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Thb
prcprd
WCUk
HADIOCHEMISTRY
by
OF NEIPTUNIIUM
G. A. krney and R. M. Harbour Savannah River Laborat cIry E. 1. du Pent de Nemours, G Co. Aiken, South Carolina U3801
Prepared for Subcommittee on Radiochwnktry National Academy of Sciences - Nationa I Research Council
IssuancffDate: Dacewnber191~1
Technical
lu~lTE~
Information
STATES
Sewices
paper was prepared in connection with work under Contract AT(07-2)-l with the U. S. Atomic Energy Cmaission. By q cceptance of this paper, the publisher and/or recipient ri[~ht to retain a nonacknowledges the U. S. Governments exclusive, royalty-free license in and to any copyright covering this paper, along with the right to reproduce and to authorize others to reproduce all or part of the copyrighted paper.
No.
This
.- ---
Foreword
The S&committee on Hadmchemiswy is one of a number of iubcommitmes working under tl~e Committee on Nuclear Sciencewithin the Natmnal Academ} of Sciences-National Research government, industrial and (UniversityIaboratories in Ihe areas Counci 1. i!s members represent of rrucfmr chemistrvand analytical chemistry. The Subcommittee has concerned itwlf with th~ are,~ of nuclear science which revolve the chemist. such as the collectmn and distribu$eon ID radiochemlcal procedures, the rtitochemicai purity of reqpnts. the piace o! radiochmnistry in college and university PfOiFams.and radiochemistrv in environmental soence. Th!mseries of rnmwxyaphs has qown out of the need for cornpilat!ons of radiochemical information, procedures. and techmques. The S@committew has endwvored to present a serws that will b d maximum use to the working scientist. Each monogrwh presents pertinent information rmqwred for radiochcrnical work with an indivm!ualelement or with a specialized technrque. Exprts in the Particulu radmcfwrnical technique have vvrittm the monographs. The Atomic Eneruv Commission has sponsod the printing of tht sems. TM Sukomrrtittee is confident these publications will te useful not only to radiochemmts but ahio to rtrwarch workers in other fiefds such as phvsic$. b ochemistrv. or nwdlcine who wish tow radiochemicat tswhniques to solve specific problems. Gregory R, Chopp in, Chatrman %bcomm!twe on Radlochemis!rV
l-
CONTENTS Paqe I. 11. III. Iv. v. General Review of the Inorganic and Analytical Chemistry of Neptunium . . . . . . . . . . . . . . General Review of the Radiochem.istry of Neptunium . . . . . . . . . . . . . . . . . . . . Discovery Isotopes and Occurrence and Nuclear of Neptunium . . . . . . . . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
s 7 8 9 12 12 12 12 14 14 16 20 20 24 24 29 31 33 39 39 39 40
Properties
of Neptunium . . . . . . . . . . . . .
. . . . . . . . ,.. . . . . ,..
Chemistry of Neptunium . . . . . . . . . A. Uetallic Neptunitm . . . . . . . , . A.l Preparation . . . . . . . . . . A.2 Physical Properties . . . . . . A.3 Chemical Properties . . . . . . Cmpmds . B. Alloys and Intexwtallic c. Coqmunds of Neptunim . . . . . . . D. Neptmium Ions in Solution . . . . . D.1 Oxidation States . . . . . . D.2 Oxidation-Reduction Reactions , D.3 Dispmportionatim of Neptunitm D.4 Radiolysis of Neptunium Sslutions D.5 Hydrolysis of Neptunim . . . . D.6 Ccqlex Ion Fomation . . . . .
VI.
Preparation of Neptunim Sa@es for Analysis . . A. Neptunium Metal and Alloys . . . . . . . . . . Co~ds . . . . . . . . . . . . . B. Neptunim c. Biological and Environmental S.qles . . . . . Separation Methods . . A. Coprecipitation and B. Solvent Extraction c. Ion Exchange . . . D. Chrowtography . . E. Other Methods . . Analytical Methods . . A. Source Preparation B. Spectmphotometry c. Controlled Potential D. Polarogmphy . . . E. Titration . . . . . . . . . . Precipitation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
VI1.
VIII.
. . . . . . . Methods . . . . . . . . . . . . . . . . . . . . . . . . . . ...123
-2-
PaiJg F. G. H. 1. J. K. L. IX. Emission Spectrometry . . . Gravimetric Methods . . . . Spot Tests . . . . . . . . Mass Spectrometry . . . . . . X-Ray Fluorescence Spectrometry Neutron Activation . . . . . Other Methods . . . . . . . . Safety Considerations . . .,.. . . . . . . . . . . .
.
, . . ,
. .
.. . . . . . . . . . . . . . . . . . . . .
. . . .
. . . . . .
.
124 12s 127 129 129 130 131 132 134 134 134 138 141 14s 1so 1s5 1S8 161
Radioactive
x.
Collection of Procedures . . . . . ,... . . . A. Introduction . . . . . ., . . . . . . ... B. Listiniz of Contents . . . . . . . . . . . ,. Procefiiire 1. Separation of NF1by lTA Extraction . . . . . . . . . . Procedure 2. Separation of P@ by TTA Extracti(nl . . . . . . , . . . Procedure 3. Determination of 23Np j.n Samples (kritaining LIBPu, and Fission Products . . . . . , . Procedure 4. Determination of Np . . . . . . Procedure 5. Determination of Small Amounts ofNpinPuMetal . . . . . . . Procedure 6. Determination of Np in Samples Containing Fission Products, U, and Other Actinides . . . . . . Procedure 7. Detensination of Np in Samples of U and Fission Products . . . Procedure 8. Extraction Chromatographic Separation of 23%p from Fission ami Activation PTOducts in the Determination of Micro and !@-microgram Quantitie:3 ofU . . . . ,, . . . Procedure 9. Separation of U, Np, Pu, and Am by Reversed Phase Partition Chromatography . . . . Method for .2;7NP. Procedure 10. An Analytical Using Anicm Exchange . . . . . of U, Np, and Pu Procedure 11. Separation Using Anion Exchange . . . . . Procedure 12. Separation of Zr, Np, and Nb Using Anion Exchange . . . . .
-3-
. .
Procedure Procedure
13. Separation 0. Np and Pu by Anion F.change . . . . . . . 14. Separation of Np andl Pu by Cation Exchange . .. . . 15. Separation and RadiQchemicaI Determination of U and Transuranium Elements Using Barium Sulfate . . . . . . . . 16. The Low-Level Radio:hemica~l Determination of 23Np in Environmental !hmplos . . . . . 17. Radiochemical Procedure for the Separation of T::ace Amounts of 237Np fn)m Reactor Effluent Mater . ,, . . . . . . 18. Determination of ~ in Urine . 19. Determination of 21:Npby Ganma Ray Spectrometry ., . . . . . . 20. Spectrophotometric [leterminationofNp . . . . . . . . . 21. Microvoltnetric Coqlexometric Method for Np with EDTA . . . . 22. Photo~tric Determination of ,h@as the Peroxide Complex . . 23. Separation of Np for Spectrographic Analysis of Impurities . . . . . . . , . . 24. Photometric Determination c)f Np as the Xylenol Orange Complex. . . . . . . . . . . . 25. Analysis for Np by ICmtrolled Potential Coulometry . . . . . . . . . . . . . . . . . . . . . . . .
. .
. .
173 175
176 179
. . . . . .
. . . . . .
,.
,
-4-
RADIOCHEMWTRY OF ~dEPTUNllUM* by G. A. Bumq and R. M. Harbcmlr Savannah River Laboratory E. 1. du Pent de Ncanurs & Co. Aikan, South Carolina 29801
I.
GENERAL REVIEWOF THE INORGANIC #J4D ANALYTICAL CHEMISTRY OF NEPTUNIIB! 1. J. J. Katz and G. T. Seaborg, The Chemh?tw of the Actinide Eh???IQnt8, Chap. VI, p 204-236, Johm Wiley and Sons, Inc. , New York (1957). C. F. Hetz and G. R. Waterbu~y, The Transuranium and F. J. Elving Actinide Elements, in 1. M. Kolthoff (Ed.), Treati8e on AnaZyticc~l Chemistry of the Eze?TW?Zt8, Volume 9, Uranium and the Ac!iinide8,, p 194-397, John Wiley and Sons, Inc., New Ycl~k (1962). Neptunium, in P. Pascal (Et.), Noxveau Trvri:e C& Chimie Minerale, Vol. XV, Trcnaurankns, p 237-324, Masson et Cie, Paris (1962]. !leptunium, in P. Pascal (Et.), No:xtwzu Traite de Chinrie Minerakz, Vcl. XV, Trcnauraniee8 fSupplement), p 1-91, Masson et Cle, Paris (1962). Il. B. Cunningham and J. C. tlindman, The Chemistry of Neptunium, in G. T. Seaborg and J. J. Katz [Ed.), The Actinide Elements, p 456-483, Vol. 14A, Chap. 12, McGrawHill Book Co., New York (19$4:). axticle was developed during A1 (07-2)-1 with the U. S.
7 e.
3.
4.
.5.
%e information=ontained in this the course of work under Contract Atomic Energy Commission.
-5-
6.
J. C. Hindman, L. B. Magnusson, end T. J. LaChapelle, Chemistry of Neptunium. The Oxidation States of Nuptunium in Aqueous Solution, in C. T. Seeborg, J. J. in Ekmenta, Katz, and W. M. Manning (Ed.), The !lmmeurun p 1032-1038, Vol. 14B, McGraw-Hill Eook Co. , New York [1949) . J. C. Hintian, L. B. Magnusson, and T. J. LaChapelle, themistry of Neptunium. Absorption Spectrm Sttiies of Aqueous Ions of Nept~ium, in G, T. Senborg, J. J. Katz, and W. H. Manning (Ed.), The fmneumniaun EZenm~, p 1039-1049, NcGraw-Hill Book Co., New York (1949). L. B. Magnussat, J. C. Hindman, and T. J. LaChapelle, Chemistry of Neptunium. First Prqamtion and Solubi li ties of Some Neptunium C~mds in Aqueous Solutions, in G. T. Seaborg, J. J. Katz, and W. ht. Manning (Ed.), The !lraetiun EZmente, p 1097-1110, McCrau-Hill Book Co. n New York (1949).
of S. Fried end N. R. Davidson, me Basic Dry Chaistry Neptuni~, in G. T. Seeborg, J. J. Katz, and W. M. Manning (Ed. ), The ~wn EZ&nants, p 1072-1096, McGraw-Hill Book Co., New York (1949).
7.
8.
9.
10. C. Keller,
p 253-332,
L1.
G. A. Burney, E. K. Dukes, and H. J, Groh, Analytical ~%amistry of Ncptuni~, in D. C. Stewart and H. A. Eliom (Ed. ), l%vgresin in Rucle~ l?ne~, Seriee IX, Anal@?al Ckmhtry, Vol. 6, p 181-211, Pergmon Press, New York (19M) . J. Korkisch, Mdexm Methode for t?w Separation of Ram?r MetaZ Ione, p 28-196, Pergamn Pre:,s, New York (1969) . J. Ulstmp,
At. he~~
Wthods
Rev. 4(4),
of Separating
3S (1966).
the Actinide
Elements ,*!
A. J. Ibses, The Ana2@imZ c~8ii~ of the Actinide l%mmte, Uacltillan Co., Nw York :1963).
A. D. Gelman, A. G. Moskvin, L. M, Zaitssv, and M. P. Mefodeva, Coqlex Compounds of Transuranides , Israel Pro~am for Scientific Translation j (1967), translated by J. Schmorak.
-6-
16.
Analytical Chwmistry of the Actinides, translated by S. Botcharsky, AERE-LIB/TRANS-787. [See alsoJ. AnaZ. Chin. USSR 12, 663 (1957)]. u%lina Nwuibuch &?P Ano~ar.iachen Tranawzne, Part C (1972]. &nelina T~suMe,
Hwuibuch
P. N. Palei,
Ckmie,
Vol-me 88
Parts
V. A. Mikhailov and Uy. P. Novikovp Advances in the Analytical Chemistry of Nepluniurn [A Review] , J. AnuZ. Chem. USSR 25, 1538 (1970). V. A. Mikhai 10V, Am Z@ica Z Chemiat~ John Wiley 6 Sons, New York (1973). of Neptunium,
B. B. Cunningham, Cheaist~- of the Act~:[ide Elements, in AnnuuZ Rev. Nucl. S&. 1+, 323 (1964). K. K. Bagnell, The co., lmdon (1972).
Actinide
EZement8,
Elsevier
Publishing
II. 1.
of the Actinide Separations El~ts, in G. T. Seaborg and J. J. Katz (Ed.), The AetJnide EZewenta, Chapter 1S, National Nuclear Energy Series, Div. IV, Vol. 14A, McGraw-Hill Book Co., hew York (1954).
E. K. Hyde, Radiochemical
2.
E. K. Hyde, Rdiochemical Separations Methods for the Actinide Elements, lnternationaZ Confemwe on the PeacefuZ Uaea of Atomic lhte~, 2nd Ceneuu, 7, 281 (195S]. H. Page Separation and Purification of Neptunium, in 2kmeumnienn, p 249-272, Masson et Cie, Paris [1962).
3.
-7-
111.
DISCOVERY ANDOCCURRENCE NEPTUNIUM OF in 1940 by NcMillan and Abelson. l with tha: low-energy neutrons was formed was an reactions:
the 2.3-day
activity
weighable
quantity
Npo2)
wa5
by Magnusson and LaChapelle to measure the specific of these quantities reactions, in nuclear in
Np is produced in r:actors
~d 23qJ
fueled
are
with used in
When fuels
enriched
235U
reactors,
the following
reactions
are increasingly
-8-
Since about 1957, the U. S. Atomic Energy Cwmission =covered and purified byprmduct Np in its for the production ~adioisotopic production
has
facilities.
of 23EPu, an isotope
p>wer sources.
The half-life
of
the earth.
Therefore?, where it
in U minerals reactions
of
is fotmed continuously
described
previously.G
of
2sNp in a s~le
was 3.10
atoms per
IV.
2s7Npand wst
Np are
sections
and resonance
integrals
Np isotopes
-9-
Maa@
224
2s
%r#,4a) Somm
13
231
3.s14 1 10
E a
6.2S
252
da
1.s44 I 10
z s.11710
af@.01) a
E
2ss
Ssda
%l[d. h) 10-)
Ea =
s
a(? x
1s4 K
S.ss 0.0
Shl[d, h) 1s%J[d,5m)
2ss
3.1141
10
a(clO-) m
m(%lo- )
S.ols(sst]
4.92s(lm 4.s64(18] = O.SII(WI) o.56(4a) U[d, n)
24s
22 h
S.m
x lo~
R(O.4S] 0-(0.s2)
a-
Zu[m, za)
lU(d.4n)
2s6= 227
q-
fr 1.s64 s 10
2.14 x 106 yr
Sf(s E 10-)
J%lm, h) urm.7)
*sU(O--dmy)
2s4
2.12 day
5.744
10
B-
B~
= 1.2S(4S11 0.26(s48)
s
lh[a-dacay) wpm,v)
%(d.h)
1.027(2SW 0.965(261)
i%(a,p)
2ss
2.ss dmy
S.la
1 10
o-q
Sf(a 1 10-)
n-
U(B. T) ?%J(B*Y)
24e
24a 241
7.s da
2.s19 m lo
e-
13-
= 2.lc[sa) I.so[nt)
6? mlm 16 mla
2.s95 s 10 1.a2 z 10
B0-
B a-
= O.m(lwl)
s
1..M
-1o-
%p
W?*
~ VW **) m+)
Spm
and panty 3.
2. :,
<.. h l).
Spm and
pvlty ml.,
5119
50s3 Lgl1 LU9.3 3916 3301 265s $6375 ?5 ?! 5727 ? 85
Sn. Wlb
v.?
%2. Y1., w?!..
F~glure . Decay Schemesof the Most hn ~rtant Neptuniun 1 237NP, 238Np,and 39Np.8 $10 Isotopes,
-11-
TAOl.E 2
CROSSSECTIONSAND RESONANCE tt4TUWtLSa FOR NEPTUNIIW ISOTOPES
Nat Nsss NudMm .. 2.34 3 ) !.(SLQ f .k%z!!l mm Cspture Fis! ion
9cm
?3s
236
148~
i? ,8(M) 1.85
600
.!37
0.02 ;.4$
o.ol)13~
23a
1.600
600
2,070
ml
2Se
[to
**NP)
.
a. Cross-sections J. For H. Lsndru. neutrons
expressed in
R. J.
l-.
,. i t? .
t J.
barns,
10- Z*C81.
V. A.
CNEMISTRY F NEPTUNXLU O
METALLIC NEPTUNIUM
A.1 Preparation Npw?al was first prepartxi by Fried and Duvidsoa in 1948
of NpF+ by excess Ca metal with iodine as a bocmter)- * was used to produce mltigrsa A.i! Physical Properties ductile three matal with s melting allotropic properties point of below in quantities of * metul.
undergoes
modifications me ~rizsd
The physical
-#z
A. B.
Appearance:
Silvery
white
[slowly ccatod with oxidel in dry air qt rcom toaperature) frtm vapor pf;ssun of liquid Np )
c.
D! .
E.
Transition teaporature to next higher phase, q C !Mtmity, glcm (at T*C) Crystal Structure
577 19<40
Tw:ragonali
h!il:h.
walue off W is reached at 140K and 7,093 cd/(aiol-e8t) Tbehigh bi~ specific Mm can k
entiwtly acmuntod
27C.*1
tho wv
in
for by
qlectronic contributions.
No imgvutie
orderIn8
a-!tp occurs *
to i.7K.a2
A.3
Chewlcal
Properties ~tal. The potential ~ta~li~~ Fl>r the couple is S~OUIYCOV@* at @out 20C,
~thin oxide
when exposed
to dry air
at higher haIogens,
with Np metal
at elevated at relatively
temperatures,
Hydrogen
solutions
Np dissolves
qt
andHzS04
elevated
t~rature. is given
solutions
in Table
4.
E!., AL1OYSAND INTERMETALLIC COWOUNDS Co@ete phase diagrams are reported for Np-Pu and N\p-U.23-2c
Complete miscibility
in both a-Fu and &.Pu. co~unds of Np with Al and Be (NpAlz, directlyby The boride:; cmrpounds reducing NpFq
with an excess
obtained
directly
-14-
Concentration W)
1.s 6 12
Observnt Ions After &ys 4 Initiai - . Very slowly atta:ked Irndiate vigorols Coql,ctely dissolved reacton i ,, ,, ,, ,,
NOvisibla mction r ., ,*
2 8 15.7
Someturbidity,
hydrated oxide
2.25
9 18
Slowreaction
,, NOnoticeable reaction
(nlcoot#
8
16
r.action
HC104
Iinim
Cone.
CQnc.
Rapid diasoluticn uha hoatai Rapid dissoluti(m whenhosted Rapid dissolutkn uhon hooted Dissolution uhal refluxod
-ls-
compoundswith noble metals, such as NpPt3 and NpPt5, have been prepareti by hydrogen presence of platinurn. other reduction of NpOZ at 1300C in the
Also, Erdinann31sed the same method u compounds, NpIr2, NpPd.3, and NpRh3.
CWPOUNDS OF NEPTUNIUM Cmpounds of Np for the III, IV, V, VI, and VII oxidation anc compositions because they
states
The solubilities
were initiallydeterminedwith smaIl amounts offNp shortly after studies oxalates discovery and therefore may be semi-quant:.tative. larger amounts of neptunium, data is available. chlorides, in s~lvating and organic acidUhere i.e.,
more quantitive
Numerous Np compounds, such a$ nitrates, possibly soiverms contai.ning thiocyanates, such as diethyl solvents are readily ether, soluble
saturated of co~nds
trivalent
rqt.unium
because
of the instability
in of Np(lII]I
of atmospheric platinum
oxygw.
