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RA OF NEPTWWMI

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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

Published by Center, office of Information

ATOMIC ENERGY (:OMMl:~l(JN

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

~-*~mdM--- ,, . -.,.-.... .... . . ....

.- ---

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.

. 4) . 41 . 54 . 88 . 104 . 107 109 109 114 119 121

VIII.

. . . . . . . and Radiow:ric . . . . . . . Coulomet~/ . . . . . . . . . . . . . .

. . . . . . . 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 . . . . .

163 16S 167 169 171

-3-

. .

Procedure Procedure Procedure

Procedure Procedure

Procedure Procedure Procedure Procedure Procedure Procedure Procedure Procedure References. . . . .

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

. . . . . .

. . . . . .

184 I 86 189 193 I 97 199 201 204 206 209

,.
,

-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.

The Chauiatq of the TM MIUWZ{WI? Zanenti, E Verlag Chem.ie, Germany [1971).

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~~

12. 13. 14. 1s.

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,

17. 18. 19.

Ckmie,

Vol-me 88

Parts

der Anoqpri8chen Chemie, Volume 8, A, B, and D (1973).

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,

20. 21. 22.

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.

GENERAL EVIEW THE RAOIOCHEMISTRY NEPTUNIU4 R OF OF

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:

Neptunium was discovered

They bombarded a thin uranium foil and showed that isotope

of

the 2.3-day

activity

element 93 produced by the nuclear

It was shown in 1941 that

the decay product quantities of 239.*,

of 23gNp was 239Pu.2 as the intermediate but because of its

23gNp is produced in large in the nuclear short half-life reactor it production

is used only as a tracer. the long-lived reactions: isotope 237Np

Wahl and Seabarg3 discovered in 1942.

It was produced by the nuclear

The first isolated

weighable

quantity

of 237Np (U5 ~g of in 1944.4 a:tivity

Npo2)

wa5

by Magnusson and LaChapelle to measure the specific of these quantities reactions, in nuclear in

These workers of 237Np.

were the first As a result relatively natural nuclear important. U. large

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.

aNp is used as target in demand for fueling

of 23EPu, an isotope

p>wer sources.

The half-life
of

of J7Np is very shofi it

compared to the age quantities

the earth.

Therefore?, where it

is found only in trace

in U minerals reactions
of

is fotmed continuously

by neutron the abundance

described

previously.G
of

It vas found that

2sNp in a s~le

Katanga pitchklende of zss~

was 2.16 x 10-12 atoms

x ]0-2

per atom of 23%, while that atcm of

230u.7

was 3.10

atoms per

IV.

ISOTOPESANDNUCLEAR PROP[:RTIESOFNEPTUNIUM and selected 1. r.uclear prope-ies chemist of works

The known isotopes Np are listed in Table

The rad.ioar.alytical short-lived important

mostly with long-lived

2s7Npand wst

2gNp and seNp. isotopes

of

The decay schemes of these presented in Figure 1.

Np are

Thermal neutrmn cross

for

sections

and resonance

integrals

Np isotopes

are shown in Table 2.

-9-

Maa@
224

Half-lifa 22s= 60sac

4.0 tin

2s

%r#,4a) Somm
13

231

3.s14 1 10

E a

6.2S

S%(d.tia) D%(d.h) l%J[d, Sm) as%(d, h)

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- )

a%[d,ln) I?a S.0SS(48)

s

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

o% Ea = 4. 7M(42t) 4.74s(m) 4.764(s8) 4.*1(5. 4.62d(6t) it)

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-

= O.?ls(?t) o.4s7(46u o.263(lm O.n?(zrb)

U(B. T) ?%J(B*Y)

O.m(ln) o.220(12b) O.llx(mb]

24e
24a 241

7.s da

2.s19 m lo

e-

13-

= 2.lc[sa) I.so[nt)

u(B-d-y) ~u(m. pal u(m. p)

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.

Vn+l (s/2+) sR7/2Ilr# .

