perkins,
226.
King.
1962.
In Czech.
Radiokhimiya
~,
357 (1 960).
[See
135 (1960 ).] Dist.
Oak Ridge,
) 176
Term.
AEC
Report
~
”
249.
R.
P.
250.
W.
M.
Larsen
251.
S. Lawroski
in Aqueous
Chap.
Solutions”
T.
Chem.
~,
253.
Gordon
Leader,
254.
S. C.
S. Laxminarayanan,
Leidt
July
J.
D.
257.
J.
McClelland,
1952).
Energ y Ser.
IH,
Vol.
2,
D. Sharma,
J. Inorg.
Nucl.
not available).
Jr. , USA EC,
Tech.’
Info.
Serv.
, A ECU-4414,
LASL,
H. A.
C.
Energ y Ser.
H. A.
C.
McKay,
McKay HI,
March
LA
1858,
A/CONF.
8/7,
III,
Vol.
and T.
1960. 2nd Ed. p 314,
1, for
V.
1958,
Chap.
Paper/441.
an amended
Healy,
23.
Progr.
(See
version.
Nucl.
slso
Progr.
)
Ener .gy Ser.
III,
Vol.
2,
p 546.
260.
D.
R.
MacKenzie,
261.
W.
J.
Maeck,
~,
1957,
HW-64170,
Nucl.
AECL-1787,
G.
L.
Booman,
L.
Booman,
1951. M.
E. Kussy,
and J.
E.
Rein,
Anal.
Chem.
E.
and J.
E.
Rein,
And.
Chem.
1874 (1960).
W.
J.
~
Maeck,
G.
M.
Kussy,
1775 (1961).
263.
C.
J.
Mandleberg,
264.
C.
J.
Mandleberg
265.
W.
J.
Jan.
UKAEA, and K.
Maraman,
A.
J.
AERE-C/M-104. E.
Beaumont,
Marcus,
Isarel
Atomic
Chem.
Rev,
~,
and H. A.
C.
267.
Y.
Marcus,
268.
T.
L.
269.
B.
Martin
Markin
J. Inor%,
and D. W.
G. W.
Mason
271.
A.
R,
Matheson
272.
E.
Maxwell,
E.
Merz,
274.
C.
F.
275.
H. W.
276.
H. W.
1951.
AERE-C/R-1088,
L.
Nances,
Feb.
LASL,
1953.
LA-1991,
Metz, Miller
Miller
HW-17265, F.
J.
139-170 McKay,
~ F.
and I.
Aviv,
Pub/UP/R-20,
1960.
(1963). J.
Nucl.
Inorg.
UKAEA,
Chem.
PG-165-W,
~,
1960.
298 (1958).
[See
also
96 (1961 ).] Peppard,
M.
Fryall,
, Tel
Comm.
Rehn,
and W.
Nucl.
Sci.
Eng.
HW-13760~
~,
247 (Oct.
1963).
1949.
H. Langham,
AEC,
Oak Ridge,
Term.
,
1947. Z.
HW-17266,
Plant,
and D.
R,
MDDC-1167, 273.
Jan.
and R.
Energy
Ockenden,
Chem.
Nucl.
270.
G.
Feb.
UKAEA,
Francis,
1956.
Y.
F.
and H.
(Date
Sanders,
JENER-48,
Ludwick,
Appendix
278.
Potentials
1959.
256.
277.
York,
Nucl.
Patil,
ANL-WMM-125
D. Lingjaerde,
266.
S. K.
and S. M.
R.
262.
New
Progr.
and Their
1301 (1964).
255.
259.
Levinson,
1863 (1960).
p 258.
252.
258.
(Prentice-Hall,
and M.
7-2,
Chem. ~, Jr. , Anal. States of the Elements
and C. A. Seils, I!The Ofidation
Latimer,
Mills
Anal.
Chem.
~
417 (1959).
Anal.
Chem.
~
1748 (1957).
and R.
J.
Brouns,
Anal.
Chem.
2A,
536 (1952).
[See
also
J.
Brouns,
Anal.
Chem.
~,
536 (1952).
[See
also
(1950 ).] and R. (1950 ).] and H.
Oak Ridge, Miner,
In German.
B.
Whetsel,
Carbide
Term. , K-1064,
Dow Chem.
Co.
Sept.
Rocky
Flats
1964. 17’7
and Carbon
Chemicals
Co.