Np(III)
catalyst),
by electro-
reduction
-m-
oxidized
of tetragonal
Np(III) phenylarsonate
t:olored
NpZ(CGHS~09)SnHZ0 when well dried; a long period lilac Np(III) h at room te~rature. fluoride c~lex were also double
and grayish-
precipitated sulfates
conditions.
of Np(iII],
increased
of Np(IV), S includes
(V), and (VIl are shown in Tables cmpounds prodtied in aqueous by other
Table
coqounis
produced
-17-
,.
5MiiTI@l
of
3olution
ScJ.ubiliw(m 1) Np/
in Di!solw.s
B1 uk ,Greea
- NaNO, to 9
either
uid
or
base
gm
lM N#Xl ~ NaNKiI
3t04
34 2s
Brwn
O.w (Mt.]@h 2.W m~ 6.3N H20Z O.m W1 O.m HF (mm qtm) lH HNog M HF lNHF0.02NlmF W 4MHF -lMIF O.lMKIO*
lM Ml -
3s 1; 36 32
37 34 m 3D
t.
32 40 41 42
HJO H*O. K203, 0.E4 0.7M 14230. O.omw!!, m SmCzll]ol lMIKl- O.m II0. #
ml 0.3N - mm KzS4. - O.a H@b
0.lM O.sn C,ll,AsO,H, Imi -
.0 13
43 44 44 3S
blm
Green
lhwll
36 0 tl
45
32 32 a 46 34
s
I 40
-18-
Color
Green
Dark broun
Np20~
Lattice Symnetz> Reference 47 Cubic 47 Hexagonal Cubic 48,49 49a Monoclinic Orthorhombic
Orthorhombic
Np~00 Np09=H20
Darkbrown Redbrown
50,s1
47
o=~~e Np(vII), of A ~a ~ap d t@-Lf ~PoLb-Y @(VI), @(V), & J@(IV) ztith ali.ali metzZa and alkaline earth mataik am know. Abo, tt$tikzr ooqounda me zwported &th the mzw earth, other aotin~.ba, and a?kmzts in Grape 4 to 7.=2
Black Cubic 53 LaFs Purple 54 Green 55 Orthorhombic Orange 52,56 A ZaWe tier of fhoro ompozde of alkali or alkalina emth wtile Uith hfp(IV) and fluoride .haoe bum raported~2a fcm .rzioh ~ozmde & th i@(V)ad @(VI) a i%O m zqwrtd. r4@2F Green Tetra~,onal S7 Green M Rhodmhudral N@F I Pink 57 NP02F2 NpCIS 11 Groan NpC1. Orangebrown 11. s8 N#)CIZ Ozmnge 59 NpBrS Green 60 Dark red NpBrb fll Brown 62 w s NpS cubic 63.64 Np# ~ (4 dj fferent 63,64 Strlx tulm) slp~ss Orthorh-ic 63,64 Np2Ss Tetrugonml 63.64 NpS ~ Mnoclinic 63,64 NpN NpF, NpF ~ NpF c
0. NEPTUNIUM IONS IN SOLUTION D.1. Oxidation States in the (III), (IV), (V), (VI), solutions. ionic and (VII)
Neptunium exists oxidation the entropy of preparation oxidation coqplexing reduction states agents. states
in aqueous individual
The heat of formation, species, and simple methods four of these of solutions;
of the
in Table
7. ions
The first
as hydrated
in the absence
The singly
oxidation
state
in solnx~ion.
concentrations,
actinides. potentials 8.
oxidation
for Np couples
in various electrode
are given
-20-
mi&tim
.s
.4
WA
lmicFam
WIH,OI W(M) 1
~,,,K
CalOr Blua violet (kal/ml) -117
-112.5
!;,,,~~
~;-,tm-K)l -, 3.9
-.
NP(>III: . Electrolytic
H,/P!
reductlm HCl] I
:
(MM;
Yalla
Cram
.5
WI
-231
- *.2L
. mm, (hat! w Np(Vr] * stoichiutric YIP(V1] . W120H Np(<i I] NP(<vl CO*: . IK1O, J < A[(II)O
.6
N@l(HIO]~
Pink
or red
-204
-.d
+7
NP2:-
Gr40n*
of die-l lY pwpuvd nissolutlm Ll,N@L In dllure qlkmlis NP(VI) . maw (or MZj, KjS#h. p9rldnta) in 0,S to 3.SM W
a.
c. e.
ii
J. J.
Ilk?m.
-.
Il.
9s2
(1970).
m,.
Latt#m
1.
927
(Iwo).
-21-
TABLE8 STANOARD NDFOR?4AL A REOOX POTENTIALSOF PAIRS OF NEPTUNIUM IONS Standaxd Potentit.ls -L -1.astl -1.42(} -0.96;! -0.92[1 -0.152 0.337 0.391 0.4s1 0.S3D 0.S64 0.749 1.149 1.219 1.310 1.9s10 0.677 0.938 0.739 1.137 0.447 0.1s5 Fonual Potentials in lM !iclob (Voits) -1.83
. .
Process
2Np + 3Hz0 = Np20J + 6H+ + 5eNp201 + H20 = 2Np02 + 2H+ + 2eNp203 + 5H20 = 2Np(OH)b + 2H+ 2eSp3 = Np*+ + eNp]+ + 2H20= N@12 + 4H+ + eNp+ + 4H2G = Np(OH~) + 4H+ + eNp3 + 2H@ = Npol + 4H+ + 2eNP(OH)* = N@~ + 2H20 + e!U@lZ= N@~ + eNpb+ + 2H20 = NpO~ + 4H+ + eN@z M NpO~+ + eZNp{OH)~ = Npz05 + 2H20 + 2H+ + 2e2NpOZ + }{zO= Np@5 + Z{+ + 2eNp205 + H20 = 2N@)3 + 2H+ 2eNp(lr + H20 = NpOl + 2H+ + cNp3 + 2H20 = N@~+ + 4H+ + 3eNpb+ + 2}{20 = NpO~+ + 4H+ + 2e-
-22-
TABLE9 REOOX POTENTIALSOF NEPTUNIUM (IN VO1.TSAT 25C) 66-6* :1. 1.(H4 HC1O, -0.477 -1.137 (-l.236)a Npo;+ L 1 .. ,2. 1.(IM Hcl -0.437 -1.13!5 NpO$+ L[ 3. l.IOMHzS% -1.084 NpO$+ NpO~ -1.04 -0.99 +0. Ii Np3+ NP*+--I N@~ -0.936 -0.670 -0.737 . -et.137 Npb- I 1 1.87 1 Np3~-0.677 rl- -0.938 -0. 1ss --Np~ J J
7
Np3+
+1.83 Np
Np .
I
4. 1.02k! HN03 -1.138 NpO; s. 1.W NaOH
NpO;
-0,39
+1.76 Np(04) Q J
+2. 2s Np(oH] ~ Np
L 0.S82
Eft = 0.600 + 0.059
Np(VII] --.---- Np(VI)b . a. Standard potential b. According to the half-reaction NpO?- + e- + H20 -Npoidependence of EO on the OH- concentration is expressed
q
+ 20H-~g by70:
the
log [OH]-
-2.3-
curves
of Np in aqueous
solutions Reactions
reagents
necessary
to change
c~xidati.on states
jlSt-~sferred,
involve
Np*+/NpQ2 and Npk/Np022+, Rate constants redox reactions Table 0.3. 11. Disproportionation
reaction periods
in lM acid
Only the Np(V) oxidation disproportionation. + 2HzC)shows that high acid stable
concentrations.
Because Np4+ and NpO;:2* form more the disproportionation agents. The of
complexes
of completing acid
constants,
K, for various
solutions
are listed
in Table 12 where
~ . JNP(IV)][NP( VI)]
[Np(V)]2
-24-
140
ml
P4W)-NP(V)
NP(W)
*(V)-
Np(vo
NPI,IV)+NP(V) Jt
I x
Hz Oi9Chq8 02 D49chOfgs 4 hd!!L#f -1.2
30 ~J(-
-Oa
-1.0
1A
Figure
2.
Current-Voltage
of Neptunium. 7*
-25-
1/:
l,;:
.1*
9+*
.1%
..4
q q
e
,.
l~;
20 ~!).!.,.
81)J
to
@8
~[wfl)
- OpIvll
?0,0,
-26-
0.*
I
q
;:
w W 6S+ *96,.,;*
q ,e*k.
&,+*+ $j%$
I *
*t * W
*
t.;
.,.
, .,.:.!+.,
,,, ,,,,. .
TA6LE 12 EQlJ1L1~[lS4 COUSTAMTS F(R D1SPROPUUIOMTION ~ m(V) IN VNtIOUS M1O SOLUTIWS AT 25C $* solution Ml Hclo, S.S4M HC1O* 8.67M HC1O* lM HISO* 1.$6H H2S0.
- Ica
4 x 10-7 0.127 200 2.4 x 102 0.16
t2. a*
1*(
-2a-
The reverse
reaction
in weakly qcid
.w)lutions.
The rate
causes (3.1
reduction other
hexavalent
radiolytic
reduction. *CO irradiation yields of O.lhl Np(VI) for mdiolysis exposed 13. in 1.lIM HCI04, of ~p solutions to a% 1 MeV
q tmospheric
oxygen]
Np(IV)
by neutron
irradiation tetravalent
clf state,*2
80 to 90% of Np is in the
-29-
. N@l* + Np02+
ion
Acid Klob 0.018 0.80 0.126 0.? il. s 3.4 0.05 o.ab 0,8
RadJolytAc Yield G (Iuabm of !hll 4.4s S.76 6.7 6.7 4,7 1.9 8.2 3.0 2.1
-so-
0.5.
Mydmlysfs of MSptunlm lib hydrolysis of a matd ion. ion is m SpOCial caso of consists molecule
Of the
coaplox
Hydrdysis water
transfer mlcculu
proton
fron
8 coordinated s.g. ,
to a wstor
in tha outer
sphorw,
with
snd extensive
hydrt}lytic
studies
of Np l%, are
!+ydmlys:,s (V),
constants,
Np ions
in dilute
solutions ionic
with ionic
increasing charge,
snd r is
to undergo
hydrolysis
increases
irreversibly
bridges.sc
constant from KI %
q
complexes icmicproduct
may be of
T 10-1.
-31
TABLE 14 FIRST HYDROLYSISCONSTANTS 4N0 SCMJBILITYPROOUCTSOR NEPTUNIUM F IONS Ion . NP+ !!YQQwS * (~)* 8P 6 X 10-S (NpOH)+ !5 x 10-3 j) x ~()-~ 8.3 X 10-l S 1.3 x 10-9 1o-1o [Np02 (OH)]+ 4.3 x IO-* Hydrolysis Produc~ -% Reference 83 84 34 86 8S 34 83
W2+
Np02(OH]
NpO@H
NpO;+
N@2(m2
2 x 10-2
-32-
tiskving
repo~s
evidence solution
for
formLtion
of polymer
fom
of
vuriety
separating
sctinidos formation
cations. reactions.
qs
Coqlex
of complex rmctions
between
the
inner
of Ihe hydrated
cation
The relative
tendency
to fom
Np+
Neptunium
exists
in aqueous
solutions
and bromide
coqlexes
cf Np(III)
in concentrated
1S).
-33-
rmt.f 15
-m -
ua U*
S.4S
6.s4
40
s,
01 - 0,04
0, b, n, 0, 0, 0, 8, - 0.24 - O.bt - 0.51
q
49
w C9
O.M
91
W* WI
w 1
Wm
14pm,)
6, E, B, n, 01 B, B, B, 0, BU B,
4.81 757
02
* Ww)r
1
B9
0.01
m=,)
- 0.16 .
q
0.24 0.24
90 tf 91
mo.
*. [m-m)]
PIP(S.I a
El 0,
0,
n 93
1.4s X47
s.a -m 4.mIan.
[NP(C,O.)]J
92
0,
4.16
9s
0, s, B, B. 8, s, 8,
B, 0, 8, 6,
q 1.ss .17.s3
[b[c@*) ,1 rmcnw,I-
96
?.7
n 97
2WCI
Z.u
4.76 7.bm 9.47
0,
0, 0. en
.I1. o
.14.7 .1?,4 .20.2
a,
0, B*
-34-
T*I.
15.
cwtlwcd
h~
l!@Il 1lbrlm Cclmtmt O.lM !6hclo, np(ml, e.
.4s.2.
~
Mfasc 98
o.lM
W,C1O,
flp[rm:.
np(mh)
B,
.46.0S
08
o.st4 (Wl)
0,
.26. S
94
O.lM
I!xF,
NP(YTA ,
. s.ls
lLM
In IKlo,
~(mp.~]
r,
29.79
101
Np, c
0, n,
0.30 ?.s1
1P: 91
B, e, e,
101 QI
et ~,-e, ~,
q
fll e, t?,
III]
. .
103 134
0, d,
fl, fll 6! B,
I 05
o.lM
N4.CIO,
N@It (01)
@l n) ~!
[w,oKl,wO.IM O,lM O,m M4, CI0, WI.CIO. Nt,clo. 3*, 10 of TI@, [l;LYC)
N@, (lAm)
.11. -
1.51
B,
;.?5
1(J7
]-
0,
1.20 fome:
105 *O,. mf
IS. dlntm. diitributim with radm elrmmdo; 3. Smbility Fer ttw comtmts twsctlm of
.8 p,
lM
q lchnll@;
to bug L, !hc
ml*ctmtlw*
Ioprltk llInMII
qIth
cemtw+t
-e-
%-k%t-%t
** Thomfon n, - 1,1,. B,
q
1,1,1,.
me.
--
-35-
Ty84n
1
WYti
a,
6, #,
q q q q
Im
Jo
% m, m, s,
110
. a.m
q
6.1s
,In
Cltnuw IClll),
Jo n n
s o Im UC1O.
% 8, 8, on B, 0, 0,
. :.*
q
K 6?
Ill
111
112
% s,
l.?
115
2s
:s ?& x n F19rl&
JI
a. s, m, 9, e, s,
I Is *I I 14 91 111
m Ulo,
Ulo.
. 6.>? .
q
:s
1 m
Um3.
n, s,
I.m a.n
Ilb
s. 3,.1.
M Ii
n, n, s, m, k,
. ho . q.u . Z.m
41
Jo
0, s, 1,
0, c,
. 6.lJ
- REfhlEth Eth
0 Eilb
+M -
-34-
Neptunium Np(IV), strong fores trated dangers. dicating studied Definitive coqlexes peroxide of Np(lV)
complexes negatively
charged
complexes
sorbed
cm anion
is soluble
in dilute
(NH~)zCOS solution
carbonate
coqle~,es, than
au~d composition
of peroxide Np(IV)
A purple-gray of Hz[hto
a solution
stability
series strength
of Iigands of the
were a::ranged,
complexes
formedi by addition
Iigand
to Np*+:
<F- <c20Q2M7ptainiwu
~-
<E~A*-
C~As-
<Qx-
(VJ
present in
aqMOUs solution
os singly completing
charged agent
because
NpOZ(HaO)6+, is u Pom
size and
comparable
-37-
complexes,
87are
than
pentavalent
uranium,
Studies Cr:~+, Fes, been mde.& From the following creasing the first
of cationic
complexes cations
of 14p(V; with
IJOt2+, have
in HCl(lt solutions
stability
constants
listed
of ligands of the
were arranged
complexes
formed >Ythe
addition
to Np02+:
?kptunim
(111) in aqueous listed solution in Table as NpOZ(H:lO]~z+. 1S, the following strength ligand From series of to
constants
of ligands the
complexes
Npf322+:
C1O* <NO?- <Cl- <9A= <CHJCOO <F- KC204 Neptuniwn(VI J of N&(VII) complexes have been uade. solution formation show that with
sulfate because
ions
than
Np022+ icm.
This
the char~
NpQzn group
:.ncreases
to heptavaIont
neptunium.
!/1. A,,
dissolves
in HC1, otlier
halogen Hl,SO~.
acids,
and
sulfamic
acid
Hot dilute
Np slowly. acid
slowly
in hot concen-
Np-Al alloys
@.05M
c[issolve actinide
separated
or centrifug~ltion
boiling
IB.
HN03-HF or HC1.
NEPTIJNIIM COWOUNDS
Np02 prepared
by
ignition
of the
oxmlate
at
in hot refluxing
addition
Fusion
in dilute
acid
Blp
teqeratures. solutions
fluorides are
in nitric
containing
aluminum or borate
39-
NpOZ.-Al
targets are soluble in hot strong nitric mercuric and fluoride ions.
acid
solu-
tions c
containing
!.
BIOLOGICALANDENVIRONMENTAL SAWLES Np in these samples ranges from readily to extrewly soluble refractory fallout
HE:
in excreted
saqles
or a basic
however,, feces,
numerous vegetaof
in tissue.
urine,
and the
dissolution
would probably
oxidizing
agents
[individually peroxide.
or sulsample i.s
carbonate:
is dissolved
in water
or dilute
-. 40 -
Wr. A. COW?ECIPITATION C!=cipitation tracer aqueous states quantities solution that exhibit from other
SEPARATICW METHODS
AND PRECIPITATIUY is the classic in radiochemical -thod analyses. fc~r s~arating llecause ,Np in
is easily markedly
converted different
to (iiffemmt
oxidation
separation
elements
is attained
of neptuni~
oxalate
:.s regularly
used to
ils
in
processing oxide.
of neptunitm
8s u) intermediate Np coapowlds
Precipitation
of other
very
of the
different
oxidation
The first
separation
of a pure
Np
LRF9 almost
U
by lanthanum
fluoride
deconsulfate
Np is reduced fluoride
to the
tetravalent ions.
adding
and lanthanum
[nsoluble
- 41 -
TA8LE
16
COPUECIPITATIOM&EMit~litI&TRACE
AMOUNTS
carrier Lanthanu
Compwnd
!!QQM.
(Y
igQgQ c Nc
NEfY1lP
NC NC
Fluoride Phosphate
Zircotiw
ThOrim Oxalate Lanthaaa9 oxalate ThOrim Zirconim ZimOniw %dim Thmhm Bismth Potassium Potassium Hydroxides Mate Phenylarsonate Benzenesulfinat,e Acetate Puroxide Plmsphate Lanthamm Uranyl Sulfate Umnyl
c c Id c c c
Nc
w
Poor K Poor M Nc K Nc K
c
Nc Nc NC
c c c c Nc c
c c
c c
a. C
-42-
includin~ carriers
the me
rare
earths
and Th also
prec:ipitatc.
Hold-back of Zr md alkaeither to
the precipitation
precipitate
is converted
by evaporating with
untjl~. fumes of HzSOU appear, alkallj. hydroxide. Oxidation Np(VI), and, stelp. state hence, After and
yields
K.uoride-solubl(e
WILthmanganese LaFt
LaFs precipitation
Phosphate. are
Tetravalent coprecipitated
io]~s of Np, Put Ce, Th, witl~ zirconium fiompson, f~fter phosphate. and !3eaborg121 ion and
elements of this
zirconium
NaBi03 are added, the hexavalent The supernatant destroy I%~(IIIj; bismuthate
::0 oxidize
Np and Pu to ions. to
state. solution
H3P04 is added to ~:arry tetravalent is treated with ferrous Isxcess hydrazine :Lonto yield but
Np is carried carried.
zirconium
pho:~phate, pho$phate
The zirconium
is dissolved
X!No3
from Zr by coprec:ipitation
-43-
Sulfatu. trace
Ce, Ba, La, and ?dp(iti) quantities in levels to 1 mg are coprecipitated sulfuric peroxide. acid solution:~ This causes
from
salts
Np was separated
by dissolutiawt
containing
Bat and La. The Np in the supematant hyclrogen After peroxi& and again coprecipitated
bariu
was filtered, ]z
and biological
{Procedure
.
Hyiraeich
Insoluble
hydroxides
copreclpilate Generally,
all the
oxidation trivalent
states
of Np except
states
solution solution
contains contains
organic thiat
contains in strong
foxm amine
insoluble
is used as preci.~itant.