-En9rgY thv 1

2. :,

<.. h l).

Spm and
pvlty ml.,

5119
50s3 Lgl1 LU9.3 3916 3301 265s $6375 ?5 ?! 5727 ? 85

!m-1 m. ml-i ml. }

?12.

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.

Nasle, N. Lindner.W3tL-sl Z63(l!l~2).

spectnu.

barns,

10- Z*C81.

with the fission For 3 MN ntmtrms. For ..reactor matrons..

V. A.

CNEMISTRY F NEPTUNXLU O

METALLIC NEPTUNIUM

A.1 Preparation Npw?al was first prepartxi by Fried and Duvidsoa in 1948

by the reduction A sitilar

of SO ug of NpFj with M vapor as 1200*C. ti snd Eyriq,, L2 Reduction

method was used by Uestmn

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.

Pure Np is a silvery 6.379C. ?%e =tal the 9eltin8 Table 3. point.

undergoes

modifications me ~rizsd

The physical

-#z

TABLE 3 PHYSICALPROPERTIES NEpTIJNI~ OF ~T~&~J7*L$

A. B.

Appearance:

Silvery

white

[slowly ccatod with oxidel in dry air qt rcom toaperature) frtm vapor pf;ssun of liquid Np )

Melting Point: Boiling Point:

c.
D! .

6376C 417S*c (extrapolated measuremmts

)ieat of Vaporization: Properties Aliotmpic of Various

Mifi-tio-:

AH 1800K H 94.3 kcall(g-mm)

a B Y

E.

Transition teaporature to next higher phase, q C !Mtmity, glcm (at T*C) Crystal Structure

280 20.48 Orthorhoabic

577 19<40
Tw:ragonali

637 18,04 Cubic

Wtphens a detmmined for Np. Ptiit The ~~ific hst

tke pressure-taqmmturw (Cp)

ofNp fis

relationship Thm Duhng and at

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,

HP is a reactive NP~3+ with

q

~thin oxide

i$ 1.83 vo~ts. layer

when exposed

to dry air

and rapid especially sulfur resets

oxidation in mist react

to Np@ occurs air. Hydrogen,

at higher haIogens,

temperatures phosphorus, and

with Np metal

at elevated at relatively

temperatures,

Hydrogen

to form the hydride F@ ferns intexnetallic

low temperatures. solid

compounds of intermediate Pd. and Rh.

solutions

with U, Pu, Se, Al, B, Cd, Ir, readily

Np dissolves
qt

in&-Kl at room tmperature The behavior

andHzS04

elevated

t~rature. is given

of l{]) toward various

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

has been reported Np is a unique

betbeen y-l$p and y-U and elment because of lts

between y-Np and Z-PU. emt-ly high volubility The intermetallic

~13,

in both a-Fu and &.Pu. co~unds of Np with Al and Be (NpAlz, directlyby The boride:; cmrpounds reducing NpFq

NPA1*, and Np8e13) are prepared of metallic

Al or Be.

with an excess

(NpBz, NpB~, NpCdG and Several

Npltc, and NPUIZ) and the intennetallic NpCdlz

qre

obtained

directly

from the elments.27-2q

-14-

TABLE 4 BEHAVIOR NCJ OF METALIN VARIOU:i SOLUTIONS1 Solution H20

HCla

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

, No reactionclear solvent So reactioncl?ar solvent $, ,, someturbidity hydratedxide o ,, NO rmctionclear solution , !, !, ,, **

2.25
9 18

Slowreaction
,, NOnoticeable reaction

(nlcoot#

8
16

Slight. initial r*actioncessed ,,

NOvisible

r.action

HC104
Iinim

Cone.

CQnc.

14s0 Jrw lConc.HNOS trace HF

z. At ambient taqwratum.

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.

10 prq?are several (;.

CWPOUNDS OF NEPTUNIUM Cmpounds of Np for the III, IV, V, VI, and VII oxidation anc compositions because they

states

have been prepared.