K-25
1953. Plant,
Denver,
Colo.
RFP-357,
279.
F.
J.
Miner,
R.
P.
DeGrazio,
and J.
R.
P.
DeGrazio,
R.
T.
Byrne,
Anal.
Chem.
~
1218
(1963). 280.
F.
J.
Anal. 281.
Miner, Chim.
Acta~,
E. I.
Moiseenko
from
Radiokhimiya,
and A.
Moore,
M.
No.
282.
F.
L.
283.
F.
L.
Moore,
284.
F.
L.
Moore,
285.
F.
L,
Moore,
Anal.
286.
F.
L.
Moore,
Natll
Anal.
Chem.
~;
908 (1958).
Chem.
~
1369 (1958).
Chem.
~,
1075 (1960).
Acad.
288.
F.
L.
Moore
and G. W.
289.
R.
H.
Moore,
290.
R.
H.
Moore
291.
K.
Z.
Morgan,
E.
of Sciences,
Anal.
Smith,
Nucleonics
and Sons,
(John Wiley
L.
March
Lyon,
New
and H.
and Sons,
Morrow,
M.
294.
A.
I.
and V.
295.
M.
N.
296.
N.
H, Nachtrieb,
297.
D.
Moskvin Myers,
Inc. , New
Linder,
Ed.
P.
H. A.
LA-387
(Del.), Joint
[Transl.
York,
Naumsnn,
Zaitseva,
O.
Z.
W.
J.
F.
Nelson,
301.
T.
W.
Newton
and F.
302.
T.
W.
Newton
and S. W.
Rabideau,
303.
J.
M.
Nielsen
and T.
Beasley,
304.
J.
P.
N’igon
305.
D. W.
Ockenden
306.
D. A.
Orth,
307.
R.
and I. T.
Overman
309.
J.
F.
Peppard,
A.
Chim.
Simi,
~,
Chemistry”
at Livermore,
”
73 (1961).
S. Wexler,
In Russian.
and B.
S. Wildi,
New
York,
JPRS -11184,
In German. Dec.
Kraus,
J.
J.
J.
LADC-5517, Phys.
Phys.
@
Chap.
365 (1959).
(Del.),
March
Develo
p. ~
Techniques
Sept.
1950. 1956.
121 (1963). “ (McGraw-Hill
5.
63 (1962). A/CONF.
~
Sot. , 3358-63,
Design
503 (1964).
1963.
LA-1079
‘Radioisotope
1960).
. ~
1962.
Chem.
Chem,
, Process
Clark,
1958.
Chromatog
HW-SA-3337,
York
Haissinsky,
Service,
LASL,
Welch,
Chem.
and H. M.
and M.
(AEC-tr-3535. D.
Eng.
R.
LASL,
Penneman,
and G.
Ind.
A.
Baker,
M.
Used
ORNL-2592,
and K. B,
7, p 391.
in Analytical
1957).
81 (1963).
Higgins,
and R. A.
Co. , Inc. , New Pag~s,
310.
R.
~,
Murase,
1,
Chap.
l_, 247 (1961 ).]
300.
Neill
Extraction
Research
Chem.
Kernerergie
Vol.
Ed.
1945.
Publications
from
Uses,!’
1956.
Patratz, Sept.
1767 (1957).
H. SneU,
Radiokhirniya
Aug.
299.
Pag~s
Series
1963.
D.
M.
(1952 ).]
1959.
Procedures
298.
M,
ORYL-1314,
66 (1955).
and Their
!! Solvent
Freiser,
HW-44987,
Naumann,
308.
[Transl.
1963.
1962) A.
York,
~
~
HIV-59147,
in “Radiochemical
UCRL-14258,
T.
also
Science
Chem.
in !ThTuclear Instruments
H. Morrison
Pub.
[See
,~uclear
Hudgens,
HW-SA-2804, and W.
(John Wiley
1961.
Jones,
1960. and J.
LASL,
C.
Deg-Inf-Ser-315-R.
Anal.
Moore
J.
UKAEA,
Anal.
L.
R.
Jr. , and T.
(1960 ).]
1660 (1957).
F.
293.
Rozen,
3, 274-80 @,
NAS-NS-3101,
G.
Forrey,
Chem.
287.
292.
P.
214 (1960).
In French. 15/1 Vol.
29, p 44, Paper/1156.