-44.
Np(IV) is sulfate
lanthanum described
to those
but does not have any advantages.lso The pentavalent cations of the uranyl transuranium tricarbonate. the coprecipitation elements 31 of tetravaare
described peroxide
and uranium
carried peroxide.
by thorium
peroxide,
to the
Other Lanthanm
thorim iodates.
and
Othfm ~cznic
zirconium the
Zirconium
phenylafionate
and of
benzenesulfinate
are specific
tetravalent ions
are separated
from other
similar
and Akimova13* have proposed concentrating from very species the tetravalent solution!;. acid-nitrate
elemmts
dilute
form he~nitrato
in nitric
-45-
and these
cations
with rwagents
of heavy organic was the -st solutions, and Pu[lV). bases, Excellent and copper
cation.
and Ce(IV)
coprecipitation mnium,
was with
quaternary
dimethyl
dibenzyl
separation
was
from rare
attained.is reagents fom soluble fomed containing cyclic 3ulfonic salts that groups, are {coprecipidye
With many organic tetravalent tstad with elements precipitates and the shove, S is carried
by the
catiom
of a ba:.:c Compami
cyclic
organic
reagent.
the precipitation
with
sodium uranyla~~tate. of macro quantities method. of Np is If other these free must from
Precipitation
or radiochernicul
cotatting
is usually
mo:re rapid
and offers
A nusber
solution; for
howevlm,
calcination
gravimetric
deternunation.
-46-
@ihti&8.
No information it is rapidly
on Np(III)
hydroxide, atmosphere.
probably
because
from mineral
as tho hydrated
volubility
is green.
in dilute
ammonium
is 0.18 g/1.35
g/l;
There
in tile early
that
is precipitated
(NH4)2NP207H20
the
volubility
is given
a:; 25 mg Np/1. 5
is the precipitant,
on the variable
some question
as to the composi-
Grayish-lilac a dilute
by adding
of Np(III)
to a solution hydrochloric
stable
to oxidation.3~ -47-
Np(IV) fluoride
is precipitated of Np(Iv),
when hydrofluoric
acid
is
added to an acid
solution
Ammonium Np(IV) pentafluoride precipitates as a bright-green granular solid when hydrofluoric acid is added I:oa solution of Np(IV) containing NH~+ ions. A similar precipitation in the presence of potassium ions yields a bright-green precipitate that X-ray diffraction indicates is KNpzF9. Tiesupcrnatant lM HF O.OIM NH,,> from precipitation of the ammo:lium salt contained 1.1 mg Np/1 two hours after precipitation; t!h:solut~ili.ty the of potassium salt was 1.7 mg Np/1 after 16 hours in O.SM HISOb -
0.5M K2SOJ4- ;!MHF.3* A double fluoride precipitate of La :md Np with an approximate composition LaIZNpFIOOXHZO obtained by ildding is hyd.rofluoric acid to an ac~d solution o equivalent amounts of La 3+ and Np&+. The
volubility of the salt in water was 4 mg/...39 Rubidium neptunyl(V) fluoride was prf:pared injecting a by chilled W.IM HN03 solution of Np02+ into a chilled solution of
%12M Rbl:at OC. The gray-green precipittlte was washed with small amounts of water, methanol, and acetone followed by air drying. 13*
0XUikt88. Brown NpZ(CZOq)3*nH20 (n ~111)is precipitated by adding oxalic acid containing Rongalite i.rto dilute acid solution a of Np(IIl) also containing Rangalite.,The compound is appreciably oxidized within a few hours.32
-48-
valence
adjustment
to Np(IV) with
ascorbic
acid, ko
HN03 by the
of the
concentration acid
varies is varied
6 and 10 mg/1 as the nitric 1 and 4M. The solukility in the tetravalent is
the neptunium
separation
dark-green
crysta..s
when treated
96% ethanol. Green neptunyl(v] when a solution of oxalic acid oxalate (Np02C20~H2}120) is precipitated with a 10% solution
oxalate (Np02C20~3H20),
a grayish-~reen
the
temperature
range
to
O to
varied
from %3.8
-49-
100r
:1::230
/
0.7[3
to-
3 0.01
~1
o. I Omlic Acid, M
of Volubility Np(lV)
1.64 _
~~
Figure
3.
oxalate
-so-
acid
concentration
varied
from WI.002M ,
Np(IV) peroxide
is precipit:lted
(V), or (VI) in >3M HNOJ by the ~o The higher valence neptunium through states
are characteristic
of the precipitation
of the concentrations
A minimum volubility
of ~lO-uM neptunium
1.5 to 2.5M HNOJ and 4.5M H::02. reproducible Precipitation Np(IV) iodate, at nitric
The solubilities
of <2.5M.
of Np(IIl) a tan-brown
HIOJ or KIOg is added to a dilute volubility 0.08 g/1.35 in lM HC1 - O.lMHIOS These solubilities oxidation
mintral
is 0.8 g/l; in lM HC1 - O.lM K103, appear states. is precipitated when to be high, possibly because
Rose-colored
that
to give
volubility
is
No sinple
carbonates precipitate
of NF(III)
A light-colored by addition
of solid
alkali
of Np(VI) with
A green
gelatinous acid
precipitate,
Np(HPOb)axHaO, in hydrochloric
is added to Np(IV)
The volubility
u g/1,
Np(lII) Np(III)
as the
sulfates
is produced
in dilute
Rongalite
mductant.
complex
teqenture.32 acid as a
concentrated
sulfuric
compound, Sulfuric
Np(SOk)2*:cH20.
The volubility
solutions
Np(IV) colpounds
Pu(IV) sulfate
fmm a solution
containing
Conpounda.
Several
Np(IV) chlorLde
been prepared.
by uixing
-52-
solution <0.DIM ~d
chloride.
19N3volubility
complex salts
reportecl.
CsSNpOC14 (turquoise),
of Np(III) at :unbient
temperature
when
-s3
B.
SOLVENT EXTRACTION Solvent extraction of Np from aqueous used most often and reliability). systems. solution for into wparation immiscible because
organic of its
solvents rapidity,
is probably simplicity,
Solvent Generally
of Np is usually ciency
from chloride
systems;
systems,such with
neptunium,and There
extraction of bath
are examples
chelate
extraction systems,
In chelate
acetylacetone,
soluble tion
compounds as hydroc~rbons.
uechanisms
In ion associa-
systems,
are possible
extractable between
organic complex
compound cation
extractable
Np extraction pentaether,
and dibutyl
which fom
of
coordination
extractability
of the various
-s4-
oxidation last
states
nd
the
two states
to bm nonextractable. by diethylether
For TBP and chelating with the uetal complex nitrates, is usually to
stable
strongest
extracted
most efficiently. is
The tendencies
of the
actinides
Thus,
conrplexing
extract
(IV) state
however, oxidation
of the
of the
in the aquebus solution. Groh and Schlealh6 and Schulz processes, and Benedictg including have reviewed solvent extraction. reagents ions have
production-scale
neptunium
in nonpolar
or CCl~rthan fluorinated
compounds,
appl:lcations. of the
17~*a total
as a part
of Np or the determination
oxidation
-55-
QElmkk ll##t
1* TW-korosem m O.sm nA-xylOm Di*thyl
Aewau Imi)*
Pmula
q Clwr
0.1
0.3
Ibx$nw
0.14
l.
9.e
0.3
1.
,a.5
~lw
-56-
Some data
0.5M TTA
for
cations
into are
1
in xylene 18.
a,cid concentrations
given
in Table Shepard
a useful
set
tion
cunres
as a function
of pi-l for
show that
by judicious
pH control,
is useful
to separate
neptunium
reduction interstates.
tetravalent
are
stabilized
in inextractable
oxidation
in lM HNOs or lM sulfamate,
femous
hydrochloride-potassium chloride.
NplIV)
If no inter-
other
pulse
height extracted
analysis.
ffrom
lM HN03, the
the Np(IV)
into
actinides oxmlate,
interfere.
phosphsI:e, phase,
present
in the aqueous
to
aro camplexed
extraction
prevent
interference. -57-
. . ..
TABLE 18
EXTRACTION COEFFICIENTS FOR VARIOUS
IONS IN1-O 0,5M TTA-XY1.ENE19
Extraction at . <3 )(
1 x 10 <5 x 10- <1 x ]()- 1 x 1.0-6 1 x 10 <l x 1.0-2 <1 x 10- 4 x 10-3 3 x
1.0 1.0
8.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 8.0 1.0 1.0 1,0 1.0 1.0
U(VI)
Fe(II) Fe(III) Co(III) Ce(IV) H(W) Aa(III) Al(III) Na m (V) Th (IV)
10-5
10-~
-S8-
standard
deviation attained
on the extraction
perchlorate Hindman.93
preceded
cycle
has
from numerous
lTA
where a combination
was used.
by ITAsolvent
extraction
and anion
were determined
ty gamma counting
chelates
a number of elements
into
O.lM
The trivalent
@i appreciable
is
occurs. into
acetylacetonate
for U and
has application
for Np.
-s9-
~7
RO(m
L
FIGURE 4. Ftercentage
-1
PO(v) p(w) cffdUI
; ;/\
Acum Am(m)
PO(v)
et(m)
10
+-
plt
Extraction Tracer Quantities of Ac(I!II), Am(III), and Pa(V) with 0.lM8-Hydroxyquinoline 1.OM 8-Hydroxyquinoline/CHCls [p = O.lM 25C]. [C. Keller and PI. Mosdzelenski, Radiodfim. Supplemented]. of
CM(III), Ada.
?, 185(1967)
-60-
Extraction of plutonium dibenzoylmethaneor salicylate has been reported. sc}lutiont separated.l 1g~ 1o Neptunium dibenzoylmethane is unstable complexes, in aqueous can be
from 3M HNCSwith
a chloroform (V),
IJOZ2+, Am(IIX],,
extracted
4-benzoyl-3-methyl-l-phenyl-ppazolin-5-one; Np(V) and (VI) are not extracted.1s3 l-nitroso-2-napthol from U and Pu.6b The TBP-HNOS system but is not, widely
the
in n-butanol
and
isopentanol
@8t4w18. processing
is a useful used
analyti~al
separation.
coordination
complex with
the metal
M(N03)149ZTBP.lb> salts
Increasing
nitrate affect
factors puritY,
the extraction
complexirlg
TBP concentration,
work with TBP has been given by Geary,lsG properties of TBP as an extracting
and chemical
for
a variety
of aqueous
solutions
by Schneider
and Harmon;
completely Na(I),
Am(III), cations
Cr[III),
Fe[II),
Fe(III),
either
of Np to the
(VI) stat{!
by extraction sequence
the
various
oxidation
> M(V).
For the
among thw hexavalent with incratsing 5 ar,d 6). are extracted coefficients from as coefsolutions couplexing of form the atomic
decreases
U(VI) > Np(VI) > PU(VI)GS The tetravalent and hexavalent similar exhibit relative
with acid
but
no maxima.
are observed
for extraction
of weak coqlexing
by the perchlorate
partially
deleterious
on actinide
extraction.
Distributicm
-62-
1on Am{III) Al Ca Co{ II) Cr(III) CU{II) Fe[II) Fe(III) Mg Na Ni(II) Np(IV) Np{vI) Th Pa Zn Ru Zr Nb Rare earths Pu(III) Pu(.IV) Pu(VI) U( IV) U(VI) HM13
Solution 4.OM HN03 4.7M 4.7M 2.14M Co(NO,)l 3.OM HN03 3.OM 4.7M 2.Cm4 4.7M 2.OM 3.OM 4.OM 4.OM 4.OM 4.(M4 2.OM Zn@03)2 2.OM HN03
2.OM 2.OM 2.OM 5.(X4 5.OM 5.(IM 4.OM 4.M 2.OM
0.003 0.0003 0.003 0.00006 3.0 12.0 2.8 2.8 0.0001 0.1s 0.09 0.03 0.02 0.012 16.6 2.7
10
23 0.26
-63-
.,
HMO,* mola/4
Figure
5).
-64-
~lgure! 6.
-6S
and hexavalent
For Np02+: 2+[aq) For analytical atta~ned in less + 3 applications than five [aq) + Bp(org) small with W02 W3) Tap] (erg) volume:;, equilibrium is
with minutes
The extraction
properties
compounds have been studied; Np have been defined. found the order Higgins
F:w separation
to be phosphate
((RO)SFY1) < phosphonate ox:~de (RsPO).i72 for I.he extraction wilh various
(R(RO)2PO)
< phosphinate
of some
trialkyl
in Table
the alkyl
depressed
increasing
of the alkyl
in the phosphate
carbon
The effect
depress
The extraction
cimapounds is
number is not
same as that
for TBP,
66-
TABLE20 DISTRIBUTIONOEFFICIENTSOR THE EXTRAC1]ON TETRAVALENT C F OF ANO HEXAVALENT CTINIDES A UITH 1.9MTRIAI.IYL PHOSPHATE/
n-DODECANE FROU ZM HNO! AT 30C7
Extractsnt
Tri-n-butyl hosphate p Triisobutyl hosphate p Tri-n-amyl phosphste Tri,imamyl phosphste Tri-n-hexyl hosphate p Tri-n-octyl hosphste p Tri-[2-ethylhexyl) 2.s phosphste Tri-[2-butyl] phosphate O*4S Tri-(3-amyl)hosphate 0.22 p Tri-(3-methyl-2-butyl) 0.18 phosphate Tri-\(4-oethyl-2-amyl) phosphste 0.047
Distribution Coefficientsa . Np(IV)b h(IV)O J(VI] Np(vI)~ PUNI) . 3.5 26 15.6 16.1 3.2 3.4 2.? 15.9 22 11.8 4,1 19.3 32 15.6 4.2 4.4 18.9 17.8 34 4.7 4.s 20.0 38 1S.6 3.6 3.9 1s.7 33 15.3 3.4 4.3 4.9 3.5 3.(? 3.5 25 28 18.1 24 22 58 42 49 47 38 25 24 23 5.7 4.6 50 S.4 4.9
a. For traceramountsof the givenelements. b. The aqueousphasecontains O.OIMFe(?WzSO~)t. u. The aqueousphssecontsins O.OIMN8NOt. d. The aqueousphasecontsins O.OIM (~)2Ce(10,1{.
- 67 -
elements.1
contact with 12M N(21+ O.lM hydroquinone separating trivalent the other contact Np(I!/) from U(VI), rare earths. Pu(III),
for
The K value
cations,mlO-l; followed
by a single pha:$e.~~
by multiple
of tl~e organic
bis(2-ethylhexyl)orthophosphoriccid(HDEWP: from HCl solutions a (Figure 7), These data offer the basis for separating Np from
many cations. The distribution coefficients of Am(Ill:], U(VI[) in HDEHPfrom HNOo are given continuity probably in the Np(V) curve in Figure Pu(IV), 8.179 NP(V), and
The disis
at high acid
concentrations
due to disproportionation
both of which are more extractable Np(V)Iin dilute Pu(IV), that nitric acid
a few percent
separated
by a single
HWH!P to purify Am(III) from other actinides in higher valence states and,to accomplish their mutual separ~a:ion.Am(III), Pu, and U were extracted from O.OIM HN03 after -68stabfl:[~ation of Np in the
Elrl$l
c N
Fr
--CAB LMtAIXCAMabmwl#.
*T1 *EN s
DatJ#TMi=ui. Ma of EMhmurJ,
+ DFP
wlks.stusiqmM4allW~da&
Scrlibitq
Xd
-.
Figure
7.
Extraction in Toluene
-69-
Log [HN03]
Figure 8. Extraction (Isooctane of Various Actinicl~!s into o.5MH(lEHP diluent) from HNO:I Solutions. lTg
-70-
pentavalent
state
with
oxidized to HP(V)
O.lM HNOs.
the HDEHPwith
and recovered
by back extraction
in the colorflbetric
et a2!7Dal
studied acid
the extraction
of several
actinides
by mono-2-ethylhexylphosphoric (Figure was ~103, Gindler counting. addition reduction 9). The distribution 104 times larger
(HzMEHP) from HC1 solutions for Np(IV) in 12M HCl species fission by studied.
coefficient than
method to puvify
2GPu for
The Np(IV) can be returned of TBP to the organic in the distribution phase,
phase
in a great
Kosyakov et U2. *79 dete~ned of Am(III), (Figure conditions 10). Np(V), ~ey than Pu(IV),
those
ROSS183
have written
a general
review
of the
properties
of tri-n-octylphosphine
c~xide ~m).
-71-
R17
-1
Figure
9.
ExtractIon H2MEHP in
-. 72 -
6.a
0 LAW[HN03]
0.5
I .()
Figure
10.
Extraction of Various Actilnldes into 0.2!4 H2MEHP (Isooctane diluent) From HN03 Solutions.~79
-73-
Extraction data for Np and other actinidos into TOPO have been sunmnarized Weaver and Homer. leb by Extraction with methyl isobutyl ketone (hcxone} is based on the solvent power of hexone for the covalent nitrates of the (VI] oxidation states. Hexone was used for large-scaleprocessing of irradiated nuclear fuels (redoxprocess) but has been supplanted by other sol,vents both in plant and labflratory applications. A twocycle extraction system for the separationof neptunium from uranium-fissionproduct mixtures has boon given by Maeck.195 Hexone extraction of Np(VI] from acid-{il:ficient Al(NOJ)S was followed by TTA extraction. Excellent separationfrom U, l%, W, and Zr was attained. Also, Np has been separa~ted frolm Pu and La. Np(VI) and IPu(VI) were produced by oxid~tion with KBr03; both were extracted into hexone from an A1(N33)3 solution. Back extraction with an aqueous sodium nitrite solution yielded Np(V) and Pu(III), neither of which is soluble in hexone. The hydroxides were precipitated and dissolved in nitric acids and ferrous sulfamate was added to give Np(IVJ and Pu(III). Np was extracted into a solution of tributylaminein he>,one, leaving the Pu in the aqueous phase.*2g Extraction coefficients for ions :.nto hexone different aqueous from several
Dieth:ylether uantitativelyextra,:ts q hexavalent Np, ?%, and Am from salted solutions containing a strong oxidant (Table 22).la6 .74-
TABLE1!1 EXTRACTION COEFFICIENTS VARIOUSSOLUTESINTOHE)(ONET 25C1 OF A Salting Agent (M) Al(N3s) s 1.3 1.3 20 2,0 1.3 1.95 1.3 1.s 0.7 1.0 1.5 1.0 1.0 1.0 1.3 1.4 8 8 11.1 ill 11.1 2.0 0.s 1.0 2.0 4.3 8.7 11.0
Nc~-
!wd!!!l
01 0.0 1.7pH 0.1 0.5 0.5 0.5 0.s 0.5 0.4 0.0 0.5 0.2s 0.10 0.20 0.4 0.2 0.2 0.5 0.5 0.5 0.3 0.3 0.3 0.3 0.3 0.3 0.3
Extraction Coefficient 0.02 <0.0001 0.011 0.0003 2.1 0.0018 1.5 <().001 1.7 0.82 1.1 0.009 0.01 0.10 0.12 0.10 0.004 0.0005 1.7 9.8 0.14 .50.0 0.1 2.0 30.0 0.18 2.0 14.0
HH,HO,
2.6 5.4 JI.5 :;. s :;.2s :i. 1 4.1 4,,6 E.2 8.2 11.6 11.6 11.6 6.3 1.8 3.3 6,3 4,6 9!0 1~ 3
Al(HO$)S A1(HOY)S
tai,tq
of a. Concentration all solutesis 2 g,f: b. h-emitting aftel 44-day 1 coolingperiod. fission products
7s ..
TABLE 22
A E.KTRACTION OFNEPTUNIIH, PLUTONIM, ND MERICIW
-. Solvent Ethyl ether Aqueous 1!4 tiW3; bN ml Dibutyl carb i no 1 W 7 HNos HNo, tflo, co w Iiuws sat Phase IWbW, 9 17 1-7 23 91 15 ~ (xv)b
!ko2.