The solubilities

of some of the compounds have not been verified

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.,

have been made with and peroxides,

more quantitive

Numerous Np compounds, such a$ nitrates, possibly soiverms contai.ning thiocyanates, such as diethyl solvents are readily ether, soluble

hexone, with water. containing

TBP, and other

saturated of co~nds

l[nvestigation has been limited aqueous solution mder

trivalent

rqt.unium

because

of the instability

in of Np(lII]I

in the presence hydrogen (on

q

of atmospheric platinum

oxygw.

Np(III)

is produced chemical at al.2 protection

catalyst),

by electro-

reduction

and with rongalite, several Np(IIl)

IW+SO2.(H2O2H;1O.Wfod$eva COWWCIS from Soiution solutions and water with were

haw prepard from oxygen.

All the reagent

-m-

purged with pure argon. operations layer acetone (centrifugation

The precipitation and washing)

and subsequent were conducted with a

of benzene over the solution. or ether and dried in a stream

rhe solids of argon.

were washed with Np(III) oxalate

was prepared, The solid

but it was appreciably

oxidized

in a few hours. prisms.

was brown and was in the fo:a is rose-lilac

of tetragonal

Np(III) phenylarsonate

t:olored

with the composition for

NpZ(CGHS~09)SnHZ0 when well dried; a long period lilac Np(III) h at room te~rature. fluoride c~lex were also double

the compound is stable Np(III) salicylate

and grayish-

precipitated sulfates

under controlled KsNp(S06)5 these even at

conditions.

of Np(iII],

and NaNp(SO~)z-nHaO,were precipitated. salts were stable to oxidation during

In the dry form, prolonged storage

increased

teqerature. coqnmnd of Np(VIl), Co(NH~)GN@S3Ha0, has

Only one solid been reported.] Coqounds and 6. solution,

qethods.

of Np(IV), S includes

(V), and (VIl are shown in Tables cmpounds prodtied in aqueous by other

Table

and Table 6 includes

coqounis

produced

-17-

,.

TABLE 5 ~ wPTuN1iM cmoums PRECIPITATED A-!;

Coqoeition
Color _ *%;

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

m Nmat dilute ~ia lM Mt,ai -

Brwn

Purple G?~yi sh 111= Green Green GM

Tm Brwn Gre,n Green Grey groeo %mm

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

Tan Greenish blu

Greenish

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

Bluish lilac 81W Green

32 32 a 46 34

s
I 40

0.04M dlIA@lll; C 0.3M ml

-18-

TABLE6 OTHERNEPTUNIWCOMPOUNDS Compound Np112 NpH ,

W2

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

are listed exist

in Table

7. ions

The first

as hydrated

in the absence

Np(VII) is stable in acid hydrated

only ir, alkaline

to Np(.VI) occurs charged,

solutions. neptunyl itm, [Np02(H20)EJ+, Because Np02

The singly

is the most probable hydrolyzes

oxidation

state

in solnx~ion.

only at pH ~7, disproportionates and forms no polynuclear pentavalent electrode

>nly at high acid complexes, it is stable

concentrations,

compared to the other potentials and formal

actinides. potentials 8.

The standard in lM HC104 of pairs

of neptunium ions The formal M solutions in the stated potentials

are shown in Table potentials

oxidation

for Np couples

in various electrode

are given

in Table 9 ~ with the hydrogen

medium as the reference.

The change in the of HCI04,

in l.OM H2S04 as compared to lM solutions strong complex formation

HCl, and HN03 indicates wlfate ions.

c,f Np4+ with

-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

* (), Np~Vi . W* ?/Po) q I-(5M

.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

(evaporme] (or tfi; ,

+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.

C. Hi diw. J. H. ~]-. R. Rraodt; J. M. MIa. * In IKlo..

J-: b. 9.-912 (i970). J.C. Sulltwsm J.Zimlcn. IllLq. hot. d A.