) J.
R.
Ferraro,
and G. W.
231 (1958). 178
Mason,
J.
Inorg.
Nucl.
Chem.
~,
311.
D.
F.
~, 312.
D.
F.
~, 313.
D,
315.
W.
Mason,
and C.
G. W.
Mason,
and S. McCarty,
G. W.
Mason,
and R.
S. W.
Moline,
and G. W.
G.
Peppard,
M. Andrejasich,
J. Inorg.
Nud.
Chem.
J.
Inorg.
Nucl.
Chem.
138 (1960). F.
g, 314.
Peppard,
1175 (1963).
Peppard,
J.
Sironen,
J.
Inorg,
Nucl.
Chem.
Mason,
J.
Inorg.
Nucl.
Chem.
117 (1959).
D.
F.
Peppard,
~,
344 (1957).
D.
F.
Peppard,
and J.
F.
SOC. ~,
M.
Mech,
H. Studier,
AEC,
R.
W.
Perkins,
Private
317.
W.
C.
Perkins,
DP-8741
318.
K,
A.
Petrov
INeorg.
319.
G.
Phillips
320.
N.
I.
G. W.
AECD-3016,
and E.
(1958).
V.
Communication, Feb.
J Russ.
et al â&#x20AC;&#x201D;. Khim.
Popov,
Mason,
J.
See also
C.
J. Am.
Sullivan, Chem.
J.
Inorg.
~
498 (1960 ).]
N.
Jenkins,
transl.
J.
Chem.
J. A.
Porter,
DP-388,
July
1959.
322.
J. A.
Porter,
DP-389,
July
1959.
323.
J. A.
Porter,
DP-621,
Aug.
324.
A.
325.
I.
and B.
M.
~
Inorg.
Nucl.
and N.
A.
AEC-tr-3459.
321.
Poskanzer
1961.
1964.
1. NIedvedovskii,
(English
M.
V. Gergel,
D. C.,
2529 (1951).
316.
Zh.
M.
Wash.
237 (1960).
Chem.
Bakh,
~,
[Transl.
from
220 (1957).
Atornnaya
Energ.
~
154
)
1961. Foreman,
Jr. , J. Inorg.
Nucl.
Chem.
@
323 (1961). Prevot,
J.
Corpel,
and P.
Regnaud,
A/CONF.
15/1,
Vol.
17, p 96,
Paper/1171. 326.
S. W. June
Rabideau,
M.
J.
Bradley,
and H. D. Cowan,
LASL,
LAMS-2236,
1958.
327.
R.
H. Rainey,
328.
M.
J.
329.
J.
E.
Feb.
ORNL,
Rasmussen Rein,
A.
CF-59-12-95,
and H. W. L.
Dec.
Crocker,
1959.
HW-72285,
Jr. , and M.
Langhorst,
C.
Jan.
1962.
Elliott,
LASL,
April
1959.
LA-2291,
1953.
330.
Reference
331.
A.
E.
Reisenauer
332.
B.
F.
Rider,
Gen. March P.
eliminated. and J.
J.
Electric
L.
Co.
L.
Russell, Vallectios
Nelson,
HW-59983,
Jr. , D, Atomic
L.
Harris,
and S: P.
Lab. , Pleasanton,
Peterson,
Cslif.
1960.
333.
F.
Roberts
and F.
P.
334.
A.
M.
Rozen
and E.
L
335.
T.
C.
Runion
and C.
V.
336.
E.
R.
Russell,
DP-447,
337.
J.
L.
Ryan,
J.
338.
J.
L.
Ryan,
AEC,
Phys.
Brauer,
HW-60552,
Moiseenko,
Russ.
Ellison,
OR NL-557,
Feb. Chem.
Oak Ridge,
J.
June Inor,q. Jan.
1959. Chem.
~,
1950.
1960. ~,
1375 (1960).
Term.
TID-7607,
179
1960,
PP 2-20.
Jr. ,
, GEAP-3373,
(1959).
339.
J.
L.
Ryan
and E, J. Wheelwright,
340.
J.
L.
341.
J.
Rydberg,
Acts
342.
J.
Rydberg,
J. Inor g,
343.
J.
Rydberg
344.
A.
Ryan
and E.
J. Wheelwright, Chem.
and B.
Samartseva,
~,
~,
J.
Ener gy.~,
At.
279 (1 960).
G.