17 6S 23 48
!P.u!l
12 !2 )1 19
!!LQIQ
w
a
70 89 8: 95
WQ!!l
100
ca(K)$)*;
0.6)4 w,
o.oSN ~~
11
?i.4M ca(ND1)2;
a. b. c. High Np(IV) Dibutyl efficiency; unstable ether. no in value W40J.
0.3
.
41
given.
Dibutyl-butyl
phosphonate,
DBBP.
15% CCIQ.
d.
@BE, * ith
-76-
Other
elements
that
extract As(V),
Au(III),
and
SC{III);
P, Cr(V1],
and Bi[III)
extracted.
back-extraction
with
dilute
acid,
orhydrazine
Np(VI) to with
for
several
a function
of nitric
concentration
are reported.loloo including mines, long-chmin and quaternary alkyl or aryl primary, react in
tertiary
amine salts
+ (aq)
+ A (aq] anion
+ R3NH ---- A-
(org)
be either
a simple
acid. anion
analogous
to anion
A (erg)
+ B (aq)
for Np(IV),
are usually
in an organic
-77-
solvent separation
(xylene,
benzene,
or chloroform).
TCI
and to prevent formation of a thixd ph8sB during s-1 amount [3 to S vol%) of a long chain phase. The lelative aliphatic
extraction,a alcohol
extractztiility the
depends
in the
> primaryJ$i
is reversed.
The distribution
and hexavalent actinides from IiCland HW~ acid solutions sequence Pu ~ Np > U > P- > Th. distributim coefficients state) for from with
decreases in the
Keder et al. 190 have rqorted several nitric xylene actinide acid elements with
solutions
(TOA) cliluted
(Figures li, 12, and 13). show a second that power depende,tce on the involves
The tetravalent ions amine concentration, two amine molecules. trilaurylamine review
indicating Extraction
the extracted
complex
of :Iiquid-liquid
high molecular
weight
amines has been publi:nrci. lg Np(IV) has been separateo fission products by extraction frm U(VI), 1u(III), Am(III), and
of Np(IV) info
tri-iso-octyhmine
-78-
1.0
P---d
I
Figww
11.
The Extractfofi of tlm QwIrawhnt Acti nt& llftrat8s by 10 vol %TOA In Xylem. ;s
-79-
r-vl
t
lo4
no+
02468
12
14
Ffgurt
12.
-80-
Ioo#
w-
-1
AQtJoan Hrws, M
-81-
acid
solution
containing
organic solution was scrubbed Sul.famate. extraction. extraction Final 19~s with purification
SM HMO$containing with
2*~AJSby
TIOA.*g
[i# > 20] froa 0.1 in xyltme. for a large fron for various
O.lM tetraheptyl
:litrata data
of elements
anmonium c~~ds
and a proc~lure
solutions have been determined, Np and Puuith Kedertiss tetra this system
separ~~ting
has been SWpOrtaX1.isC the distribution coefficients from into than TOA Np(IV]
has reported
Np, Pu, and U from HICl solutions Pu(lV) is much more extractable and the hemnmlent :\ystem.
(Figures
actinides
extractable
were strongly
by the
primary
amine Primene*
JH-T in XYlonc.
from mlfate
*n) ~re
sndi
by each extractant
Rohm q nd
-a2-
Jd-L-Ld_d.-s
024 SOK) Hcl. l!
Figure 14.
by 10X TM
ExtractlonoVU(IV) and NpI(IV) and Pu(IV) b{$!,m Tu frm MCI Solutl on%
q
8s
too
10
E. . . /
2 4 6
10 ExtractIon of Hexavalent U, NP, ml with 1.0% TOA Pu fmm HCl 5olutlon in Xylene.19
Figure
15.
-64-
taken
separately.
described
understood. Although
of this
con~iderable
for Np.
a procedure
to determine
daughter of curium
containing
quantities
and fission
O.lM l-phenyl-
(PMBP) and 0.2SM tributylphosphate separate lM HIP04. other gm Np(IV~ from Zr, More than
99% of the
Np wa~ extracted
by measurement
the
diluent
of chlorofl}rm,
on the
extraction
structure,, other
interaction Figures
between
complex
and diluent,
factors.
of variation
of diluent
mixtures
on the
-8s-
. ,. . .
--E
L 0.1 v --d
. /
4
I .0
2
k
002 OA 0.6 0.8 Mds Fmctiom of Dilusnts
Heptunlm ExtractIon W HNOS Into Dlluent 0
: c.
Figure
16.
-a6-
Mol. Fructions
Figure 17.
d Dihmts
Of stri button Coefflc<lunts fclr WO( IV ) Extraction with 10-2N Tetrat@ylkmontum Nitrate from 3M NtKIs Using Mixtures of Different Dfluer~ts.203
-87-
c.
ION EXCHANGE hhny variations of ion exchange are used for separating
14pfrom other ions. Np ions in dilute nineral acids with no strong completing ions are sorbed by strongly acidic cation exchange resins, of cations increasing of sorbability
~22+ > W}*
polystyrene. on cation
and decreasing
radius. .Np is
on cation
exchangers
tions and eluted with high uoncentraticms of mineral acids; elutio,~ NpO~ proceeds first and Np(I\) Ss last. Some anions of form neutral or anionic complexes with different oxidation states of Np, so that Np may be eluted by this mechanism. Both Np(V) and Np(VI) are slowly reduced to Np(IV) by common organic base resins. For this reason and because cation exchange of Np(IV) offers limited selectivity in the separation from other multivalent cations$ this method has not been used ~idely for analytical
mc)stuseclfor
separation of Np in analytical and process applications. The method is simple to perfom and yields excellent separation from many other elements, including most of the fission products. Ion exchange ha~ been the subject cf many reviews. The books of Helfferich,20 Samuelson,zos Anrphlett,20& and Rieman ant
-88-
Waltonzo
to the
theory
of
of ion exchange
Massart,20e
and Faris
and 8uchanan. :10 forms anionic sorbed by anion nitrate resins; and chloride the anionic elements. sorbed
Np(IV) strongly
complexes. elements
sep:ltation
:;ystem than
The distribution
of nitric
acid
have been
given
In a typical is adjusted
exchange
containing
Np
of Np(W~)G2-
ions, all
and 0.01
that
is heated
sufficient e.rcess
sultlmate
gassing acid
cationic howevez,
femous
contaminants.
washing with
sulfamate-0.05M
reduces
to
-09-
Figure
18.
Sorption of by Strongly
the
Basic
Elements Anion
Solutions
Pu(III),
which Th.
column. with
Washing with
greatly
as elution superior
to gel-type
of Pu from Np. 21sa A number of similar in acid concentration for hydrazine and substitution have been reported. amounts of Np(VI],
procedures
of semicarbazide
of tracer acid
Th(IV),
Am(III),
by anion
exchznge
The feed was adjusted to 7.2M HN03-0.054 NaN02 at 50C to yield Np(VI) and Pu(IV). After sorption on Jowex l-X4 resin, the 2+ and Np02 , 0.35M NN03 of these because
Am(III)
with
to elute cations
work with
separation Also,
of Np probably
Th([V]
separated.
reductmnt
pure with
for
production cycle
of
exchange
and two
anion
exchange
concentrations -91-
These data
exchange
are used
(Figure
to design
separation
systems
:forchloride :}eparated by
anion
19).*2*zi9
chloride
anion
exchange
chl~oro-complexes
NHI+Iin 8M HC1, NH20H-NH41 in 12M HC1 or Fe;12in 8MHC1; Th is not retained; and Np is eluted with 0.3M HC1.iss220 Distribution data for 65 elements on Dowex*l-X8 from 2 to 17.4M acetic in water acid
have been reported221 (Figure 20), E)(~Flles several of given. Distribution data for
60 elements on cation exchange resin from 1 to 17.4M acetic acid in water have also been reported.222 With !lp(VI) in 7.9M HC?HSOZ,
A method to separate and determine Np, Pu, U, Zr, Nb, and MO in uixed fission products by anion exchange with HC1-HF solutions has been developed.223 Trace quantities of Np have been separated from macro amounts of Zr and trace amounts clfNb by elution with HC1-HF solutions.22 Also, HCI and HF solutions have been used to separate U, PUB and Np from each other ard from alkali metals,
alkaline earths, rare earths, trivalent actinides, Al, Sc, Ac, 7%, Y, and Ni (Figure 21).225 Controlled elution with a series of solvent mixtures was used to separate Np, Pu, Zr, Nb, Mo, Tc,
Te, and U from fission products.22G The chloro complexes were sorbed on anion resin and sequential washes with 12M HC1-NHZOH-NH41 (PU)B 10M HC1-Aq H20z(Np), 9M HCi-Aq Hz02(Np and 2r), 9M HC1-ethanol (l:i, Zr), 6MHC1-ethanol (1:1, Nb), ethanol-lM HC1(4:1, Te],
q
I u)
I!iil D1
-J
@1
I 1
w. p
WI
Em-1 lEm
m n
w
ZI+I.1
4a.1
I 4
id Q
w..
d
~E Cdq .,
Ei34 HJ#
,,
81
ml m ::5..
1!1
ULlIiLi.1
L$l w RI
km).
4-4
w
L pd#i
IalIEwF#l
H EfElEEEw
-F4
cl
tl
m.
*I
.,
Ewu
Figure 20. Sorption of
EiEili
the
Elenwnts from Acetic Acid Solutions by an Anion-Exchange Resin ?2J
T-----71
4
k-
!50
VdUCWB9
Figure
211.
400
-9s
ethanol-W
IK1(4:I,
*),
O.IM Kl(ll)o
and 4M tMls(Tc).
Other teristics
literature
has
included
a study
of
the elution
qnd ~b~h
charac-
af xp,
Imos,
data
~y~t~s each
with acid
Skuex-2
fm O.lV da:a of resin. were
wru
given for
CO concentrated, were
pss~ble
separations
data
bmsed on
wre 8iven
eqvilfbrifor a
summarized.*
Equilibrium
ndmr
elements
lnclwl~ng
ofSp
Np in 0.1
frtmCs
Separation erratic.~a
andleuas
Sp ukth
has hem
fmm
Pa by elution
has also
uith hem
Pa elut{ng u~th
Separation
by
clution f~rst.zz*
S!UIUl
case Sp elutes
!JJ(IV)
Sa2CD1
quant~tat~vely
or dilute
on *R-l
MC1.YO
fsxm O.IN
qnd elutod
Np(Vll] .Sovikov
soluble
fores
stahlc
studid
mlkal~nc
the anion
as sk behavlw
:+OSof
Ion.
this
a: (x:.z
complex
as a
poss~ble
has~s
from other
experimts; this
elmts.
was attributed
lhe
sorption
to the
was irreversible
redxtion of
the ~(~11]
by the
resin.
-%-
An anion exchange method using the nitrate system has been reported for removal of Np before spectrochemicaldetermination
of catioinic istpuritiesz]z (Procedure23, p 200), In several or ignited after reported instances, acid anion exchatn:le resin ni:rate exploded
or strong
Tlw!se qccidents of the exchange presence should carefully The nitric col,un
of
of the reaction
leading
heat.
Anion exchange
concentration
should
particularly
of radioactivity
acid
type
resins
applications
reduced
for
Np separations resin.:Sh
S1OU1Y by the
reported
of $ip.
Y. A. Zolotov
D. Nishanov235
fissioc
separation
of Np from U, PI),and
products
a
by elution
of Np(V) qhead of U(~1) with IN MNOj form. bmsate. Np was initially oxiSeparation Also, of Np
frou
cation
resin
cation
used
and Zr(lV).
Np was
ox~d~zed
to Np(V) in dilute
-97.
acid
before
sorption
on the resin,
was reduced to hlp(IV) by the Dowex-5OWrosin separated from the other cations.23G
coefficients
elements
were
Conditions
separation
of U(VI) and Np(IV) and separation of Np(IJ) and (Figures 22 and 23), Mary other separation
be devised
(Figure 24).237 Np and Pu have been separated by elution from cation resin
with HF after reduction to Np(IV) and Pu(III) with S02.238 Np(IV) was eluted with with first with Also, 0.02M HFZ3, and then Np was separated Pu(III) was eluted exchange
0.5M HF.
from Pu by cution
HBr follGwecl
by TTA extraction.20
elution
development
on cation
resin
70 to 90*C with a-hydroxyisobutyric separation and with of trivalent macroscopic type actinide quantities,z~~ for
Although
no specific
of this radioactive
Np are reported,
solutions. for many of the eleme~ts acid concentrations on Dowe3@,-50resin and also over a
data
of hydrochloric acid
of perchloric
concentrations
a-
Smp18
C)-2
.44J-.-JQ 6 8
Column Volumos
Figure
22.
Separation
(Oowex
!iO-X4
3
-m
Sarrrpk 6M HBr 9M
HBr-CL2M HF
2 ~MfJ(lv)
t, ,{ 0
4 8 12
-EkJ#..
Column Volumes Figure 23. Separation of Pu(III) and Np(I\) by Cation Ex$~~nge (Oouex5O-X4, 0.28m2 x 3 m COl~~, 600).
-99-
Figure
24.
Sorption
of
the
Elements
from
tiBr
Solutfons
by a Catfon
Exchange
Resln,2$7
Figure 26,
Inorganic resins
exchangers
superseded capacities
principally
the synthetic resins. However, inorganic exchangers have the advantage of greater resistance to radiation dumage. The distribution coefficients oxide, of 60 cations, zirconium phosphate, including Np, on hydrous
zirconium
phosphate. Np(V) is not retained while trivalent elements are readily eluted with lM HNOq. Pu(IV) containing quinone. of Np{V). HF solutions reducing Zirconium agents is eluted with 0.5M HN03 or hydrostate
such as ferrcus
sulfamate
phosphate
the oxidation
of Np, Th, and U from HN03, HzSOb, and molybdophosphale of so~ltion (AMP) colunns has been
conditions
103
D.
CHRWATMRAPHY
Emhwction
C?w0watog3up@. separation
Extrac::ion
chromatography
has 100%
was
to the
of Np, PUB Am, and U with The diatomaceous vapor, Nitric then acid, :~hase.zho
of NF
on diatomaceous exposed
silica.
silica
treated with
Other
were required
to prevent
reduction
separation
same system
with
0.5 to 2M HN03.
was of
and Np[VI).
It is probable
Np(VI) occurred. 23gNp was separated of TM sorbed on glass from fission powder.251 than proclucts and U on a column method gave recovery However, Zr. was -
separation isotopic
so that
dilution
column separations
Np frm
and activation
products
on Poropak..Q impregnated
or ~eflon** phase
stationary Co.
Registered
tradename tradename
K. Kellogg
q *Registered
of Ou Pent. - 104 -
separations.
Kel-F
powder
:oated
with
trilaurylamine
.lMHN03
HzS04 - HN03.
selective
for Np(IV) and has yielded chemically ratio of U to Np was >1010 in the feed?s3
The separation requires one to two days. A :imilar method was developed for the coseparation of Np and Pu from U.zs PapeY C?uwmatograp)qf. elements with Ac through Paper chromatography of either Rf values for
Am in many mixtures
and butanol
methanol,
ethanol,
have been determined Np(VI) to Np(V) or Np(VI) is slowly of the bi~nds. with
Keller.zss before
to reduce because
starting
reduced
in poor
separation
12M HC1-butanol
and
>8M HN03-butanol U(VI) was attained from U(VI) with Clanet2sb numbers
good separation
of Np(IV) from
>lM HC1-butanol;
Rf values
90 through
96 in mixtures
of mineral
.~cids with
applications. (V), and (VI) have been reported 0.5M HN03 developer solutions for
TOA using
105
are well
actinides.zs with
(20:1)
were also
solutions
using
in acetoneand petrchloric
developer
acid.2se Twelve fission have been separated fkuoric and neutron from irradiated capture isotope:; with acid including aqueous mixtures 23gNp, hydroas
uranium
and methylethyl
ketone-hydrofluoric
developers.259 Thin Layer (%rcxnatography. valence elements saturated states by thin with Rapid separation and from ether on 7eflcm-4O solution of different actinide powder has been
O.lM tetrabutylhypophosphate e
demonstrated.2
transuranium
has been were synthesized gas. colums The maintained Cm, Am,
demonstrated.z
A12C16 vapors
carried than
at %2500C with
less
in order as lighter
experiment.
The retention
- 106 -
of A12C16 condensate at the exit of the c:olumn. The actinide hydroxides are carried with La from strcxlgly basic solution and separated from Al. Then the actinide is deposited, anclthe alpha spectrum is measured with a surface barrjer detector and channel pulse height analyzer.
multi-
F. .
OTHER METHODS
Volatilization.
from PuIIII) chloride and other less volatile chlorides has been reported. 261262 The actinide chlorides were prepared by passing carbon tetrachloride vapor at 650C over mixtures of pl.utoniumneptunium oxides or oxalates. The nepturium chloride sublimate was collected with a separation factor of%3 x 103 for Np initially containing 4% Pu; the yield was w96%. Tie method is useful for obtaining quite pure Np where a quantitative separation is not ~equired.
NpFG is quite volatile, intermediatebetween UFG SLndPuFG. Separation was attained from UFG by co-scrption of the hexafluorides on NaF. Then the F@FGONaF complex was reduced, and the UF6 desorbect. After refluorination,the NpF:cwas desorbed.263 EZectrophore8i8. Clanet256 has developed m electrophoretic
method on cellulose acetate membranes tclseparate the charged species formed by elements with atomic rmrnbers90 to 96 in 1 to
107
12M HC1 and HN03. Mobility curves have beer obtai:ned for the acid concentrationrange for both acids. A large number of potential separations of these elements and the solution conditions are tabulated, Some of the separations of Np irclude !Jp(IV) ctr(V) from U(VI:); Np(IV) from Pu(IV) or (VI); Np(lV), (V), or (Vi) from AmlIiI) Cm(III); and separationof the clxidation and states of Np. Electrodepoeition. to prepare
mOUMS
has been one report not been used as a separation method. Ther(! that U, PtJ. and Np were separated by electrtllysis from HIWls by
var:ying the pH. Optimum conditions were slulted current density as 7S0 to 1000 mA/cm2 with volume of 20 to 30 ml. Pu and U are completely a plating time of 2 to 3 hours and solution
Np from other
ac-:inicles. l:ations
no useful separation
Mi808zkneim8.
scheme Ih,is beer) described uhich elements fissile including dlememt.z$ Np renaining The of isotopic ion methods.
yields after
sequential neutron
exposure
of 1 mg of and isolated
spectrometry
using
extra~ction,
chromatography,
prccipitution
108 -
Counting.
Because
for identifying and quantitativelydetenaining Np. The two most common Np isotopes by alpha MeV. it counting are its 237Np ~d two major for 23*Np. 237Vp is uwally alpha a period transitions of shout $~t 4.781 6 months of its determined and 4.762 or longer,
can be dete~ined
by gama
ray spectroscopy
2y]Pa
daughter. gam
:?ay, the
239Np is determined 228 md 273 keV.*O The gross proportional alpha counter
counting
transitions
activity or plastic
of 23Np
can
b41
determined cout~ter.
with
scintillation)
qn
If other
q lpha-eaitting q nalysis
with
nuclidcs
q
are present,
barrier
q iphm pulse
height of
surface
detector
8111cws a detemimtion
the percentage
Liquid
of the
total alpha
scintillationcounting with
qlmost
q lpha activity
100$ q fficiency
presence
other
in giquid
%C!intillmtion
-1o9-
as
coward
to
surface with
barrier either
--ray detector
or a Ge(Li)
detector (228,
the
tw]ergyresolution of a
detector
1.0 KeV) is much better such Ge(Li) is 3 to 1S% for the (LEP)
to a 3 x 3 in. Ge(Li)
low-energy
detectors efficiency.
resolution
lower
determinating
237Np was
coincidence
determining
Thf!activation product is
short-lived 23@NP, which is determined by t:ountingits 1.0 MeV gama before ray. To obtain maximum sensitivity, irradiation. and sel,?ctivil:y of radiometric the Np should be purified
neutron of tho
sensitivity
methods alpha
In summary,
advancements in nuclear and 239Np. Because of the contirr~ing radiation accuracy detection of the systems, the sensitivity, precision, and discussed above could be
radiometric
methods
- 110 -
O.ostoo.lmg
s m 10-b
1O-B . . m -. so o. z m1 10-~ . . 50 -. M 10 . . 5m Jo- . . Icm . . ,@l M sm Ir .. . so . . . . co (0.1 1]
I a [0.1 CO 1] ... .. Iw . . Iw
O.u
10 to so
O.oa , ,1 O.OJ
,.,s
111
Ill
0.1 to 0.s ~
Yoto
100
1,1
0.0s
It
lo tow
0.01 to 0.1 q
G.1 I 1
..