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
. .

Electrode Np = Np+ + 3e-

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;

-0.48 Np02[OH);Z Npo20H (-0.43)

-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-

The current-voltage reactions [).2.

curves

for oxidat~on.reduction are sliown in Figure 2.

of Np in aqueous

solutions Reactions

Olxjdation-Reduct~on Table 10 lists

reagents

and condition\ For cases

necessary

to change

c~xidati.on states
jlSt-~sferred,

for Np ions. e.g.,

w~ere only one electron

NpJ+/Np@+ and NpOZ+/Np022+, the establishis rapid. Redox reactions

that

ment of redox equilibria fomaing or rupturing

involve

of the neptunium-oxygen have a slower

bond, e.g., rate. of the in

Np*+/NpQ2 and Npk/Np022+, Rate constants redox reactions Table 0.3. 11. Disproportionation

reaction periods

(k) and half-conversic,n solutions

in lM acid

at ;!:)*C are given

of Neptunim state under~oes appreciable

Only the Np(V) oxidation disproportionation. + 2HzC)shows that high acid stable

The reaction disproportionation

2Np02+ + 4H+ - Np4+ + NpOZ2+ of Np(V) is favored by

concentrations.

Because Np4+ and NpO;:2* form more the disproportionation agents. The of

complexes

than the Np02+ ion, by the addition

Np(V) is promted equilibrium

of completing acid

constants,

K, for various

solutions

are listed

in Table 12 where
~ . JNP(IV)][NP( VI)]

[Np(V)]2

-24-

140

ml

90 V+ 80 -d Iwxn--*[lv) 4 Np( )-NP(IV) Em -%0 ii 3 ~o v w 20 10 0 0 -a2 -OA -04

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

-!.6 -1.8 -2.0

Figure

2.

Current-Voltage

Curve for Red(tx Reactions

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*(

IV)] [NP( VI ~ PJPm2

-2a-

The reverse

reaction

takes place rapidly constant 0.4.

in weakly qcid

.w)lutions.

The rate

in lhl K1O+ is 2.69

(M*ain]l*. J* Soluttcms of 2J7Np of

Rdiolysis o~Neptunlm The radiolysis

of Np(VI) by self-radimtion to Np(V) with see-] (0.5 a rate constmt

causes (3.1

reduction tO.2) X 10-s yield

to 1.7N HCIO~) and a radiolytic ions/100 Np(Vl) ek.-~ fh~ared rate to of

reduction other

(G) of 6.4 actinides,

hexavalent

has a much lower

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

For the ~ m 3.4. (saturated electron tively Np(V).

The radiolytic with bean?s: high stability

q tmospheric

oxygen]

are shown in Tablo to radiolysis.

Np(V) has a comparais oxidized to

Np(IV)

When 23gNp is prepared uranyl salts,

by neutron

irradiation tetravalent

clf state,*2

80 to 90% of Np is in the

-29-

Acid ConCent SW ion

. 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

fON%i On with ~of

q

Hydrdysis water

transfer mlcculu

proton

fron

8 coordinated s.g. ,

to a wstor

in tha outer

sphorw,

with

TheJ most recant

snd extensive

hydrt}lytic

studies

of Np l%, are

were msde by A. 1. Moskvin. listed for in Table 14 for Pip(IV), acid

!+ydmlys:,s (V),

constants,

and (W] .* to undergo

The ttmdency hydrolysis

Np ions

in dilute

solutions ionic

increases Z is the tendency

with ionic

increasing charge,

potent ill the ionic

[d) where d = Z/r, radius, in the Thus, the order:

snd r is

to undergo

hydrolysis

increases

]W2+ <N@22+Npoaa+N#+<N#+, < <

Successive in the sumably formation forms hydrolysis of colloidal reactions in Pu(IV) solutions result pre-

aggregates. with oxygen

Tho polymer cm hyd:roxyl

irreversibly

bridges.sc

*The stability calculated water,,

constant from KI %
q

KI of the Np hydroxo ~ here iY the

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]

9.s x 10-1 8 X 10-10

NpO@H

NpO;+

N@2(m2

2 x 10-2

-32-

tiskving

repo~s

evidence solution

for

formLtion

of polymer

fom

of

Np(IV) in queous 0.6. ~l~x

mt [H+] :0. 3M.