Radiokhimiya
~,
647 (1962).
346.
G. Samartseva,
Radiokhimiya
~,
28 (1963).
347.
A.
G.
Radiokhirniya
~,
526 (1962).
348.
o
samuel~on,
S. M. D.
Samart.seva,
Samartseva,
llIon x Separations
Stockholm, Saders,
Scargill,
J. Inorg.
Scheicfhauer
352.
J.
Scheidhauer,
353.
C.
S, Schlea,
C.
J.
Chem.
~,
and L. L.
JX&Z39,
R.
Caverly,
H.
E.
Henry,
W.
Sept.
A.
Schneider,
Anal.
359.
K.
Schwabe
360.
L.
C.
Schwendiman
C.
A.
Seils,
Clinton
McKay,
462 (1961).
CEA-2354,
R. Jenkins,
R.
F.
Shepard,
363.
J.
C.
Sheppard,
364.
V.
B.
Shevchenko from
S er.
Jenkins,
1953.
DP-808<
and W.
C.
Perkins,
V.
B.
929 (1960).
V.
B.
~,
1367 (1960).
V.
B.
N.
Shevchenko,
Shevchenko,
I.
from
[Transl.
Shevchenko
A. (USSR)
(1962).
Anal.
Chem.
~,
1673
.)
Radiochemistry
and A.
3-6,
(USSR)
~
1 (1 961).
Neorgan. and Y.
Zh.
Prorr.
F.
Mezhov, Khim.
Soviet
Nucl.
~,
At.
J.
Inorg.
Chem.
1911 (1960 ).] Russ,
Khim. J.
Russ.
~,
Zhdanov,
Neorgan.
S. Smelov,
S. Solovkin,
S. Solovkin,
p 217. and E. A.
Zh.
Energiys
~,
339-54 78 (1958).
6 (1960 ).]
Shilin, from
and V.
Atomnaya
Shevchenko,
~
S. Schmidt,
V.
Larsen,
)
1945.
1957.
Federov,
S. PovitskiJ
V.
P.
@
Term. , TID-1883~
3, Chap.
[Transl.
HW-SA-2216.
219-220,
Nucleonics
and R.
Aug.
and I. A.
Vol.
(Alfio
1955.
HW-51958,
HI,
1961.
Term. , CN-1873, Chem.
Hesly,
J. Meyer,
Feb.
522 (1962).
Physik.
Oak Ridge,
Radiokhimiya
~,
from
Z.
HW-3271O,
Shevchenko,
~
, Oak Ridge,
and J. W.
AEC,
HW-533 68,
Harmon,
Chem.
Labs.
Jr. , R.
(Also
Radiochemistry
M.
and D. Nebel,
D.
B.
C.
deleted.
362.
V.
and
1962.
Schubert,
369.
~
Meiraneisio,
M.
R.
[Transl.
M.
and W.
J.
368.
and A.
(Paris)
Henry,
358.
367.
(Almq~st
and H. A.
Anal.
E.
357.
366.
Chim.
H,
and K.
B.
Hesford,
E.
Caverly,
Schneider
En errv
Fletcher,
Messainguiral,
R. A.
V.
M.
R.
356.
365.
â&#x20AC;&#x153;
304 (1957).
M.
Reference
[Transl.
In Russian. Chemistw
1963.
S. Schlea,
(1963).
In Russian. In Russian.
in Analytical
Messtinguird,
355.
361.
Atomnaya
1956.
Alcock,
Nucl.
J.
April
from
1963).
PL2!L K.
351.
354.
[Transl.
324 (1960 ).]
A.
350.
Paper/1915.
79 (1957).
A.
349.
17, p 137,
1252 (1955).
Chem.
345.
Wiksell,
1959.
Vol.
Bernstrbm,
Soviet
~,
Energiya,
15/1,
A/ CONTF.
Stand.
Nucl.
Feb.
~
~,
J. Inorg.
Chem.
2832 (1960 ).]
Ener,gy
~,
76 (1960).
140 (1959 ).]
L.
186 (1962).
180
M.
Kirillov,
[Transl.
from
and A.
I.
Ivantsev,
Radiokhimiya
~,
503 (1961 ).]
370.
V.
B.
Shevchenko,
RadioChemistry 371.
V.
B.
Shevchenko,
and V.
V.
V.
B.
Part 373.
V.
~,
B.
M.