1 1
0.1
0.s
Iq
101
uJtozQ
10-m -i
0. 0.
In
10
10 W1
10 tm
Stoa
10- 10
Ic
q o* q 18
0.1
5t000
10-1 KI
. .
0.1
I
1
. . [10s)
T-w- tm #
1 ~sa qIw
*I
F?
. .
111 -
Preparation.
Direct
uethod
sample pulse
disadvantage of the deposit, particles. (S0 pg/cm2) evaporated homogeneous and bums a suitable evaporated flamed collodion
analysis
absorption
of the alpha
a drop resu,~ting
polymerizes
sample steel
is transferred disk,
to prevent cooled,
to dull
red heat,
solution,
a mixture
to be resolved.
Electrodepositionresults in excellent sample solutions that evaporate very slowly that or leave contain
solutions
from
a vmriety
of
qnd under
sewral
Gravessgg
described
112 -
a semiquantitativemethod
for
depositing
Ko27~) reported a method for quantitativedeposition of Np from O.ZM HC1OQ - 0.15M NH4COOH, and Mitche11271 used NH+C1 - HCl to obtain a yield of94%. Some systems used by other workers272-274 are formic acid-ammoniumformate, ammonium coalate, ammonium acetate, ethanol,, isopropanol,and Nli4Cl witt uranium carrier. Donnan and Dukes275 developed one of the!fastest procedures for quantitativedepositions by combining Mj,l/chells methocl with uranium carrier addition. 23aU is added as
ii
carrier in three
increments to the NH%Cl electrolyte to ensurf! quantitative yield; only 20 minutes deposition time is required. An average recovery of 99.8% with a relative standard deviation {IftO.2% (n = 10) was obtaind with Pu. Similar results were obtained with Np. Resolution of 20 keV is achieved consistentlywith electrodepcsited mounts and a silicon surface-barrierdetector. Parker and Colonomos276reviewed electrodepos;Ltionrocedures p and described two new methods. One is a co-depositionmethod for alpha-spectrometry,and the other for preparation of carrier-free m layers as fission detectors. In the co-depc,sitionethod with 237N was deposited quantil.atively 10 min at in uranium carrier,, P 170(0 with stainless steel as the cathode. V In other recent work, Np was deposited quantitativelyfrom ammonium oxalate or ambonium acetate solutifm or mixed ammonium
- 113 -
oxalate-ammoniumchloride electrolyte .z-zgo Alcohol is an excellent plating medium for aqueous and orgalic samples. Methods have been reported with for ethanol, isopropanol,
Deposition
saturated hydrochloric,
on Np and
actinide Other
methods
with
excellent
resolution
vacuum sublimation
and electrohave
spraying.28b-2g1 several
and (!lectrospraying a longer including time than a specially high electrode voltage for
equipment
capillary
spraying.zGG
bands,
spectrophotometric
analysis
rmdiometric
procedures
anu opermtion
procedures
single
from
the nlar
extinction
- 114 -
..-.
solution at the proper wavelength. When more than one oxidation state is present, appropriateequations ma:~be formulated for the concentrationof each component.=g= Abaoz@ion
Bade.
Important
extinction coefficientsof the different oxidation states are listed in Table 24. Most of the sharp bands can be used for
qualitative or quantitativework even though they only obey Beers Law over a limited concentrationrange. The best band to
obeys
Law.
The strongest bands for Np(I\)(960 mp, Law, but they slit can be used with The strongest
723 mp)
and constant
width.
Np(V) (at 980 mu in lM HNOS) does obey Be{:r~s Law;2qo a highresolution should mmochromator (e.g., a double-grating and coworker:;2go nuclear state obtained Correction monochromator) have developed fuels a
be used.
Cauchatier
Np in irradiated
by measuring by
The pentavalent
uixture
hydrazine
to a Np(V]-Np(VI) acid
evaporation
of the nitric
solution.
Pu(VI)
is necessary. The most useful Colvin nitrate developed solution.*9 state with a method using In this sodiID
1.23 urn; in
hexavmlent
is
q djusted
to 1 to 2U.
The qbsorbance
is measured
- 115 -
TABLE24
IMPORTANT ABSORPTION PEAKSOF NEPlUNIltN2g-2s
Np(II1)
MolaI Extinction .
~la,d ,86b,d 84E+ 991b 1363b 50CF ~wa,d 590.5=~d WOCF cd ~71s
7z3b
Np(IV)
74fd
m(v)
800C ad 825 961# 975= 428a ~l,b,d ~17cJa 98& W39CF 476a 55P 1223bJd 1230cd 412* 618e
NPwl)
Np(VII)
Coefficient 44.5 25.8 30.5 44 (50to 60C) %25 W27 -39 %15 22.9 16.1 % 7.5 ~ 3.7 127 43.0 %2] 24.5 162 %32 11,1 22 --18 395 %]80 6.4 6,8 45 %43 1370?40 382 *1O
- 116 -
against a reference HN03 solution that i:;the same HN33 concentration as the sample. The method has a relativu ?0.5% at 3 g/k. A number of ions, ten times salts including that standard deviation of
in amounts
of neptunium region
in wh:.ch numerous
well-defined by
methods
for Np lack
extinction [1,
coefficients
A uethod
6-disulfonic reported.301-303
acid-2,
benzenn
is measured intensity
and its
4 to 6M HN03.
coefficient at 665 mp is %105. Chudinov and Yakovlev separated U{IV), Pu(IV), and Th(IV), with which fozm colored di-2-ethylhexylphosphoric extraction, The lower accuracy complexes, acid from (HDEHP) in to Np[IV], is
NpC)2+by extraction
carbon tetrachloride.
After is added.
III
is between
1 and 7t,
- 117 -
Bryan and Waterbury 302 separated Np from U cnd Pu by extraction with tri(iso-octyl)amine(TIOA) before d~!termining the arsenazo 111 complex. They found that of 4S ~!lements teste:i, only Pd, Th, U, Pu, and Zr interfered, The :r{!lative standard deviation was between 7.2 and 1.1$ in 200-mg :;amples 8.S to of 330 ppm of Np.
(Procedure 20, p192.)
studjed the color complex of Np(IV) with Arse]lazo M.30 At 664 mu the molar extinction coefficient is 1.18 x 10s in 7M HCl and 9.5 x 10 in O.SM HC1. Thorln was used by several. workers to analyze ?Jp.30S30G The absorbance is measured at 540 mu against a reference solution not containing Np. The molar extinction coefficientmeasured with a Beckman DIJspectrophotometeri.s ~~14,500. The precision of the method at the 95% confidence limits is t2.1% fo:r0.63 Ug of ?Jp/ml Chudinov and Yakovlev used extraction to separate Np from . U
and
with the Technican AutoAnalyzer, and the pr~cision has been, improved. Np reacts in weakly acidic solution (pHv2) with xylencl orange to form a colored complex with an absorbance maximum at S50 mv and molar extinction coefficient of 5,S x 10*.3*8 X,ylenol orange is three times more sens~tive than thcrin but only clne-half as sensitive as arsenazo 111 as a reagent fcj~ Np(IV), The greatest
- 118 -
advantage
of xylenol
orange
Fe(III), Zr, Th, and Bi interfere. Np(IV) forms a color complex with quercetin that is stable in the pH range 3 to 7 and obeys Beeris Law ove:ra concentration range 0.4 to 4.0 ug/ml. z2,3 x 10b at 425 mu. The molar extinction coefficient is
to remove cations and traces of organic i:npuritie~,30g The color complex of Np(V) and arsen~zo narrow pH range and was studied by Chudinov 111 exists md Yakovlev. over a 310 A
method with the green-coloredcomplex of llp(V)and chlorophosphonazo 111 was also developed by these workers.~:] Chemical separation or masking agents are required for a nurbcrr elements. Chudinov of has studied spectrophotometrically the interactionof 12 organic dyes of different types with Np02+.312 He concluded promising rt?sorcinol reagents for pentavalent neptunium are that the most
(PAR), arsenazo
x 10 at 510 mu.
c.
CONTROLLED POTENTIAL
COULOMETRY
Determination
of Neptunium
ConcentratLo~.
Alpha counting is
generally superior to coulometry for determining less than a few micrograms of Np; however, controlled potential coulometry is an accurate and precise method for determining; above the 10-Dg Np level. 313 The electrolysiscell contains n platinum electrode at which the Np(V/VI) couple is titrated in OSM HzSOd. First,
- 119 -
the Np is oxidized to Np(VI) with Ce(IV), the Np(k1] and Ce{IV) are electrolyticallyreduced to Np(V) and Ce(IIl], and then Np(V)
is coulometri(callyxidized to Np(VI). Tleintegrated current, o in the last step is ~lsedtc calculate the concentrationof Np. The standard deviation ranged from 6%for 7 Bg to 0.05% for about
1 mg of Np. AS little as 2 ug was detectl>d. Elements which
significantlyinterfere are Au, Pt$ Hg, rl,and Cl ; Pu and Pd cause only slight interference. Stromatts method was used successfullywith a gold electrode insteall a platinum electrode of to eliminate the Pt/Pt(OH)2 reaction repw:ted by Fulda.9i~ Fulda obtained a precision of tO.6% for [5mg of Np. In another
of variation for the coulometricmethod o~:*0.8% for neptunium solutions. o~ide and ?1.11$(n = 11) for neptunium nil:rate Delvin and Duncan316 used the same method in the presence of nitrate with H2S04 electrolyte. Plock an(lPolkinghorne]17used coulometry to analyze solutions of dissoltred alloys for both U and 3 iJp without prior chemical separation. Plropst18 has reported a coulomtericmethod for Np using a conducltlng glass electrode in a thin-layer electrochemicalcell. Organic contaminants interfered and were removed
by bisulfate fusion befo:.e coulometry.
- 120 -
This method
applies
to
and (VI) states and was reportej by strOmatt. l on the fact that Np(IV) i; not clxidized, nor
The analysis
depends
is Np(V) reduced at a significantrate at a pl~tinum electrode in lM H2SO~ electrolyte. at the controlled The procedure potential electrode is: (1) ~ potential is applied
to reduc:
Np(V1) to Np(V);
(2) Np(V) is electrolyticallyoxidized to Np(V[); (3) Ce(IV) is added to oxidize Np(IV) to Np(VI); (4) excess :e(IV)
an?
and Np(VI)
is electrolyticallyoxidized to Np(VI). Np[VI) is determined in the first step. The difference between the integrated currents for the first and second titrations corresponds to Np(V], and
the
difference
between
the
integrated
currents
for
Step
S and
of &idation-l?e&ction
Pot.e~tia2.
The potential
nitric acids with a platinum electrode.g2 The ~tential in HC1 was not obtained because of reduction of Np(VI) by chloride. The inability of the method to measure irreversiblecouples, such as Nap/, the Np(III)/(IV)
D. POLAROGRAPHY Alternating current polarography with square-wave
is a serious couple
limitation. with
for
was obtained
or pulse
small
concentrations
- 121 -
an analytical
method pre-
square-wave
separation
to determine
%@in Pu after
Pu by 77X extraction.
!tp is Ihack-
froa nitric
After
sewer41 evapora-
and uet
oxidize
residue
is taken
is to
in i ml of (IKI.
and
;! mg of W hydmxyiis evapwated
to
hydrochloride
q dded,
IS1.
to
the solution
reduce the
the wlw
0.S
Then,
@i S.S
6.$ with
2 IUI
several
drops
of
amsonia transferred
The
to S ql.
Exactly
of the dilution
with the
are
to a polarographic
is recorded at
cell
and
\pargedl a~ainst
nitrogen.
IS4WCUXY pl
Nppeak
about
-0.8V
electrodo measured
added to
polarograph. Np soiutin
the cell, and the !Wpconcentration in the ori,ginal is calculated from the
EUrA
increase of chloride
to shift the half-wave potential. the Np peak. of for the reduction than for of the the well defined. EDTAcomplex
of
The patential
reduction
neptunium
of chloride ions
precision of f2$ and $10% for concentrationrarlges 500 and of 25 ppm, respectively.
122 -
ut al,**O couplo
fuels
reported
for
determining
nuclear
qnd 2Xp
targets.
of .
standard
repeated content
The method
to U,
solutions
Cr,
>20 mg/t
coatainigq
and fission
and other
to coq~re Jenkins
the umd a
aZ.)2*
and
to study
the
nature
stability
of EMA,
wem
Np(II1)
and Np(IV).a
Np(IIl)
in chloride *
and perchlorate
media by Hiwken
Kritchevsky,8*
Np was included
qctinides
studid
in a review
of
eiectroch,aistry
complexai of
by Milner.2* polarographically
E.
TITRATIW
Potenthmetfia.
cf
Np were
detomined
by redox
titration.
perchlorate
llp(VI)
same ~lliquot
ceri~: oxidation
and chloride
ion is absent
would be oxidi:~ed
to chlorine).
123 -
..--!...
.,
.!-...
.. . .
.. . .
. . . . .
Stoppered
weight
burets
adding
reagents,
plmtinu-cal~l
standmd deviations
determination titers.
fezmus
Colnpbttiu
Tftzution.
Np(IV) xylenol
is titrated
with
rose
yellofNp
molar
1 to 2%.
in 0.01
Th+,
reductant. Reasonably
Pu+,
acid
interfere.
rare
earth
do
elements,
Zn2+,
and U022+
There salts
quantitatively an qccuracy
F.
EMISS1(M
SPECTROMETRY
emission 3999.5,
spectra
of Np than for
used only
elements. lines
interferenceby the
numerous
or
the
distillation
- 124 -
A quantitative
method
for determinaticw
of impurities
in Np
is reported a modification
oxide is dissolved in HNOy, reduced to the tetravalent state with hydrazine and sulfamic acid, and then sorbed on anion exchange resin. Two cycles of anion exchange are Np. The second effluent is evaporated is made water and dissolved to dryness soluble with
IJWd to
to separate decompose
regia,
hydrazine,,
evaporated
aqua
in 6M HC1 containing Co as
the internal standard for the spectrographicanaiy:$is. The coefficient of variation for a single determinationof a numbe:r common metal of ion impurities ranges from 9 to 24%. For a 50-mg sample, the minimum concentrationof impuritiesthat cam be analyzed is 0.5 to ;LO ppm, G.
GRAVIMETRIC METHODS
Precipitationof Np for gravimetric determination is not a useful method. If other ions which form insoluble salts are present, these must be separated first. When the solution is
number of Np compounds have low solubilities in aqueous sc~lution; however, indefinite stoichiometryor necessity for calcination
to
determination. Often the small quantity orlow concentrationof neptunium precludes the use of gravimeery.
- 125 -
Np(IV)
is cqletoly
precipitated
by Na, K, or MibOH as the hydrated The broun-green but asily is q gelatinous redissalvd solid
to filter
in qcids.
!Up(V] %ydruxid.
in a sodiuw nitrate-sodiuu
qs
solution.
precipitated
dark scid
excess
NH*OHfrom minaral
Np(IV)
is precipitated excess
NpFh by adding
fluoridl~
double salt KBIp2F3or NHklUpFs is produced. Pertmide,~. large excess Purple Np(lV) peroxide iS precipitated when a
state.
Reduction always
acid.
Np(lV) peroxide
SOW! of the
depending on the acid concentrationof the supematant, separated peroxide. from many cations ~t Green Np(lV) oxalate solution with oxalic he:ukhydrate a~cid. by precipitnl;ion of neptunium
is prl~cipitated quantitative
Because
is not attained
a reducing
- 126 -
q gent,
such as ascorbic
A
acid,
to Np(Iv]. under
granular,
easily-filtered
controlled
conditions.o
(Nli~)4Np(C20~)k
from P@(IV) and Np(V) solution. icxiate potassium is precipitated iodate.s KNp02C03, is acid solution
from
dilute
mineral
acid
Cdwnata produced
by adding
to a d:llute
of Np(V], until the resulting solution is O.IM The solution light is heated salt.- Sodium neptunium lS pink dioxytriacetate, light acid at 90C for 3 to 4 hours
by transmitted
green KBrOs at
by
Np is oxidized
in dilute
Sodium neptunylacetate
is precipitated
by adding
%08DhUte .
[Np(Hpo~) z~zo] , a pale-green gel, is precipitated by adding phosphoric acid to a dilute acid solution of Np(IV).35
ii.
SPOT TESTS Spot tests for determining for 36 organic oxidation and inorganic states of Np and Pu coimnonly used
were obtained
reagents
- 127 -
paper for
with
traces
chromatography
The paper
WBS
treated
with emitters
Because
of hazamis
of radioactive an identification
measurement, limit
spot
than
to
of colors
was used
for comparison. In most cases, a color reaction was obtained with less than 1 ug of actinide, but the color was the sall oxidation states of both Np and Pu. Diphenylcarbazide Np(V); solution, however, Pu(VI] gives gives a color the reaction with Np(VI] but not ~e~tian. give In acid a color with for
same color
sodium alizarinsulfonate
or arsenazo
Pu(IV) and Pu(VI), but no color with Np(V) and Np(VI). Four of the reagents, and pyrocatechol, with all oxidation Pu(III). from 2s& chromazural-S, give arsenazo, spots 4,2-ppidyl under -azo-resorcinol, ultraviolet acid fluoresces light
fluorescent
states
only with
The oxidation states of Np and Pu were characterized color reactions on chromatograms and electrclpherograms.
- 128 -
give
characteristic
colors
with
alizarin,
however,
diphenylcarbaxide
spectrometerby Landrum, et al.sgz The instrumentwas a doublefocusing, 60-degree source sector type, with a 12-inch radius. The
chamber contained
filament filament
mass analysjs,
were collected in a Faraday cup. The method uses isotopic dilution with 35Np or preferably 236~p. rapid than This method is much more
times grecrer. The standard deviation fo:0.1 to 0.S nanogram of Np was 1 to 2%. applied to determine source Isotope dilution with *gNp has also 237Np.333 is ussful fc~r less
it
been
Spark measurements
mass spectrometry
quantitative
is
of many elements
including
Np; however,
most
often used for determining cationic impurities ~LnNp and other actinides.334 J. X-RAY FLUORESCENCE SPECTROMETRY The ease of production and simplicityof the X-ray spectra of high atomic number allow mixtures of
- 129 -
to be analyzed precision
with
can be analyzed
stsnd,mi at ra:ios
to standard
counting.
1:8 without
affecting
of 1:10, present
L series
of elements
by Kofocxi.s35 to determine
fluorescence solutions
amounts of Np in pme Pu. standard including The sensitivity error s~ple was
or in solutions
30 to 40 minutes.
K.
subnanogram with
quantities Np
of
237NP.332
another same
sample avemge
in the
neutron
After
irradiation,
- 130 -
mass quantities
recovery.
L.