Ion Fomstlon of w~lex states spocios with the

q

Tho fo~tion different jmtential fmm other coqmting oxidation for

by the sctinides of ligands fmm each other and hydrolysis

in offors and are

vuriety

separating

sctinidos formation

cations. reactions.
qs

Coqlex

The ~chanism successive sphere

of complex rmctions

ion formation water and

can be repromnted mleculos anions,

from

between

the

inner

of Ihe hydrated

cation

A, e.g., Np(H*O)/+ +A=NpA(HzO)7:+ + H20 is dependent on the of

The ability =gnitude Np ions

of an ion to form complexes of the ionic co@exes potential. is usual]):

The relative

tendency

to fom
Np+

>Np+ >Np023+ NpOZ2+ >Np02+

(111)

Neptunium

Np(III) The chloride spectroscopically (see Table

exists

in aqueous

solutions

as Np(HaO)es+. have been studied

and bromide

coqlexes

cf Np(III)

in concentrated

LiCl and LiBr solutions

1S).

-33-

rmt.f 15

-m -

ua U*

Bs&A t] 2.42 h - 4.s s,

S.4S
6.s4

40

s,

1.a4m% I.m mob 2.a ncm, 4.* =10. i.a ml%

01 - 0,04
0, b, n, 0, 0, 0, 8, - 0.24 - O.bt - 0.51
q

49

w C9

O.M

- 0.16 - 0,10 - 0,10

q q

91

W* WI
w 1
Wm
14pm,)

6, E, B, n, 01 B, B, B, 0, BU B,

4.81 757

02

. 9.s1 %11 . 0.24

q

l.a ml% I.m mm. z m mob

a.m UIO. 0.2 to m 14210. z. a

* Ww)r
1

B9

0.01

m=,)

- 0.16 .
q

0.24 0.24

90 tf 91

- 0.15 - 0.7s .11.:

q q

mo.

*. [m-m)]
PIP(S.I a

El 0,
0,

n 93

1.4s X47

s.a -m 4.mIan.
[NP(C,O.)]J

2.49 n, 5.57 n, 2.70

B, *
q q

92

0,

4.16
9s

*(CA%] a l.m mom l.m 2cI0. 0.1 to

o. m 0.s ~

0, s, B, B. 8, s, 8,
B, 0, 8, 6,

q 1.ss .17.s3

[b[c@*) ,1 rmcnw,I-

.25.98 .27.40 - 7.40 .1s, 62 .19.44

. 0.19 .16.42 . q q q

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

s,7-olchlomI-hmwI@mllutm m-) Etl@aDdlAwcat~ata lE~A)

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

2.CN Hcl d,ml Hclo.

Np, c

0, n,

0.30 ?.s1

1P: 91

[t.yo,m,j I.w =10. up*lml,

B, e, e,

1.ss 0.25 1.6 1.4 !..1 74 d6

101 QI

4.OM tclo. [N@,: 1O-M 1oo, N@,al KI,,, ]-

et ~,-e, ~,
q

4 :.15 S.KI 2.41 4,0

[N@,s~,)~ [N@ so,l;-

fll e, t?,

III]

. .