S. Solovkin,
I.
V.
Radiochemistry
V.
G.
~,
and Y.
W.
H. Shipman
T.
H, Siddall
Ill,
~
376.
T.
H. Siddall
III,
J.
Inorg.
Nucl.
377.
T.
H. Siddall
DI,
J.
Phys.
Chem.
and H.
V.
Weiss,
Chem. ~,
H. Siddall
ILT, DP-541.,
Jan.
1961.
H. Siddall
III,
Feb.
1961.
380.
S. Siekierski,
383.
T.
Sikkeland
G. S. Sinitsyna,
A.
386.
H. Sl~tis,
387.
A.
389.
Smales,
391.
L.
Smith,
L.
K,
Sokhina
Airey,
J.
Nucl.
Energya
(USSR)
~,
231 (1962).
1960.
151 (1960).
Research,
Warsaw,
489 (1961).
Aug.
1956.
M.
Sukhodolov,
Radiokhimiya
UCRL-Trans-1083
(L),
Livermore,
Calif.
~,
)
1961.
G.
Ray Spectroscopy” Ed. , Chap.
N.
Dec.
and A.
S. Salovkin, 1307 (1959).
A.
S. Solovkin,
1. E.
~,
transl.
Siegbahn,
DP-700J
A.
~
Volkova,
of Nucl.
and G.
(English
Feb.
K,
French
Walton,
(Inters
VIII
and R,
cience
Pubs.
Inc. ,
(II). O.
R.
Brooks,
UKAEA,
A.
D. Shelman,
“Extraction
393.
D. C.
Stewart,
394.
D. C.
Stewart
P.
Ratner,
and T.
Cslif.
UCRL-861,
395.
F.
W.
E.
396.
M.
Taube,
Labs, E.
Aug.
Strelow, J. Inorg.
M.
transl.
Clinton
V.
transl.
A.
Pasvik,
NP-tr-741, , Oak Ridge,
Hicks,
from
Nucl.
~
1013 (1960).
Lawrence
Chem. Chem.
~,
181
Nitric
J.
Acid
zovaniyu )
and F.
L.
UKAI?A, Term.
Chem.
Solutions
by
Curve s,”
Atomnoi
Ginzburg, Harwell,
CN-3905,
Radiation
174 (1959).
Inor@,
of the Distribution
po Ispol!
1185 (1960). ~,
Russ,
AEC-tr-4671.
1950.
Anal.
Khim.
Renard,
Calculation
Upravlenie
(English
(English
Neorgan,
of Electrolytes
Glavnoe
1960.
A.
and E.
Solvents.
Ministrov.
545 (1959).
Zh.
CEA-TR/R-1515.
I. Ivantsov,
Moscow,
Starik,
1962.
transl.
Organophosphoric
USSR Soviet
392.
JENER-44,
Faddeev,
and Gamma
L.
~
Energii,
Rodionov,
from
1950.
L.
Neutral
Nukleonika
Laboratory,
1955).
In Russian. 390.
Juul,
DP-554,
AER.E-c/R-533, 388.
V.
1955.
S. L.
in “Beta
York, A.
Taube,
and J.
Slade,
~,
of Sci. , Inst.
JENER-38,
Radiation
385.
A.
[Transl.
1960.
In Russian.
Lawrence
New
Acad.
and M.
295 (1959).
L.
DP-548,
Polish
384.
Kirilov,
1863 (1960).
T.
Sept.
A.
USNRDL-TR-451,
T.
Sikkeland,
M.
77 (1961).
1957.
378.
T.
L.
~,
Radiochemistry
379.
382.
I. Ivantaov,
676 (1961 ).]
375.
S. Siekierski
Shilin,
and A.
Zhdanov, ~,
374.
NP-9695,
and A.
211 (1960).
F.
Radiokhimiya
381.
Krilov,
(USSR)
Timoshev,
Technol.
Shevchenko from
L.
186 (1962).
281 (1960 ).]
Reactor
[Tranal.
~
A.
Shevchenko, B:
S. Solovkin,
Balandina,
Radiokhimiya 372.
A. (USSR)
Radiokhimiya Berks,
England.
1945 (Revised
Laboratory,
Berkeley,
)
1951).
Nucl.
Inorg.
Chem.
@
171 (1960).
397.
M.
Taube,
J.
398.
M.
Taube,
Nukleonika
~,
531 (1960).