OTHER METHODS
Gamma counting 239Np, the decay product of 2k3Am, has been used to determine 23Am in solutions containing large amounts of Cm. The ratio of the equilibrium amount of 3gNp to the amount of 2b3Am was determined by separating (by TTA extraction) and and analyzing (gamma counting) 239Np from jample~ in whi,:h~hq.km 239Np were known to be in secular equilibrium. The method was compared to determining 243AM by the isotope dilution-mass spectrometric method. The precision of the msthod was 7% at.the 95% confi~ence limits (n = 16) for sample ali~uots that contained 0.1 to 5 Llgof 243AM.33B A similar approach #as reported hy Lebedev et aZ.202 2]3Pa, the daughter of 2;7Np decay, has more-abundant gamma rays, which are easier to measure than 237Np. Cofield33g used this as a basis for determining 237Np-233Pa in human lungs by in uivo gamma spectrometrywith a large NaI SC:ntillation detector in a low-backgroundcounting chamber. The neutron capture cross section of 23BU
was
measured by
analysis of 239Np produced [23@U(n,y)23gll~-23gNp]. The procedure uses isotope dilution with 237Np to dttermine chemical yield, ITA extraction for separationof Np ard U, electrodepositionfor
- 131 -
Np source
of the
-6.9 cm/sec to +5 cm/sec for the individualoxijation states of +7 to +3 and are clearly defined.3*132 The isomer shift characteristicof each oxidation state is useful for !,tudy of
bondi~g in Np compounds. Dunlop and Kalvius have also made
Ix.
RADIOACTIVE
SAFETY CONSIDERATIONS
TfieSipisotopes emit high-energy alpha pa]hticles, mediumencrgy beta particles, and low-energy gamma rays. The tendency
of Np tu concentrate in the bones with a biolo~;ical half-life of 7.3 x 104 years makes ingestion the primary hazard to personnel. Studies of the distributionof 239Np in animal tissue showed 60 to SO% of the ?Jpwas Csposited in the bone-.131 Studies have ii[so been ~de
of the inhalation, pulmonary
absorption, gastro2:17Np
in rats.33
Because 237Np (T$ = 2.14 x 106Y) is the only isotope of Np which is available in weighable amounts, it presents the
hazard. The riidiatim only serious
hazard
is small
low energy
gamma radiation.
- 132 -
handling Iarge quantities of 237Np, standa~.d gloved-boxe:j aintained m at a negative ~ir pressure with respect to the laboratory airq~s should be considered for containment. the bare critical Criticality is no problem for 237Np belcause mass for a sphere of density 20.4S g/m3 is 68.6 kg.kG
Isotope
2sNp (s01.:)
Organ
Bone
Maximum Permissible Concentration for 40-hr Week (pCi/cc) ~~ . Air 9 x 10-5 4 x 10-12 2 x 10- 4 x 10-4 6 X 10-* 9 x 10-4 : x 10-*2 ;? x 10-11 2 X 10-]1
;!
Kidney Total Liver GI(LLI] tinsel.:t Lung z ~~~ (sol .:) G](LLI) GI (LLI) Bane Kidney Total Liver (insol,j GI(LLI) Lung Body Body
0.5 0.s
x 10-7 1o-1o
- 133 -
x. A. INTRODUCTION
COLLECTION OF PROCWLJRE!i
are divided
into
three
n.athods utilize
alpha
height
gaxna
spectroscopy,
is not detailed
Miscellaneous procedures for quantitativedetermination, including absorption spectrometryof color complexes, coulometry, and gamma spectrometry.
B.
Procedure
Extraction > ,. DorsettlS* Separation (IfNp by TTA Extraction .3 Smilh37 Determinati(mof 239NP in Samples Containing U, Pu and Fission Products 4 s Landrum34B Slee et C7t.zo Detenninatilmof Np Determinati4mof Small Amounts of :* in FuMetal
138
141.
14s 150
1s5
-134-
Procedure . 6
Author Schneider)qb
Title or Method . . Determination0!?Np in Samples Contain:~ng Fission Product!;, and u Other Actjnides
1s8
Maeck et aL.185
Wehner et UZ.252
Extraction Chromatographic Separation of 2]9?4p from Fission and Act:Lvation Products in the
[determi-
nation of Micro and Submicrogram @I;Nitit!Lt3S of U 9 Eschrich29 Separation of U, Np, Pu,, and Am by Reversed Phase Partiticm Chromatography 16S 163
.10
11
R,oberts2*
Nelson et 220223
12
13
Jackson et al,kg
14
Zagrai et aZ.23g
Separatism of Np and Pu
by
Caticnl Exchange
17s
1s
Sill123,
124,12S
Separatism and Radiochernical Determin$ltionf U and o Transurallium Elements Using Bti~bium Sulfate
13s
176
Procedure T@? II 16
Author
Title . Method or The Low-Level Determination Envinmmertal Radiochemical of 237Np in Samples Procedure of Trace Uater of Np in 21-Np from for
Page
Taylorso
179
17
Perkins]ss
Reactor 18 8utler35~
Effluent
184
Detemina:ion Urine
186
~pe 19
20
Bryan et aL.302
Spectrophotometric Deteminution * OF 193 Coeplexofor Np with 197 Determination 199 of Np for Analysis 201 Determination 204
21
SmimovAverin
et
22
Photometric Complex
of Np as the Peroxide
23
Uheat 2 2
Separatim of Impurities
Spectrographic
24
Ermoloev
et aZ.30s
Photometric
- 136 -
Procedure 2s
Author Stromatt31
- 137 -
Procedure
1.
Separation of Np by HA F. L. Fbore*o
Extraction
i?utl~~
Np is separated elements,
and nonradioactive
elements After
by extraction separal:ion,
alpha
counting
of 237Np or gamma
Reagent8
q q q
Chemica28)
HC1,
lM
Dissolve
FeC12*4Hz0 in a dark
stoppered bottle.
E@@n3ent
q q q q q q
vessel
with
mixing
device
steel
counting
plates
plate heater
Meeker burner
- 138 -
q q q
Asbestos board Sample carrier Alpha proportional counter (or gamma counter)
cipitated as the hydroxide. The hydroxide precipitates are dissolved in lMHNO~, and LaFs
The is precipitated to carry Np(IV).
fluoride
precipitates
HC1.
are dissolved
of 2M A1(NOS)S HNOI
iB
and dilute
possible Fe(III)
if
wch
A 237Np spike
1. Pipet a suitable aliquot of the swnple into a separator funnel or other extraction vessel, 2. Adjust the solution to lM HCl - llf NH20HHC1- 0.25M FeCla.
KI may be used as a reductant in place of FeC12, 3. Mix the solution for 5 uin at ambient temperature. 10 uin.
4. Add an equal volume of 0.5M ITA and mix for 5. Allow the phases phase and discard to separate; it. 139 then
6.
phase
by mixing
k)ith an equal
volume of
to s,~patte and
aqueous
T t.
by mixing
with an
volume of 1CB4 HIWs foL 2 min., is too high last traces in g~ activity
of radioactive of the
volume of ITA. the small amount of Fe in the ITA causes in counting, and the plate. by TTA If
self
absorption
is attained
is prepared counting
- 140 -
Procedure
2.
Separation of R. S. Dorsett15
by llA
Extraction
OutZine
Np is determined in the presence and other acetone alpha-emitting (TTA) followed nuclides by alpha
by extraction counting
acid and oxidation state are adjusted, (2) the extraction in which Np is quantitatively and alpha counting extracted into ITA, and (3) the mounting When additional purififron the TTA, acid extraction and
is done.
The precision of the method is dependent on the type and quantities of interferences. The interferencescaused by sulfate, phosphate, fluoride, and oxalate ions which complexes obtained with these relatively ions. pure are eliminated
A
hy addition
of A1(N03)?
Reagenta
q
(NaN02),
lM, is prepared
by dissolving
69 g of C.P.
grade
- 141 -
sulfamate iron
by diswith dis-
powder in an excess
minimum heating.
2M, is prepared
by disto
acid
solutions
arl? prepared
as required
grade
Collodion
solution,
S00 ug of collodion in one llter of l-to-l ethyl alcohol. ethyl ether. E@ipmen:!
q q q q q q
Centrifuge Vortex
cones
(with
caps)
mixer
plate:;
Meeker burner
Asbestos
s
q
board
o o
Pretreatment FZuotide present La(OH)J. in the method. solution, When it is not knc}tin what impurities
Np(Pu)
are with
The hydroxide
is dissolved - 142 -
reprecipitated
as the fluoride.
@ in Mbut~Zpho@uzte
(TBP).
If Np :.s present
in TBP or
Sepamtion
ofNp
and U.
this separation. In the analysis of low-level Np solutions that contain large quantities of U, the prcblem is complicated because 237Np and 230U have the same alpha energies. Also, the specific activity of 2ghU is 10 times greater than 237Np. Pm accurate analysis is assured by (1) close control of .:heextraction acidity, (1 tO.lM), (2) a double
a fluorophotometric
extraction
cycle,
and (3)
in extreme
cases,
determination
extract.
.%oaedme 1. Pipet 103 to 104 dis/min alpha of 29;Np into centrifuge cone.
7
a lS-ml
3. Add 1 ml of 2M Fe(NHzSOq)z solution. Mix and let solution stand for 5 min.
the
4. Add 3 ml of O.SM ~A in xylene, and mix for vortex mixer. to separate; it. then
5 min in a
s.
6.
activity
to Step 9. to Step 7.
aqueous
7.
Remove the
phase
it.
uixer.
phase. plate
2 through
5.
9. WITI on the counting Id place heater. 10. Pipet an aliquot twice a clean
stainless
counting
phase
that
droptiise dry.
over
flame until
the plate
red color.
on an asbestos
- 144 -
Procedure
3.
Contalnfng
Smlth3k7
Introduction The procedure for determining 23gNp affords excellent decontamination from milligram quantities of
U,
the
fissim products
obtained from 1013 fissions, and Pu. The decontaminationfactor for Pu is about 104. An initial fuming with H2SO~ is required to ensure exchange between U(WI] . the 237Np tracer employed and also to complex and 23gN11,
before the fuming step to convert U to the VI oxidation state, NPIIV) and (V] are carried by LaFg precipitations in the presence
of Zr and Sr holdback carriers. l%epreci~itationsprovide decontaminationfrom the activities of Zr and Sr as well as from IJ LaFs scavenging . with Np in the VI oxidation state decontaminates
from the lanthanides md partially from Pu. The chemical yield is about 50%, and eight samples can be analyzed in one day. Reagen ta
q
in
H20
Sr carrier: 10 mg Sr/ml, added as Sr(N03]z. 4H@ in H20 10 mg Zr/ml, added as ZrOC12 in H2C) counts/(min-ml)
Zr carrier:
q q q q q q q q q q q
HC1:
O.lM;
2M; concentrated
H2SO~: HN03:
H3B03: HF:
concentrated
concentrated
saturated
solution HF
equal
parts
by volume of 2M solutions
100 to 200 or 200 to 4n0 mesh, slurry in H20* %ocedure Step 1. Pipet 1 ml of 237Np standard into a clean 12S-ml
pipet
sides of the flask with a little H20, add IC drops of concentrated H2W4,** and evaporate nearly to dryness on a hot IPlate. (No harm is done if the solution is permitted to evarorate to hard dryness.) Step of 2M I+Cl. 2. Dissolve the residue by boilirg briefly in a minimum Transfer the solution to a clear 40-ml Pyrex centrifuge
Oow Chemical Co. * [f the s~le has been obtained from more than the equivalent of 50 ug of soil, do not add any H2SOk sj.nce CaSOh will precipitate and carry NP to some extent.
- 146 -
tube;
wash
the
The
fla>..
once
wit
H20,
and transfer
the washings
to
the tube.
(Ignore
any small residue.) Step 3. Add 5 drops of La carrier and 3 drops of Zr hold-
back carrier. Add 2 drops of NH20HHCI for each ml of soIution, stir, and Iet stand for a few minutes. Add HF dropwise until the becomes yellow color of the solution disappears and the solutio.1 cloudy (LaFJ). Centrifuge. Remove ant discard the supetmate. Wash the precipitate Step 4. with 1 to 5 ml of HF-HN03,
any small residue.) Add 3 ml of 2M HC1 and precipitate La(OH)g by adding about discard with the
1 ml of concentratedNH40H.
and it briefly
supemate. milliliters
several
Reprecipitate LaF3 by adding 10 drops of HF; centrifuge, and discard the supemate. If the precipitate Wash the precipitate with 1 ml of HF-HN03.
volume is greater
hydroxide and fluoride precipitationsuntil the volume of LaF9 precipitate does not exceed 0.2 ml.
- 147 -
6.
Dissolve
the
fluoride
precipitate
solution to stand for a few minutes. Centrifuge, and transfer the supernate to a clean centrifuge tube. Wash the precipitate
with 1 ml of one. HF-HN03, Discard centrifuge, the and add the supernate to the
previous
precipitate.
Step
7.
centrifuge, and transfer the supernate to :1clean centrifuge tube. Wash the
precipitate with
the prec:Lpitate. washings to the previous supernate, and di!;card Step u. Add 5 drops of NHzOH*HC1 and 2 drops of Zr carrier,
of and let stand for a few minutes. Add 2 drc~ps La carrier, stir well, cent.rifugep and discard the supernatc. Wash the prec~icate with 1 ml of HF-HN03, centrifuge, and discmd the supermtc. Step 9. Repeat Steps 6 and 7,
Step
10.
back carrier, and let stand for a few minwtes. Add 2 drops of La carrier, stir well, centrifuge~ and discard the supermate. Wash the precipitate with 1 ml of HF-HN03, centr:Lfuge, and discard the supernate.
- 148 -
Step
11.
H@C)3 and 10 drops of concentratedHCI. Pass the solution through a Dowex 1-XIC) anion exchange column, 3 crIx 3 mm, and wash the column with 1 ml of concentratedttC1. The Np, now in the
It
oxidation state, is sorbed on the column. rf necessary, remove Pu from the column with H1-HC1.+ Add applm~ximately ml of 1 the fi:rst drops 2 O.lM HCI to the reservoir of the column. I)iscard that come off the column, and then collect approximately0.2S ml in a clean, dry centrifuge tube. Use no aLr pressure when eluting the Np.
Pick
by stippling on a 2.5 cm Pt plate. If possible keep the deposit within a 1.3 cm circle. Flame the sample to duI; red in a burner, mount with double-sided Scotch tap~ in the center of an Al plate, and a- and $-count on 3 successive da:?:;.**
...
* The procedure should remove 9S% of the Fuinitially present in the sample. If, at this point, there remains enough Pu to interfere with the determinationof the Np yield, that is, more than 1% of the Np tracer, Pu may be removed more efficiently in the following way: Allow 1 ml of HI-HC1 solution to drip through the column with no added pressure. Wash the column with several ml of concentratedHCl, and discard the effluent, which contains Pu in the III oxidation, state, and proceed with the rest of Step 11. One elution step such as the one just described removes 99,5% of the Pu. * Alpha-counting: The sample is counted in a 7.5 cm id. methaneflow proportional counter with a loop :.node, ~peratecl the in a-pllateau region. Beta counting: The sample is placed on the third shelf of a methane-flowproportional counter with a window thickness of 4.8 mg/cm2. An absorber (about 5 mg A1/cm2), placed on the first shelf, stops soft lletas and alphas. The individual counts are corrected to to,, using a half-life of 56.6 hr, and are then averaged.
- 149 -
Procedure
4.
J.
Determination Landrum34e
of Np
NaOH to separate Al. The precipitate is d:.ssolved concentrated in H71, and Np is separated from many impurities by chloride anion exchange. Further separation is attained by performing in order: ITA extraction, cupferron extraction, and {:hloride anion exchange. The plate for counting is prepared by electrolysis. Reagent8
q q
50$ NaOH
in La carrier, 5 mg La/ml (as La(NO:l)g06Hz0
H20)
s
q q q q q q q q q q q
Concentrated HC1 55% HI solution HC1 gas Bio-Rad AG 1 x 8, 50 to 100 mesh resin 10M HC1 - O.SM HI 5M HCl lM HCl 0.4M lhenoyltrifluoroacetone(TM) in xylene 6% Cupferron CHC13 Saturated NHkCl solution ConcentratedNH@H
150 -
l+ocedure 1. To the sample add about 3 x 10: alpha counts/rein dardized reduced cient 1iquid. 2.
Wash the precipitate with
237NP stan-
Add W2 mg of La3+ carrier and boil 10 ml. centrifuge, the sclution until Transfer
(no inhibitor),
to a 40-ml cone.
may be present.
in a water
the
supematant
in 10 ml of concentrated
HC1.
Add 2 drops
4.
gas.
(If
white Pass
centrifuge
through
6 ma I.D.
save the
three
or so between
7.
to ne~.r drfless.
Transfer
to
151 -
8.
Add 10 ml of 0.4M ITA in benzene, and equilibrate centrifuging, clean 0.4M ITA for 40-ml cone. for 30 uin. Repeat and transfer 10 min.
5 ml of
Discard the aqueous fraction. 9. Wash the organic fuge, 10. and discard with 5 ml of IM HC1 for 2 min. Centri-
the aqueous. the TTA with layers cone. S min. Repeat 2 ml the
1 ml of 9M HC1 for
11.
combined
aqueous
phases, layer).
cupferron
Add S ml of CHC13 and Nb activity. flask, (CA~ION: until add 1 ml The if too
to remove trou~lesome
12. Transfer
solution
concentratedHNOS, and boil to near dryness. Add 5 ml of 9M HC1 and 1 ul of concentrated reaction between much HN03 is present.) been destroyed. Np(IV) . 13. Add 5 ml of fresh should solution I.D. wash. through concentrated a Dowex l-X8, pretreated HC1 (final necessary). with Discard 10Y HC1. HC1 concentration Pass the 6-mm and Wash the This HNOSand formic step may be violent
column with
5 ul of 10M HC1.
- 152 -
14. Elute the Np as in Step 6, but with 10 ml of SM HC1. Collect 1s. 16. Repeat in a 125-ml Erlenmeyer Steps 7, 8, 9, and 10. flask. (ITA extraction) contamination. If plate the sample.
is radiochemically
the solution
from Step
10 to near
dryness.
red indicator,
lM HC1 so that
solution
red.
solution
to an electroplating diameter
the
Pt disc for
Pass approximately
cell
Add I ml of concentrated is in progress. the solution Continue from the cell, If appreciable without the
plating
15 to 30 sec.
and check it for activity in a well is present, of NH4C1. Pt disc to a dull count red, for
and
counter. procedure
activity
repeat
the plating
for chemical
23gNp
and 290Np. Notea 1. Using this procedure, Np is separated from solutions whose contents underwent 10 15 fissions soil. [one week previous) and up to one gram of dissolved (:amma-ray spectroscopy
- 1s3
2. 3.
for
six
samples.
is 30 to 60%.
- 154 -
.-. .
ocedure
5.
Determination
of
Small
Amounts
of
Np in
Pu Metal
L. J. titZine Pu metal
Slee,
G. PhIlllps
gnd E. N. Jenklns320
of Method is dissolved in HC1. The Np (lCI to 2000 ppm) is and determined with a square-
Distilled
28 g of 2xylene,
q q
Ferrous
(EDTA) in distilllsd
ananonia solution,
Piwoduw
1. 2.
water
add 0.5 ml of
add 1 ml of ICR14 Cl H
3.
Dilute allow
to 10 ml with
distilled
state
writer,
djustmnt.
4.
Transfer
5 ul of O.SMTlA.
1s5 -
5.
Repeat
the
extraction
with phases
1 m.1of I.MHCI, and stir for 1 min (to remove entrained Pu. Remove the aqueous phase. 7. Add 5 ml of 10M HN03, and stir for I.(1 t~ strip the nin Np. 13. Remove the aqueous phase into a clear, vessel, and repeat Steps 7 and 8. !3 Evaporate the 10M HN03 to m3 ml and then add 5 ml c~f . analytical-gradeconcentratedHN03. 10. Evaporate! W1 ml, and repeat evaporation with twc} to more 5-ml. portions of concentratedHN03. 1:1 Add 3 ml of analytical-gradeperchlcnic acid (6C%) and . more concentrated HNOS and evaporate to complete wet oxidation of organic matter.
