Radiochemistry of Plutonium

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
2’0
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)
—
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
> SO”; > 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 500”
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 500”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.
i’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 ‘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)
“
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)
, –.
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.
7’0(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 solutions’. 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 —
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 –
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
14’
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
[email protected]
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+
—
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
@@.36g’
with
pure
diluent
of the dipoles
37’
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
[email protected] 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
–
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
1’
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
‘/
I
I
1
1 (2
-101
1
1
3
I
,4,
a
‘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: NC’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 1-14”
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 ‘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 —
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.
—
(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 — 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
‘
source
in ml.
efficiency
plutonium
‘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.
HN’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 —
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
— 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 –
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
50”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
sat’. 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 60”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.
9’77.
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 —
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 -ml’ 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 ~20H”
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 NH20H”
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 second” 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
“ 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 —
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 Pu23’
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 Pu23’
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 —
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 90”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,
—
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 600”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 —
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 “Altuglas
MZD” 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
(—) 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 —
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 —
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 80”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 —
M
and complete.
Procedure
The
purification
then undertaken.
dissolved
for
The h’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 —
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
‘c 104’
(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 “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
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DP
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I.
du Pent
EUR4EC
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Hw
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So.
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States
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Products
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Richland,
Wash.
JENER
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KAPL
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LASL
- Los
(LA -,
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Alamos
LAMS-,
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USNRDL
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UKAEA
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AERE
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Energy
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followed
Energy
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Establishment,
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York.
Mexico.
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Energy
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IGO & IGR
PG
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and Engineering
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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