In English.
~,
371 (1961).
In English.
399.
M.
Taube,
Nukleonika
400.
M.
Taube,
CEA-TR-R-1672,
401.
S. G. Vol.
Thompson
5-1. and E.
402.
F.
W.
Tober
403.
T.
Y.
Toribara,
Atomic 404.
and G.
1, Chap.
R.
Energy
Project,
Toribara,
C.
Atomic
Energy
Project,
Trowell,
UKAEA,
406.
D.
G. Tuck,
Anal.
407.
D.
G. Tuck,
J. Inor,g.
408.
H.
Umezawa,
Nippon
409.
G.
Valentini,
Russel,
DP-349, and C.
UR-607,
Chim.
Taglioni,
11. H. Van Tuyl,
HW-28530, and M.
Vdovenko
(See
Paper/2216. V.
M.
~,
143 (1962).
V.
M.
~,
44 (1960).
414.
A.
415.
A.
l?.
N.
Y.
Univ.
Rochester,
Hargrave,
N.
Y.
Univ.
1962.
271 (1957). ~
252 (1958).
Gakkaishi
~,
Mostin,
478 (1960).
Centrc
pour II Industrie
d’Etude
Nucleaire,
de 1) Energie Brussels.
Vdovenko,
A.
A.
A.
from
A.
Vorobev
Radiokhimiya
from
Kant,
h’.
P.
Sleight,
Transuranium Kuzrnina,
III,
Vol.
Vol.
Nikitivo,
~,
R.
15/1,
Ser.
Radiochemistry
Nikitivo,
(USSR)
Radiochemistry
~,
307 (1960 ).]
E.
Hein,
J.
M.
Wright,
s,’i p 162,
Element
Gigiena
17, p 329,
3, p 221. )
396 (1961 ).]
and S. A.
Radiokhimiya R.
in “The
and V.
Ener~y
and S. A.
Lepovskii,
[Transl.
Voigt,
Nucl.
Lepovskii
A.
A/CONF.
Kovalskaya,
Progr.
[Transl.
Vdovenko,
1953.
P.
also
and H. D. Brown, M.
Rochester,
1964.
V.
413.
~,
and N.
Beige
1959.
1964.
Chem.
Genshiryoku
411.
412.
A.
Jan,
Acts
III,
1962.
and P.
Nucl.
410.
M.
Feb.
Jan.
Enerp y Ser.
hTucl.
Predmore,
AWRE-O-19/64,
and Societe
EURAEC-837,
in Progr.
Morken,
UR-606,
F.
L.
Seaborg,
Predmore,
405.
Nucleaire,
T.
D. A.
Y.
T.
1961.
i Sanit. , No.
F.
(USSR)
J. Walter,
Paper/3.8.
9, 54 (Sept.
1963).
In Russian. 416.
R.
Wagner.
Atomique
Process
for
Energie,
Paris)
417.
B.
Warren,
418.
C.
G. Warren,
LASL,
419.
K.
Watanabe,
420.
B.
Weaver
421.
H.
V.
Weiss
and W.
422.
H. V.
Weiss
and W.
Canadian
LA-1567,
LASL, J. At.
and D.
E.
Homer,
J.
626,
1954, July
Ener,g y SOC. Japan.
Rev.
~,
Anal.
Chem.
H. Shipman,
USNRDL-TR-541J
Wenzel
and C,
AERE-CE/M-19, E.
Pietri,
425.
L.
B.
Werner
and G,
E.
Moore,
NOV. Anal. Clinton
Nov.
29,
~ 1,
1961.
1955.
497 (1961).
H. Shipman,
W.
Comfissariat
Aug.
1953.
Eng.
I. WaJls,
(t.
591,
Chem.
A.
E.
10,
(Del),
424.
426.
of Plutonium.
Patent
Sept.
LA-1843
423.
~
UKAEA,
the Reduction
Data ~, ~,
260 (1960).
37 (1961). Oct.
1961.
1950.
Chem. Labs.
X,
1324 (1963).
, Oak Ridge,
Term.
1944. F.
Westrum,
Jr, , in “The
Transuranium
182
Elements,’!
p 118,5, Paper/16.2.
427.
J.
C.
White
Series
and W.
428.
V.
J. Wilkinson
429.
A.
S. Wilson,
430.
A.
S. Wilson,
R.