1.2.
bake.
13. Dissolve the residue in 1 ml of warm 6M HC1 and 1 rnl of water. 15. Add 2 ml of 5M NH20H=HCl and evaporal:e slowly to W.5 ml.
15. Add 0.5 ml of lM EDTA and 4 to 7 dro~~s armnonia of to adjust p}{to 5.5 to 6.5. ml 16. Dilute to 5.00 ml, and mix thoroughljr.Transfer 2.,00 to a polarograph cell, and de-aerate with N2 (pre-saturated with water) for N3 min. 17. Record the Np peak at about -0.8 V al~ainst the mercury-
pool anode on the square wave polaro~:raph. 18. Add vO.2 ml of a standard Np solution prepared in EDTA so that the original peak height is ~~pproximatelyioubled. f Deduce the Np concentrationof the o:?iginal solution from
- 156 -
the increase in peak height, Interferencefrom the oxidation of chloride ions is decreased by adding EDTA to shift the half-wave potential of tho Np peak. The precision is t2 and tlO% for concentrationsof S00 and 25 ppm, respectively.
- 157 -
Procedure
6.
Ffssfon
Intro&Wion This procedure method for separating describes ~ an analytical. solvent extraction
from Pu, Am, Cm, lJ, TII, and fission (TIOA) and thenoyltrifluoroacetone
products using
tri-iso-octylamine
(TTA). Np is separated from Pu, Am, Cm, and fission products by extraction of Np(IV) into reducing agent. Further the amine from iiN03 containing is obtained a
purification
by stripping
Np from the amine with dilute HCl ani then extracting the Np into TTA. Reagenta
q
.
q
.
q q q
Procedure 1. To a 5-ml extraction glass-covered 2. Pipet magnetic vial add 1.5 ml of 5M HN03 and a bar. 200 DE) into the HN03
stirring
the sample
(not to exceed
and stir.
158 -
3.
Add 3 drops
2M Fe(NH2S03]2
and
Stir 4.
and allow
to stand
for
Add 1.0 ul of 10% TIOA in xy.lene and stir produce Separate an emulsion. the phases, the organic containing Allow the phases and discard phase
to separete.
s.
from the
vial
1.5 ml of SM ~03,
Stir
3 drops
the
of
Fe@H2S03)2,
the phases
and discard
6.
Transfer vial
exactly
0.7S 2.5
ml of the organic
phase
to
a clean
containing
ml of IM HCl and 1.5 ml of xylene. in t}e xylene phase of the new the phases to separate.
Rinse Discard 7.
the
0.75-ml
pipet
vial. Stir for 3 min and allow the organic exactly phase.
Transfer clean
HC1
phase 3 min.
to a of Remove
vial.
Add 3 drops
emulsion. alpha
to reparate. of 2q7Np.
phase contains the purified Np. This phase is for counting for measurement
Notes 1. The presence lower the Chloride of these size of fluoride, sul~ate,
tixalate, and phosphate
extraction
coefficimt interfere.
of Np(IV) by reducing
into
TIOA; effect
The deleterious
is circumventl:d Al ion.
the sample
or by adding
- 159 -
!,
recovery. For U-bearing samples, the!recoveries are dependent on the amount of U taken, ~heextraction conditions are reproducible,and for control analyseis the 3. recovery factors are included in l,he calculations, system achieves
In routine use, the combined e~tracti{m a separation from common fission prodticts Zr, C% and Sr) of about
factor of 5 to SO x 10s. 4. Control of the method for samples of lmknowr composition is maintained by spiking a portion of the sample solution with 237Np or 219Np and evaluating th~ recovery of the spike. An alpha pulse height analysis may be necessary if large amounts of Pu are initially present in the sample.
- 160 -
Procedure
7.
Determination Products J.
of
Np fn
Samples H. [.
of
Introduction This procedure determination methyl isobutyl describes a method for separation and using
of Np in solutions ketone
of U and fission
products
(TTA) e,xtractants.
Np is oxidized
to the hexavalent
as a nitrate complex into methyl isobutyl ke:one from an aciddeficient A1[N03:)3 solution containing with tetral]ropylammonium lM HCl c{mtaining 7TA-:qrlene nitrate.
Np is stripped
and then
reductants
quantitatively
into
to complete
the
separation. Reagente Al(N03]lJ mixing, solution solution salting and cool until ail solution: to SOC. solid Dissol\e 1050 g of NH401{with and stir Dilute the the
A1(N03)39Hz0,
Reducing-strip
solution:
().25M FeCIZ solution. 0,>2SMKMn04 Methyl isobutyl ketone (),5M lTAin xylene Ethylenediamine
161 -
0.1 ml of 0.2SM KMnOK. Then p:,pet sample into the tube and mix. 2. 3 4. Add 3 ml of methyl isobutyl kel:one, Centrifuge to separate the pha:~os.
1 ml or loss of the
3 minutes.
5,,
3 ml of the aqueous
6.
phase.
7.
of the organic
phase,
and dry it
on a
under
1,
from acid-deficient ketone yields with lTA gives the only 80-day
A1(IW3:1)3with methyl from Zr, and from Pu and U. respectively, that products good separation cooled fission
of U and Pu is separated
2.
An alpha used
scintillation height
chamber,
2S6-channel
analysis.
- 162 -
procedure
8.
ExtractIon ChromatoqraDhic Semlratiorl of 23*ND From Fission and Activation P~]ducts in the Determination of Micro and S@nntc~gram Quantities of u
H. Wehnar,
Int2vduotion This
S. A1-Nurab,
qnd H. Stoeppler2s2
procedure
describes
separaneutron with
tion
is Poropak-Q that
resin
impregnated
radioactive chromatography
analyzed
extraction. ReagentB
q q q q q q
Poropak-Q
resin,
sample
in 2M WI or convext
to c~hloride
with
and
solution to a column
Q impregnated with
- 163 -
4.
When the feed has passed 2 ul of lM HCl and then Discard the effluents.
througlh
the column,
5. 6.
Pass
S ml of 10M HNOSthrough
the Np.
containiltg a 3 x 3 in pulse-he:!ght
NaI(TL)
analyzer
the 0.106-MeV photopeak. Not%e 1. The method was suggested for det[mnining low concentrations content mining of U by irradiating at the the 23gNp content a stan{lard of both sample of known U deterA
same time as the Imknown and then samples. for IL%1 hour
sensitivity
irradiation, with a
of 2 IC 10]3 n/cm2-sec
WilUh
a longer imadiation,
- 164 -
Procedure
9.
U,
H. Eschrlch240 Introduction This procedure tion describes extraction chromatographic is Hyflo tributyl Super-Cel phosphate (TBP) separa-
of U, Np, Pu, and Am. The system silica) impregnated of the with
actinidos.
q q q q q
phosphate
(TBF)
solution
[NazCrzOT]
Rwceduw 1.
Add Na2CrzOT to
the
actinides, U,
and heat
at 75C for
hexavalent
Np, and Pu. 2. Wash the packed at relatively and nonsorbed 3. Md the extractable sample column with v1O column volumes flow and pressure of NIM HNO~
high
TBP.
volume per
(not greater
than
100 mg of silaned
- 16S -
4.
s.
After wash.
Pu(VI)
elution,
(Np 1s reduced
If U, Np, and Pu are present The feed NP(IV), The order is adjusted 0.7M HNO, -
, no oxidation
0.02M
step
to
Fe(S03NH2):1
is Pu(III),
- 166 -
Procedure
10.
An Analytical
F. P.
Method
for
*slip
Usln9
AnIon
Exchange
Robertszlh
OutLine of Method This products estimation tracer method separates by anion exch~e Np from Pu, U, Am, Cm, and fission in HNOSsolutions The sample and loaded to permit 2Y7Np 2ssNp
to permit
colum
of Oowex l-X4
30 to 40 column
the
Fe(NH2SOy)Z
semicarbazide,
eluted
HNOs containing
Np
recovery
a Pu decontamination
interfere.
can be increased
10 to 100 by following
Np
cable
containing
high
salt
COnCentratjLOnS.
(C.P.
Chmn%a28) HNOs
Concentrated
s
q
MtZte2%Uz8
q q
?~~wextf
1.x4,
1oo-2OO mesh
Glass
column,
Counting equip-n t
an aliquot
of sample
3. 4.
Add 23$Np tracer (vIOS dis/min). Pass the adjusted sample through the column at 3 to 6 drops/rein.
s.
Rinse the reservoir several times tiitha few drcps of. 8!4NNOs, pass through the column, md discard.
6.
Pass
Fe@H2.S03)2 through the column at .5to 6 drops per minute (Pu frnction).
7. 8.
Pass 2 ml of 8M HNOs rinse through the column. Elute the Np with 2 ml of 0.005M
Catch the
~f!(S04)2 in 0.25M WW3.
9.
Mount an aliquct of the Np product on a Pt disc for alpha counting and alpha energy analysis. (The yield is determined by comparative counting of the 0.23 MeV 239Np gansnafrom the disc with that of a standard 239Np disc.)
- 168 -
Procedure
11.
Separation F. Nelson,
GutZine of Method
This U, Np,
uethod
utilizes
anion
exchange
.n ml
for
separating alkali
elements
which include
metals, alkaline earths, trf.val-,~t actinides, rare earths, and a number of other Sorption solutions not elements such as Al, Sc, Y, Ac, Ih, and Ni. by anion exchangers from HCl states but as Pu is
can occur
U is sorbed state.
to PuIIII)
sorbed.
The latter
are then
in separate
(C.P.
ChmicaZe)
O.lMHF
0.5MHC1 - lMHF
Matefia2a
q q
Dowex
Column, device.
and 12 cm in length,
q q
Resin Plastic
bed, test
- 169 -
..
e e
i%ooedure
:1,, ) . ..
Evaporate sample to near dryne!ss. Add 1 ml of 9M HCi - O.OSM HNCl~ and heat for S min. Do not boil.
3 -.
Heat
column
to
50
and maintain
throughout
elution.
4.
Pretreat
resin
Use air pressure to obtain flolw (J.8cm3/min. of 5. Pass sample through resin bed ac 0.8 c.mimin.
6. 7
Wash bed with 4 coiumn volumes of 9M E!Cl. Wash bed with 8 column volumes {~f9M HC1 (PLI fraction).
0.05M
NH41
8.
Washi bed with 4 column volumes clf4M HC1 - 0.1,?4 HF (Np fraction].
9,
10. Regenerate the column with 3 column volumes of 9M IiCl. The total time for the column operation is about 80 min.
170
Procedure
12.
Outline This
of Method
procedure is used to separate trace mounts of Np and It makes use of the fact that Zr(IV)
in HCl - HF media at high HC1 concentrationsi:jessentially nonsorbabl.e anion exchange resin under conditions where Np(VI) and by Nb(V) are strongly sorbed.
lkgenta
. @ o o
e o o a
Teflon evaporating dishes Plastic transfer pipettes Plastic test tubes Chlorine gas
2, Add 1 ml of 6M HCI - lM HF - C12, and warm. 3, Transfer the sample to a plastic tube and bubble C12 gas through it for 53 min. - 171 -
4. 5.
Chlorinate
the resin,
and add it
an additional
3.5 column volumes 6. Wash with Np. 7. Wash with to elute 8. Regenerate
3 column volumes
3 column volumes
of 6M HCl - IM HF - Clz.
-. 172
Procedure 13.
N.
OAtZine of Method This and Np. procedure describes separation of macro umounts of W
anion exchange resin, while Np(IV) is strongly sorbed at high HC1 concentrations. The valence adjustment is done before sorption on the column by dissolving the hydroxides in a concentrated HC1 solution that has been saturated with NHQI. The Np is removed from the column with 2 M HC1. The separation is quantitative and complete.
Bocedure The
of PU239 was then undertaken. The Np and Pu were precipitated as hydroxides, centrifuged, and dissolved in 210 ml of concentrated HC1 saturated with NH41. The solution 30 min and poured onto a Deacidite was allowed to stand for
FF*anion
2.5 cm diameter, while a flow rate of 1 ml/nin was maintained. The first 200 ml of effluent were pale blue [PU(III)]. The column was then washed with collected separately. 100 ml of concentrated No activity HCl, and wash was
at the end of the washing, The Np was eluted dark eluate green with 2M HC1. It was possible to follow the
band of the Np down the column, and the first 4C pl of with the concentrated HCl wash. All England. the Np
was included
q Deacidite
is supplied
by Permutit
Co. Ltd.,
- 173 -
was, collected in the next SO ml of eluate. No activity w{asfound in any eluate on the glass to be 23Pa,
after
wool at the top of the resin cf}lumn and was assumed the daughter of Np237.
- 174 -
,,.,
Procedure
14.
!Separatfon
of
Exchange
i.
Se14c1wMcov29
of Method
and Pu(III)
q re
adsorbed qf~er
on tho
cation
resin
KUl or
reduction with
with
!#p is eluted
0.0i91HF,
P2%w31iu2w
1. To 6 tc)8 al
&nd Pu,
Dg mounts
c~f Np
x
cc)]water.
(1 IUSdiameter
high]
heatinl
on a boiling
water
mnd Plug
bath.
the
solution
the resin
to room t~rature,
CO]W
with
a pipette.
with cotton,
CO1-.
s.nd pass
the remaining
solution
4.
with
10 ql of 0.2S PI WI,
follouedl
by 10
5*
Np into
s Pt dish
or a *7eflon
beaker
with
6.
- )75 -
Procedure
15.
c. w. slll~23012*,125
Intrv&uth Large trivalent and tetravalent
Ea!50t
ions
~re
precipitated
with
uhile mnomlent
procedure outlines
precipitated.
This
el-ts
of U and tronsuranium
oxygenated cations
into
Cm
too
large
to
fit
the
Ibe
iJa!Xl~
lattice
and
are
not
carried.
The
!kWt
precipitate
alpha
c~~ted
directly
with
92% counting
efficiency, or
the
radionuclidus
Rmgmti d
can be electrodqxmited
E@gment
HIS06
C0ncontr8ted
Im)
ConC8ntrwed
perchloric
qcid
(HClO~)
C.P.
KRO$
dichremate p@roxido flask (K2CrzO~l]
C.P. potassium
30t
hydrogen
(H203)
Erletmeycr
Centrifuge
and special
tubes
Counting
s~lies
and qui~t
- 176 -
KzSO~ 2 ml of concentrated My
8aC1202H2C) the elements (S /rng of to em) to
HzSO*, ml
the in
each of concentrated
be precipitated
flask there
md
is
evapo]ate
quc!;tion
until about
fumes
of
HzSO*
appear.
(If
any
removal
of organic 2.
Mtter$
Heat the solution over s blast burncIr with the excess H2SOb and lKIOti are melt
aelt,
until
volatilized
a clear
pyrosulfate
is obtained.
2 al of
.3.
COIOI the
add
and
heat
to boiling
or until
the
pyrosulfate
is dissolved.
00 not volatilize
4.
of
Np.
heat
becBuse
will
1% Mill
be oxidixed
decomposed
%. t).
the
excess
he the]~nlly
Cool
to
v40*C
boil
for
the
I minute.
%p and
Cool,
U are
centrifuge,
in the
7.
Md 0.S ml of SO% H~02 and 2.00 ad] of 0.4Si supernate, reduce and evaporate until ftmes any Pu that
the H~SOb to
KtCr20T
folloued cool
for
8.
Heat %10 q
minutes,
of
9.
qnd boil
wilwte;
~rom
cool. Step 6.
centrifuge,
supemate
la.
2S ml.
- 177 -,
11. Cool and add BaCIZ; then boil, the BaSO~ which contains in the supernate. the tively Not88 1. Seweral other shorter
centrifuj~e, 27Np.
TIN) U remains
procedures
fo]: Np are
when
in the
that
holhler
andl also
designed
holder,,
An alternative
electrodeposition
of th~! radianuclides
spectrometry.
- 178-
Procedure 16.
Intro&40t~on Np, along exchange with Pu and U,is removed frcm 8M HC1 by anion element can be indifirst with 8M
to triisooctylamine
(TIOA). Pu
Eac:h
is sl:ripped will
large
of Fe Much of it is
actinide
elesmts
bu stripped
easily
removed
extraction
decontamination ?@ is
of Np is accomplished
by solid
ion
by alpha
emhange. pulse
height
final 1y electrodepositet
for rsdioassmy
foliou
the
on the
plate.
and
a 9TMp .Mve
be distiny~c~ by
from
Np can
of ~ ~. to 2SPtI will
Also,
decreas~s
irradiations activity
qt a flux
cd 1 x 10*S n/(cm2-see)
7 to 10 times
level
about
greater
thsn
- 179
the original
R6!agt?nt% o o
e
12M, 8M
30%
c
q q
NMkOH, 1.SM f
KOH, 12M O.OSM
8M HC1 -
NHuI: This rm~gent must be prepared fresh Discard a:lyunusef reagent at the
TIOA in 10% TIOA (triisooctylaminc): 10% vcilume/volume xylene. funnel Clean with half the its reagent b:y shaking in a separator Repeat water. the Store
cleaned
-
flask.
4M HCl
O.OSMHF
o
*
Isopropyl
sample
to be analy:z(sd directly;
MM HCl; and
to 8M HC1. irlsoluble
aqueous
Soluble materials
may be
may be leached
samples
brought
up in 8M W1.
The sample should be adjusted 1:0a ccmvenient volume of from 200 to 400 ml. 2!. Add S m: 80C until of 303 }1202 to the effervescence
!umple wnd heat nt
about to about
ceaso:~.
COCJIthe
sample
room temperature.
- 180 -
3.
funnel,
Add
Shake the funnel for one minute. the original sa~le. Allow the phases to separate, and drain the bottom (aqueous) phase.
4.
Add
10 to
drain, and discard the aqueous. 5, To strip Pu from the TIOA, add to the an amount of 8M HC1 - O.OX NHu1 equal voluune of TIOA. separator funnel
to one-half the
to separate. Drain the aqueous and retain fcm Pu analysis. Repeat the Pu strip ~ith a fresh Flortionof 8M w] - O.OSMNd~I. Combine t$e two strips, and save
for Pu analysis. 6, To remove Np from the TIOA, ad(d to tho for o]ms minute. separatcry funnel the
an amount of 4M HCl - O.OSM HF equal volume of TIOA and shake phases W* to separate,
Repeat the strip and combine
to one-half
Allow the
and drain
with
a f:rl!sh
O.OSM HF,
the
U can now be
stripped 7.
Add an equal amount of 12M HCl 1:0the combined strips, and transfer to a clean separatt~ry fumnel. Add 2S ml isopropyl ether and shake
the the one m:lnute.
separator
aqueous,
frequentl:r
while
in accordance
with with
8.
safety a fresh
of ether. phase frornl Step times 7 to dryness. 4 hours. 3 or 4 ml with Place Wet
Evaporate
in
the the
a muffle
furnace
400*C fo] at
least
oxidize
181 -
16M HWS
and
30~ HzOZ.
to dryness.
the
12M lKl
evaporation. through
the sample in 10 sl of 8M HC1 and pass 200 to 400 mesh, anion bed should passes
a Dowex 2-X8,
exchange colm.
be 50 m long and 6 m in diameter; with 5 sl of &Ml HC1. the column, Elute Evaporate pass it. After an additional
5 ul of 8M ICl through
with
of O.lM HC1.
dryms. to
10.
Md 2 ml of 1(MIHNOSto the sample, dryness. Cool, cell. water, the cell Repeat the W3 waporation. to the sa@e, and heat gently the sa~le beaker cell, twice the rinse
md waporate dissolution.
Add 2 ul IM HKls
to ensure with
qnd transfer
Rinse and the
transfer full.
11.
Electrodeposit
three hours.
of the solution
electrodeposition. period,
the cell , rinse
A: the end of the with distilled and flame analysis. it. If 2g7Mp In 2% by conThe
water
1 min.
remove the is
~ty
the plate.
plate by
12.