Nflz(lrn,) O.ow m.clo., [NpY,czo. )1 -

103 134

0, d,

.-.3 . . . . . 1.3! 1.80 I.at !.s5 6.s1 s0 lo~ ILM

NPz (W [N@,AC;,l1.5M M1.clo,

fl, fll 6! B,

I 05

8-htirow~lmllmca (01) Glymlmto (GLTC)Lactara (wm)-

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

[NpO,:Wl), U9r, cm!tmt8. daflnd

q ,:

]-

0,

1.20 fome:

105 *O,. mf

IS. dlntm. diitributim with radm elrmmdo; 3. Smbility Fer ttw comtmts twsctlm of

.8 p,

Ls; I*1, @ Wtfd. m

u

lM

q lchnll@;
to bug L, !hc

tpsct-qhotmmrf; tha qu K ml llbrim B

qm

ml*ctmtlw*

W@ Ilnn # cnt L.m

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

2.17 S.07 1.s1 a.n l.=

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

. 4.m . . . . 7.m z.S.40 S.SJ

111

112

% s,

l.?

115

. 6.09 . 4.00 . ?.l J 11s

2s

[w,m-ml 01 P, l*, (EmA)lo al Uclo. a lclo, o n

I a 4cI0.

:s ?& x n F19rl&
JI

a. s, m, 9, e, s,

- 0.1: - 0.1s - O.n . O.M . 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

. 4.U . b.m . J.u 117

Jo

0, s, 1,

. ~.n . 6.0 . a.m !10

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)

(I1r.J which exists with as Np(H@)c@+ in aqueous Analogous solution, forms

complexes negatively

most anions. chloro

to Ll and Pu, Np(IV) coraplexes in concenexin-

charged

and nitrate are

H(3 and HN03; these Np(C20s)2 that the

complexes

sorbed

cm anion

is soluble

in dilute

(NH~)zCOS solution

carbonate

coqle~,es, than

which have not been the oxalote complexes.e

in detail, studies in solution precipitate in nitric

are more stable of the nature

au~d composition

of peroxide Np(IV)

have not beml made. is formed by !Iddition acid. constants listed

A purple-gray of Hz[hto

a solution

From the following creasing first

stability

in TabI@ 15, the according to inof the

series strength

of Iigands of the

were a::ranged,

complexes

formedi by addition

Iigand

to Np*+:

C104- <Cl- CNOS- <S0~2- U:H@30-

<F- <c20Q2M7ptainiwu

~-

<E~A*-

C~As-

<Qx-

(VJ
present in

~~), neptunyl of its which ion,

large q re

aqMOUs solution

os singly completing

charged agent
because

NpOZ(HaO)6+, is u Pom
size and

low charge. in stability

comparable

The n~aptunyl complexes, 2+ to Mg2*$ Ca , snd Zn2+

-37-

complexes,

87are

much more stable

than

pentavalent

uranium,

P~lJtG~iU.!7!F and alIR3riciuIB COlUpi8X8S.

Studies Cr:~+, Fes, been mde.& From the following creasing the first

of cationic

complexes cations

of 14p(V; with

IJOt2+, have

1%+, and other

in HCl(lt solutions

stability

constants

listed

:bt Table ;lccording

1S, th{e to inof

serit?s strength ligand

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

Np(VI) exists the stability

constants

of ligands the

were ~rr =:iged according formed by the addition

to increasing of the first

complexes

Npf322+:

C1O* <NO?- <Cl- <9A= <CHJCOO <F- KC204 Neptuniwn(VI J of N&(VII) complexes have been uade. solution formation show that with

Very few >tudies Sulfate compiexes

of the Np023+ ion in acid tendency towards -38complex

Np02 + has a higher

sulfate because

ions

than

the neptunyl of the

Np022+ icm.

This

is reasonable from hexav~lent

the char~

NpQzn group

:.ncreases

to heptavaIont

neptunium.

!/1. A,,

PREPARATION NEPTUNIUM OF SAMP1)ES FORANALYSIIS

NEPTUNIIM METAL ANDALLOYS

Neptunim

metal but not

dissolves

in HC1, otlier

halogen Hl,SO~.

acids,

and

sulfamic

acid

in HN03 or concentr~ted Np is dissolved fluoride.