S. Winchester
Nucl.
431.
J.
Ross,
NAS-NS-3102,
National
Academy
of Sciences,
Nuclear
Science
1961.
and J. A. A/CONF.
Ener gy Ser.
Peacegood,
15/1,
~,
Vol.
UKAEA,
VcJ.
17, p 341,
3, Chap.
HW-68207,
3-5,
RDB-(W)/TN-77, Paper/544.
June
(See
also
1953.
Progr.
p 211. )
1961.
and W.
J.
Maraman,
A/ CONF,
15/1,
Vol.
17, p 168,
Paper/530. 432.
L.
Wish,
433.
L.
Wish,
434.
L.
Wish
435.
V.
D.
Anal.
Y.
Zagrai
437.
(No author),
(No
p.47, 439,
A.
(No
author),
~
161 (1962).
(USSR)
~,
217 (1962).
(1962 ).] Progr.
Report
in DP-7MI,
Tech.
Div.
1951, ” ORNL
“Quarterly
“Report
(No author), March,
241,
(Quoted
P 47,
Quarterly
1141,
Progress
1953, ” HW-27727,
August-October 441.
(USSR)
February-April Ref.
28.)
Progress
1952,
Secret.
1951, ”
Report (Quoted
for
Period
in DP-700,
20. )
H. Bushey,
March, 440.
20,
1956.
Radiochemistry
~,
Processes,
“chemistry
Oct.
Radiochemistry
181 (1962 ).]
Nishanov,
p. 17 Secret.
Ref.
~
Radiokhimiya
August
1957.
Sel!chenkov,
“Separations
author),
Ending
Oct.
USNRDL-TR-117t
I.
and D.
from
KAPL-523, 438.
326 (1959).
Radiokhimiya
Zolotov
[Transl.
Rowell,
and L.
from
A.
~,
USNRDL-TR-185, and M.
[Transl. 436.
Chem.
1953,
Report
of the Chemistry
1953, ” I!Chemical
- Chemistry
& Chemical
KAPL-1OO2,
1953,
Engineering
Division
1954, ” 4NL-5254,
pp 11-15,
442.
Reference
443.
(No
author),
“ORNL
444.
(No
author),
“Nuclear
Safety
“Special
Report
Unit,
January-
Secret.
p 42,
Engineering
Section
for
Secret.
Summa~
Report
for
January-
Secret.
deleted. Reactor
Fuel
Processing, AEC
Guide, ”
” 1960,
Vol.
Oak Ridge,
3, p 16.
Term.
TID-7016,
Rev.
1961. 445.
(No
author),
& Societe
Beige
pour
l! Industrie
446.
(No
author),
UKAEA,
447,
(No
author),
“Procedures
Progress 448.
(No
Report,
author),
NR L-170, 449.
(No
450.
J.
author), M.
Aug.
Nucleaire,
de llEnergie
Brussels,
1962, ”
Nucleaire
EURAEC-708.
1962.
Np and Pu, ” excerpt Calif.
Progress 1960, ”
dlEtude
, Oct. Report
New
15,
from
Tracerlab
(On Chemistry)
Brunmvick
Quarterly
1962.
Lab.
, AEC,
for
the Period
New Jersey,
1961.
UKAEA,
Fletcher,
Brussels,
for
“Richmond,
December
11,!’ Centre
PG-372-W,
“Semiannual
July through
No.
PG-309,
in “Aqueous
Belgium,
1963,
1962. Reprocessing
Eurochemic.
183
Chemistry,
” Symposium
at
1,
451.
C.
E.
Honey,
Ellinger, 452. 453.
and C.
R.
F.
E.
Withers,
Std.
Mitchell.
~
454.
H.
Evans,
455.
R.
Ko,
G.
Bjorklund,
E.
and C.
communication. ~
Huber, 15/1,
Jr., Vol.
E.
L.
Head,
6, p 215,
Paper
F.
H. 701.
326 (1960).
457 (1944).
Chem.
J.
A/ CON3?.
~
Schlecht,
451,
private
Anal.
W.
Anal. Chem. W.
363,
R. N. R. Mulford,
Jr.,
274 (1956).
164
L.
Gordon,
J.
Research
Nat Il.