Count
there
q lpha plse
q ml if
no
U present
there
radimssay
of U
the presence
is wry
increased
of ZIq) to
of % the ~
by neutron
verified
for
count. tm hours qt to
13.
Irradlato
q
aaqsle
approximately
flux
of 1 x 1013 n/(cm2-see).
A1lCIUtha plmte
- 182 -
cool
to pemit
decay
Pt activities
the
23 Np to decay height
to 2s Pu.
Recount
analysis.
amount of on the
present formula.
amount of Np present
- 183 -
Prowdure
17.
Radiochemical Procedure for tle Separation of Trace Amounts of 2g9Np from Reactor Effluent Water R. W. Perklns1s5
Intmduotion This procedure accommodates a relative:{ large volume of reactor effluent water, and emphasis is pla{csdon speed of separation and high radiochemical purity ratler than high yield.
%ocedure 1. Acid 20 mg of La carrier and S ml of concentrated %Sclml. 2. Cool the solution, dissolve 0.25 g >f Fe@H2.SOJ]2, and let stand for S min. 3. Transfer to a 100-ml plastic tube, ~dd 5 ml of concentrated
HF,
HC1 to
4.
Centrifuge, and discard the liquid phase. Dissolve the precipitate in 20 to S0 ml of 1?4 HCl, and dilute to 75 ml with IM HC1.
5.
6.
Add 5
Repeat Steps 5 through 7. Transfer the precipitate to a 50-ml beaker containing 3 ml of concentrated HC104, and evaporate to dryness.
1.0. Dissolve!the residue in 20 ml of lM HC1 by boiling. Cool the solution and dissolve 0.2S g of Fe[NHzSOg]z. Il. Transfer the solution to a 12S-Ial separator funnel and mix, Add 20 ml of ITAin benzene, and extract fcm 10 min.
12. Wash the organic phase with three 20-ml portions lM HCI for
13.
of
5 min each.
Discard
the aqueous
solutions.
14.
in
a SO-ml beaker
containing to dr:yness
3 ml of under a
concentrated lamp.
and evaporate
15.
beaker,
to
16.
Dilute
the
solution
to a measured
volume
and analyze
by
gaama counting.
Note
The analysis
requires
ti
hours,
and tle
yield
is
~90%.
18S -
Procedure 18.
F.
Outline
o~lfetbd
Urine is wet ashed with HN03 and H202 to destroy organic matter. The salts are dissolved in BM HCI and extracted with TIOA (tri-isooctylamine). The Np is the alpha activity
on low
then
and and
is
determined
by direct
counting
background
solid-state
counters.
A variation mination
provides
for
sequential
deter-
of actinides
and en~ironmental
samples.
Es are
N, N-diethylcarbamyl
phosphonate). The
actinidcs of interest are back-extracted sequentially for quantative detezminations. P2qmwztion Urine ofthmpk in polyethylene bottles is transferred per to an liter).
collected
added to the
urine
in the
polyethylene
bottle
container. residue
acidified ashed
- J86 -
Reqen ib and Equipment The liquid anion exchanger, TIOA (Brain Chemical Co. ) is
diluted to 10 VOI % with xylene and washed with half its volume of O.lN HC1 before use. The alpha-detection equ~pment are 211solid-state counters. The counters arc equipped with detectors ::hathave an active area of 350 mmz and .me capable of accepting l-in. stainless steel planchets. All other reagents used in the procecurc are prepa:redfrom analytical grade chemicals.
Firoccdure 1. Wet ash urine with HN03 and H202; then add 113ml of 8M HC1 to the white salts twice and evaporate the solution to dryness each time. 2. Dissolve the salts in freshly prepared 8M HC!,- 0.05M NH41 (50ml ofacid/250 ml of urine in sample), andheat to complete solution. 3. Transfer a 50-ml aliquot of the solution with 25 ml TIOA-xylene into a separator funnel and shake for 1 min.
the flask twice with
ls)er
for
5.
Rinse the organic phase with 25 ml of EM HC1 - O.OSM NHkI at 80C and shake for 1 min. Discard the rinse solution or combine with solution stored for other actinide analysis.
- 187 -
6.
Add 25 ml of 4M HC1
0.02M
HF tn
iOL1-mI breaker.
Repeat a second time and combine the two 25-ml solutions. the organic phase or strip with O.lM IIC1 for uranium
Evaporate dryness.
the Np strip
8.
Add
Flame the dried planchet tc dull red, cool, nnd count on lowlCVC1 solid state alpha counters.
10. Calculation:
Np activity on planchct is determined as follows:
total count - Bk d dis/(min-planchet) ~t)(cout=r ~ff ~ = . where: Bkgd. = counter background (3 to 10 counts/24 hr) t counter cff = counting time in minutes = counter efficiency (normally0.30) as a fraction
The sensitivityof this analysis is 0.02 ~ 0.01 dis/[min-samplel. The recovery efficiency is determined by adding a known amount of Np standard to an aliquot of urine sample and followingthe same procedure for analysis.
188 -
Procedur? 19.
the rapid determinationof Np in process solLtions containing fission products. The method is unaffectedky highly salted, corrosive,or organic mcdii3. 237Np is dctcrninedby ,iymma
The detector system consists of an Ortcc model 3113-10200, low-energyphoton detector with cooled FIiT przamp and a resolution of 900-keV full width at half maximum [FhHM) ~t 86.&heV. 4096-channelpulse height imaly~er
,!
and storage of the gamma s;)ectra. The data are read onto magnetic tape or printed out directly from a high-speej digital printer. Data reduction is performed using an IBM 360.:iystcm nd FORTRAN a programs developed to calculate nuclide abundmccs from multichannel gamma ray spectra.: %wcedwe Calibration. 233Pa, the daughter of 237Np, has a 0,017
abundant gamma ray at 86.6-keV that interfereswith the measurement of the 237Np gamma my of the same encrg}. 233Pa also has
u 0.34 abundant gamma ray at 311.9-keV that i: not associatedwith a 237Np gamma ray. In order to determine the 233Pa contribution - 189 -
a pure
stancard
solution
of
233Pa is purified
by passing
an equilibrium
level
by alpha Aliquots
counting
of the
peak.
to the total
detected
at the 86.6-keV
rays is determinedby calibrationwith known gamma standards between 43.5 and 511.6-kcV.
tkaly~i
Tnc standards
and sample
amplifier is adjusted to provide a peak width of 7 to 10 channels (FWUM)to allow reliable integrationof the photopeak area. For a Gaussian distribution,99% of a peak area is contained in 2,1 x Fwllhl . Therefore a peak area of 24 channels is used with a gain
setting giving 10 channels FWtB1. The net counts per minute of 237Np is calculated by subtracting
- 190 -
total photopeak
bmckgromd average of is the
amm.
The contributia be
of
wdcrlying
Co~con
a~sumed to comts
linear
over
An
from 4 channels
on each side
of the peak
sinus
the
backgrotmd
should
be greater
50 I +
thanz:
1 .
{[
W.
Sum 12.5
1}
is of hy rhc product detector and the
me
absolute
obtaind by dividing
the gray ahmhince
uinute
(photon/disintegration)
efficiency
An aliquot
of I.Ob x 10s
using [organic] comt-
dis/(min-ml)
A standard andone that
237Np standard
geometry sa~le
solution
was =de
was cxtractcd
from the lTA
from
phase.
gama
shoued
97% of agreement
into
the
lTA
the
phase.
Close
between
two mnthods
demonstrated
reliability counted
of the gs in organic
pulse
height
analysis. uffects.
Samples
can be limit
A lower
of detection
191 -
F?u,%?rw?lm
* -.
!4. A. Itakat
[1970).
and E. K. mkcs,
c. .%d~J@H@t.
Cwm. +, 109
.;.
*.
F.
Ilidcr.
Scieeai
tii~:icul
KAPL-890
P?tiodr
( 19S3).
for
Fwws I%vmea
L.mcr r:.
IEAEC Rqort
192
Procedure 20C
Spectrophotometric
Determqillation
of Np
as the
arsenazo
Ill
separation
elements
by liquid-
liquid extraction. U is removed first by extraction from 4M HC1 into triisooctyl amine (lIOA)-carbon tetr:~chloride, while Np(IV) and Pu(III) are stabilized in their nonexl:ractable oxidation is extracted The absorbance
states tJyFe(II] and ascorbic acid. Then Sp(IV) from 8MHC1 into ?ip.arsenazo is measured
TIOA
and
back-extracted
into
in 6.lM I!Cl,
nm.
.7eag%~t8 o Arsenazo 111, 0.2$ [~,8-dihydrox:plapthal,ene acid]. containing -3, 6-disulfonic 1 g two KOHpellets. acid in
Dissolve
acid,
6 gr:~ms of ascorbic
of 8t4W1.
tatrachloride, (CClk) reaglmt
grade.
12M, reagent
grade.
o
q
Np stock Phosphoric
solution.
Dissolve
higlh purity
Np metal
in
12M HC1.
acid,
grade.
KOH, pellets,
reagent
- 193 -
Reducing
solution,
5% ascorbic Dissolve
acid
ion in 4M HC1.
2.5 It of ascorbic
1.75 g of Fe(NH2S03)z
q
Tri(iso-octyl)amine-xylenc
Equipment
q q
(see
figure
glassware flasks).
Spectrophotometer,
uatched
with
fused-silica
Pretreatment The sample material chlorofom. is of metal or alloy oil is inspected, and extraneous
Cutting Pu uetal
sample,
200
weighed
than on a
mg and
determinations quantity of
containing solution.
and on the
- 194 -
Procedure 1. Place each accurately weighed sample Mhen the in a glass sample extractor
and add 1.5 ml of 12M I{Cl. add 1 ml of the 2, Prepare reagent reducing blank
has dissolved,
solution
solutions
of
Np
approximately
in the
sample
and Dilute
solution
to 5 ml with
Add 5 ml of
in previous allow 5. 6. 7.
Separate
for 1 min.
the phases
the
for
TIOA-CCl~
and discard.
Repeat
Steps
4 and 5.
12M HC1 and 10 ml of TIOA-xylene uix the
Add 5 ul of
to each
the
phases
for
Remove
phases
con-
for Pu.
1 min.
phase
the
inside HC1,
of
the
extractor
wit~h 53 ascorbic
mix
the
phases
for
the phase.
phases 9.
to separate inside
for of the
1 min. extractor
the
aqueous
Wash the
phases
with
RV IIC1. for
Mix the
for
2 rein, aqueous
to separlatc
1 min.
Remove the
10.
Add
for
for
1 min.
- 195 -
11.
Remove
the
aqueous
phase
into
a 25-ml volumetric
flask
I{Cl,and 12.7 ml of 12N HC1. Steps 10 and 11. Ar~ena~~ III ~o]ution water. to the Stopper vol~tric and mix
Repeat
contents the
of the absorbance
paths (As-Ah) at
14.
Measure
solution
of 66S
in cells nm.
having
(sqle
wt in grama
standard
deviations
range
between
7.2
and 1.1S in
Of 45 elements but
interference,
only
if
present
in concentrations
greater
than
0.8%.
However,
initial extraction from 4N }ICIinto TIOA remves is not significantly extracted from HC; solution. affecting remved the
conplcxcs
up to 1 mg of Zr without unless
and IINOI cause low results method *aPu tolerates as Iargc the intense
by volatilization.
fxom
radioactiqrity
quantities
of
as 100 mg.
- 196 -
Procedure 21.
Krot:26
Outline
Np(IV]
of Method
is
with xylenol orange as indicator. The ;?eacticm c)fNp(IV) with EDTA is stoichiometric and the color changes from bright rose , to light yellow at equal molar concent:riltions. The determination takes approximately two hours; the erro:-is tC1.03mg.
Reagenti
o
and Equipmnr
Hcl, reagent grade Test solution, 10 mg Mn2+ and ,50mg NH20H*MC1 per ml 30(%KOH 10% NaCl in
4M
o e a s @ @
HC1
Pswcedwe
1.
Add
1 to
4 ml of
Np solution
and
2 ml of test solution
containing 10 mg Mn2+ and !50mg of Ni120H*HCl per ml into a centrifuge tube. 2. Dilute to 6 to 8 ml, and heat to 60C; add 30% KOH with mixing until the pti>10. 3, 4, Centrifuge the precipitate, and discard the solution. Add 10% NaCl in 4M HC1 dropwise until the precipitate is dissolved. - 197 -
5.
Add 1 to
1.S ml of 4M HC1 COnta:Lning 50 ug of NIIZOHHC1 and heat the solution for 20 min on a boiling
Cool the
1 to 2 drops
7.
of 0.1% xylenol or.mge. 2 x lLI-lM EI.)TAfrom a microburet until the from rose
to
Titrate color
with changes
brig~t
yellw..
lio tes
1,
[ICI solutions are preferred in xder Np to the acid interfere tetravalent state since with its is not suitable,
to reduce
all
the
2.
Doubly charged readily hydrolyzable ions U3Z2+), which used as carriers. with amounts an error of alkali, do not interfere with the
3.
of tO.03 alkaline
Cd2+,
large
earths
elements, by strong
Anions
because
- 198 -
Procedure 22.
lip
as the E. V.
Peroxide
Yu. P. Novikov, S. A. Ivanova, and A. A. Nemodruk3s3 Outline of Method an intensely ofNp(V) of the colored complex
Bezrogova,
in alkaline is
The ratio
complex
absorptivities
respectively.
The method
NaOtl,
Cl)
grade
Pzwcedurw 1. Add the dilute acid (HN03, HCl, or IIC1(14) solution, 5 to 50 Ug of Np into 0.1 for
a test
%2.5 ml containing
7 A.
tube.
Adjust
solution,
to pl{ 1 to 3 with
NaOi,
add an extra
1 ml
to exactly the
4 ml with
water,
absorbance
in a 1 cm cell
430 or 370 nm
- 199 -
Note8
1.
Np(V),
or N:J(VI),
gives
a color
reaction
with 11:02. 2. The stability increases the 3. absorbance the for of th(? colored as the pH is rem~ins Np(li) peroxide for complex
increased. unchanged
?l~sorbance. constant
4.
the
NaOH.
Greatm
amounts
of the the
Np(V)
complex.
absorbance carbonate,
of the
and sulfate
When iron
is present, Four-fold
by centrifugation,
Up to 300-fold amounts
interfere.
200
procedure
23.
Separation Impurities J. A.
of
Np for
Spectrographic
Analysis
of
Uheat232
Outline
ofllethod are dissolved to dryness. in concentrated The residue state adjustment anionic the is HN03, and the in
NzH4
is heated
is dissolved
is made with
sulfamic
is
sorbed not
on strong by the
c~tionic rspeated,
sorbed
effluents in
are evaporated
6M
is dissolved by emission
spectroscopy. Reagente
q q q q q q q
column
Spectrograph
Pxx%?dure 1. Dissolve evaporate 2. Dissolve fourth least SO mg of sample to dryness. solid residue valance in 2 ml of 0.35M HN03 and add onesolut.,on adjx-:ment. of N2H@. Wait at in concentrated HN03, and
- 201
3.
Add one-half
ml of
acid
thrwgh
at <3 ml/(min-cm2j,
resin with
the
Np from
resin
with
and condition
the 7.
coluam with
8M HNOs for
2 through
(99.96% of the
exchange].
8.
Evaporate to dryness
effluents
from Step
9.
Dissolve to dryness.
aqua regia,
and evaporate
10.
Dissolved
the
last
residue serves
in as
Bg of ths
top of a l/4-inch-diameter 12. Excite large the sample region. filter is for
flat-top
electrode. using a
Littrow
wavelength
step neutral
inserted
relatively be carried
used, Doubly
blank
should
throu,~h
202
Recovery 65%.
all
elements
of variation varies
for a single
determination an average of
of
is affected of cationic
volumes
of reagents resin
and
inco~lete
from the
Fe, Cr,
column.
to determination
- 203 -
Procedure 24.
P.
V.
Ermoloev, J.
G.
S.
t(ovalenko,
N.
N.
Krot,
Blokhin30n
Outline
Np(IV)
of Metiwd reacts
in weakly acidic solution (pH %2) with
xylenol
orange
to form a color
maximum at 550
Xylenol
one-half
orange
as
more sensitive
and Arsena:o
is the relatively
minor
interference
Test
solution,
10 q
xylcnol
orange
1.
M tube, @
solution
containing to
S to
20 us of then
Sp to a centrifuge
and dilute
S to 8 ql;
>10. test
:.
Add 1 ml of
50 mK of
solution
ine=
contrnlnlnr
the
ccntrihl:c
10 mg of
C*C.
$hlJ*
and
.SHZCMI-IKI
-m4-
3.
Mix
and centrifuge
Discard
the
liquid;
the precipitate
in 2 ml cf 7M HC1 contain-
Heat the
25
on a water
bath
for
min to obtain
5.
Dilute
1 ml of 0.05%
xylenol
6.
orange, and adjust to #l 2.0 to 2.2 with 2NI.Nl@ll. the solution quantitatively to a 2S ml volmetric
Transfer flask,
and dilute
to vol-e
the optical
with water.
density of the solution m an
7.
Mix
FEK-M
fitted
with
green
filter
and using
cells
sith
a path
of 5 cm at 550 nm.
The reference
is detcrminrd
from a standard
cume.
* -.
The
determination
wq~ircs -3
hours,
usually
{s <slug. 3.
~p
c=
be detcmined
by the abovr
method
in IKI,
IMI,
an9J also
I,a solutions
by the strong
base
precipitation:
flmride
interfere.
-ms-
Procedure
25.
Analysis
for
R. W. Stro.matt
Intrv&ctwn
Controlled little as 2 ug potential coulmetry is useful for detecting as
7 vg can
be dettnnined
with
6% standard
deviation.
The
procedure then
to
is to first
oxidize
all
Np
the Np(VI)
Np(V)
and excess
Np(V)
oxidized
to Np(VI)
concentration
of Np. RmgeRta
q q q q
and ~uipment
metal sulfate gas solution coulo~ter electrode Pt wirt Pt gauze, and saturated isolated calomel (working electrode reference) potential cell
heli=
Q
q q
Plvra2df4n2
1.
Np sample
the
and the
titration
medium into is
the
cell,
hydrogen
ion and sulfate ion concentrations ion concer,t~tion the electrc,de by the there sulfate
not
critical of the
potential
co~le
is affected until
concentration). as evidenced
2.
Add Ce(lV)
solution
is an excess
by a persistent
color. -206-
3.
De-aerate
the
solution excess
with Cc(IV)
He for has
5 min.
[If
during
this
time
the
rc.~ctcd,
add additional
the until
\p(v1)
and
cxccss
chc current
bccomcs
and extrapolate
integrated
time. a blank and after solution titrations containing at the the same amount of perform reduction as used
6.
S min of de-aeration
and oxidation
same potentials
the Np titration.
the
to zero
time.
tlm mount
(lor
from
based
on the the
instrument
in into the
Illg!lcst migration
Np lost
taken
are
account.)
couple
quantitatit-cly
more
and
112SO~.
Pu(III)/(I\)
anlJ Sp(Vj/(\l)
separated better
in ll@~.
207
2.
Ce(IV] ?Jp is
ion rapid
is used
for
oxidation
because
oxidation
of
and quantitative,
contaminants are often slow and yield low values. 4. The concentration states of Np in the the different oxidation
cell. The
Pt electrode
ANP(J1/(VI) couple Cm be titrat~!d from oxidation of Np(IV). Np(VI) is determined then oxidized these The Np(V) is initially
uined
without
s.
reported
a coulometric
a conducting
fusion
procedure.
- 208
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E. McMillan
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c, Id.
( i968).
~. Ckw. &w@. i?wip
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(196SjI.
(1964].
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1S6.
1s7.
U. Lindner,
II. P. NoIco*,
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W&L- lJ~SB
0$ -$86
USAEC Report
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8.
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personal ]i.
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c~icaeion.
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USCIUL-(;l-W-l-n
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M. E.
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..-.
Y (lYbUJ
.. ...
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W. J.
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