Hot dilute

H2SO~ attacks trated nitric

Np slowly. acid

slowly

in hot concen-

containing are soluble

Np-Al alloys

in 6 to 1(IMHN03 containing are also sclluble

@.05M

iilg(NO~lz and W.02M KF; they Am alternative solution are method

in HCl and HClO~. the Ail in a elements

is to selectively Np and other

c[issolve actinide

of NaOH-NaNOs; the by filtration

separated

or centrifug~ltion

and are :501uble in

boiling
IB.

HN03-HF or HC1.

NEPTIJNIIM COWOUNDS
Np02 prepared
by

ignition

of the

oxmlate

at

400 to 600C is temperaeven with bisulfate

soluble tures, the

in hot refluxing

10M HNOs. in strong

When ignition nitric acid

is done at higher for a long period, with is potassium useful

addition

of HF, is required. of the melt

Fusion

and dissolution NpOZ fired soluble

in dilute

acid
Blp

for dissolving readily ions.

at very high acid

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:

metabolized fallout environstep

neptunium sqles. mental which

in excreted

saqles

Most procedures samples renders involve Np soluble

for dissolving, treatment in acids. types with

or othler fusion little

or a basic

There has been of samples; bcme,

investigation cleterminations tion, soil,

of Np in these of plutonium and water

however,, feces,

numerous vegetaof

in tissue.

urine,

have been reported be applicable many of these and vegetation or a combination

and the

same methods and

dissolution

would probably

for Np; Nielsen methods.

Beas ley 11 have smrized of biological multiple sa~ies

Dissolution accomplished In and by

is l;enerally of \let sucli as

wet ashing strong

and dry ashing. perchloric acid

wet ashing nitric furic fused acid acid with

oxidizing

agents

are used and hydrogen sodiun

[individually peroxide.

or iii combination), In some cases the

or sulsample i.s

ox potassium acid. 120

carbonate:

and the stelt

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

lbl~havior in coprecipitation, However, extraction more co~lete ion

separation

elements

can be aft~ained. and solvemt Ix:cause

{exchange , extraction :separaticm separation are

chromatography, exclusively rapidly.

used alaost mre

is attained

Precipitation large-scale neptunium limited.

of neptuni~

oxalate

:.s regularly

used to
ils

in

processing oxide.

of neptunitm

8s u) intermediate Np coapowlds

Precipitation

of other

very

The coprecipitation states of Np is sh~n

Lantha?u4m Fkwid%.

behavior in Table 16.

of the

different

oxidation

The first

separation

of a pure

Np

compound described ,coprecipitation. lquantitativcly

by Magnusson Np[IV), Pu(III),

and LaChrnpelle4 used and RJ(IV)

LRF9 almost
U

are carried acids. uranyl

by lanthanum

fluoride

from mineral of the strong state

deconsulfate

tamination i!;best from H2SO~ because complexes.

by

Np is reduced fluoride

to the

tetravalent ions.

and precipitated fluorides

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

Barium Sulfate Carbonate

c c c c Nc c

c c

c c

a. C

indicates co-precipitation ulwier proper condition.

near.llj complete than a few

b. NC indicates co-precipitation less percant under proper conditions.

-42-

includin~ carriers

the me

rare

earths

and Th also

prec:ipitatc.

Hold-back of Zr md alkaeither to

added to decrease The fluoride sulfates

the precipitation

line earths. acid-soluble

precipitate

is converted

by evaporating with

untjl~. fumes of HzSOU appear, alkallj. hydroxide. Oxidation Np(VI), and, stelp. state hence, After and

oIrto hydroxides at room temperature but other acti.nides

by metathesis with bromate

yields

K.uoride-solubl(e

and lanthanides in a subsequent Np is reduced with the LaFS.

are m}t oxidized LaFs pre[:ipitation to the Ix)travalent

are precipitated removal again dioxide of solids, coprecipitated preceding

Pa is co~trecipitated zis required.12i

WILthmanganese LaFt

LaFs precipitation

precipitation Np(VI). 122 Zimoni.wn and other A variation it; based

has been used to separate

NI~(IV) and Np[Vl from

Phosphate. are

Tetravalent coprecipitated

io]~s of Np, Put Ce, Th, witl~ zirconium fiompson, f~fter phosphate. and !3eaborg121 ion and

elements of this

method by Magnusson, cycles. is heated

on oxidation-reduction the solution

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

and then with with

Nlp(IV) and Pu(III) and in with LaF$.