Bureau
MONOGRAPHS
IN THE
R.ADIOCHEMISTRY TECHNIQUE
AND
THE
RADIOCHEMICAL
SERIES
Copies of the following monogmphs are available from the Clearinghouse for Fedeml Scientific and Technical Information, National Bureau of Standards, U. S. Department of Commerce, Springfield, Va. 22151
Aluminum Americium $0.75
and Gallium, NAS-NS-3032, and Curium, NAS-NS-3006,
$0.50
Antimony, NAS-NS-3033, $0.50 Arsenic, NAS-NS-3002, (Rev. )1965 $1.00 Astatine, NAS-NS-3012, $0.50 Barium,
Calcium,
and Strontium,
NAS-NS-
3010, $1.25 Beryllium, NAS-NS-3013, $0.75 Cadmium, NAS-NS-3001, $0.75 Carbon, Nitrogen, and Oxygen, NAS-NS3019, $0.50
Cesium, NAS-NS-3035, $0.75 Chromium, NAS-NS-3007, (Rev. )1964 $0.75 Cobalt, NAS-NS-3041, $1,00 Copper, NAS-NS-3027, $0.75 Fluorine, Chlorine, Bromine, and Iodine, NAS-NS-3005, $0.50 Francium, NAS-NS-”3003, $0.50 Germanium, NAS-NS-3043, $0.50 Gold, NAS-NS-3036, $0.50 Iridium, NAS-NS-3014, $0.50 Iridium, NAS-NS-3045, $0.50 Iron, NAS-NS-3017, $0.50 Lead, NAs-NS-3040, $1.75 Magnesium, NAS-NS-3024, $0.50 Manganese, NAS-NS-3018, $0.50 Mercury, NAS-NS-3026, $0.50 Molybdenum, NAS-NS-3009, $0.50 Nickel, NAS-NS-3051, $0.50 Niobium and Tantalum, NAS-NS-3039, $0,75 Osmium, NAS-NS-3046, $0.50 Palladium, NAS-NS- 3052, $0.75 Phosphorus, NAS-NS-3056, $0,50 Platinum, NAS-NS-3044, $0,50 Plutonium, NAS-NS-3056, $2.00 Polonium, NAS-NS-3037, $0.75 Potassium, NAS-NS-3048, $0.50 Protactinium, NAS-NS-3016, $1,00 Radium, NAS-NS-3057, $2.25 Rare Earths— Scandium, Yttrium, and Actinium, NAS-NS-3020, $3.00 Rare Gases, NAS-NS-3025, $0.75 Rhenium, NAS-NS-3028, $0,50 Rhodium, NAS-NS-3008, (Rev. )1965 $1.00
Rubidium, NAS-NS-3053, $0.50 Ruthenium, NAS-NS-3029, $1.00 Selenium, NAS-NS-3030, (Rev. )1965 $1.00 Silicon, NAS-NS-3049, $0.50 Silver, NAS-NS-3047, $0.75 Sodium, NAS-NS-3055, $0.50 Sulfur, NAS-NS-3054, $0,50 Technetium, NAS-NS-3021, $0.50 Tellurium, NAS-NS-3038, $0.50 Thorium, NAS-NS-3004, $0.75 Tin, NAS-NS-3023, $0.75 Titanium, NAS-NS-30W, $0.50 Transcunurn Elements, NAS-NS-3031, $0.50 Tungsten, NAS-NS-3042, $0.50 Umnium, NAS-NS-3050, $3.50 Vanadium, NAS-NS-3022, $0.75 Zinc, NAS-NS-3015, $0.75 Zirconium and Hafrdum, NAS-NS-3011, $0.50 -, Activation Analysis with Charged Particles, NAS-NS-311O, $1.00 Applications of Computers to Nuclear and Radiochemistry, NAs-Ns-3107, $2.50 ‘ Application of Distillation Techniques to Radiochemical Sepamtions, NAS-NS3108, $0.50 Detection and Measurement of Nuclear Radiation, NAS-NS-3105, $1,50 Liquid-liquid Extraction with Highmolecular-weight Amines, NAS-NS3101, $1.00 Low-level Radiochemical Separations, NASNS-3103, $0.50 Paper Chromatographic and Electromigration Techniques in Radiochemistry, NASNS-3106, $0.50 Processing of Counting Data, NAS-NS3109, $1.75 Rapid Radiochemical Separations, NAS-NS3104, $1.25 Separations by Solvent Extinction with Trin-octylphosphine Oxide, NAS-NS-3102, $0.75