Np is carried carried.

zirconium

pho:~phate, pho$phate

U(VIj are not

The zirconium

is dissolved

X!No3

HF, and Np is separated

from Zr by coprec:ipitation

-43-

Barium carrier-fne barium potassim sulfate

Sulfatu. trace

Ce, Ba, La, and ?dp(iti) quantities in levels to 1 mg are coprecipitated sulfuric peroxide. acid solution:~ This causes

from

>99.7% by containing a separation of sulfuric the Ce,

from strong and hydrogen ele~nts,

salts

frcm most other the bariw acid sulfate

Np was separated

by dissolutiawt

and reprecipitation chromic acid;

from concentrated carried with

containing

,p N (IV) was net

Bat and La. The Np in the supematant hyclrogen After peroxi& and again coprecipitated

was reduced with

to Np(IV) with sulfate. by gamma modified~z

bariu

the precipitate of the applied filter.

was filtered, ]z

23Np \/as determined

co{mting ami also sal@es125

The method has been further of envi::onaental

to a wide variety 1s, p176).

and biological

{Procedure
.

Hyiraeich

Insoluble

hydroxides

copreclpilate Generally,

all the

oxidation trivalent

states

of Np except

Np(VII).4SS127-129 are carried depends

and tetravalent of reagent solution. that

states

most effectively, on the composition

The choice of the cations

for precipitation Strong bases (Al, ligands. complexes

are used when the

solution solution

contains contains

are amphoteric coaplexing

Pb, Zn) cm when the When the or are solution

organic thiat

contains in strong

cations base (Cu,

foxm amine

insoluble

Cc), Ni, Ca, Mg), mnia

is used as preci.~itant.

-44.

Other In.qmnio with bismuth potassium. nate sulfate gives phosphate

Copmtipitants. and the double with

Np(IV) is sulfate

coprecipitated and sele -

of lanthanum pot~:ji~ for double the double

Coprecipitation results similar

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

cop~cipitated Dupetit lent actinides

with potassium and Aten132 with thorim

described peroxide

and uranium

peroxide. but results

Neptunium were pmr presence

is completely with uranium

carried peroxide.

by thorium

peroxide,

l%is was attributed

to the

of Np[V). less oxalates coauon carriers and zirconium,

t@%?&p~t~t8.

Other Lanthanm

for Np(IV) thorium,

include and eerie

thorim iodates.

and

Othfm ~cznic
zirconium the

Zirconium

phenylafionate

and of

benzenesulfinate

are specific

fo? coprecipitation The twtnsuranium

tetravalent ions

from solution. cations steps 133

elements by a series for

are separated

from other

and from each other to those outlined

of oxidation-reduction zirconium phosphate.

similar

Kuznetsov reagents uranium for

and Akimova13* have proposed concentrating from very species the tetravalent solution!;. acid-nitrate

a number of organic cations of the txzms-

elemmts

dilute

Np(IV) and Pu(IV] salt solutions,

form he~nitrato

in nitric

-45-

and these

cations

are coprecipitated cations. Of the organic

with rwagents

the nitrate ~tudied,

precipitates butylrhodamine nitrate Np[IV) ammonitan colqounds. manganese,

of heavy organic was the -st solutions, and Pu[lV). bases, Excellent and copper

effective U(IV), Other fi(IV),

cation.

In mncentrated coprecipitate! with

and Ce(IV)

coprecipitation mnium,

was with

quaternary

dimethyl

dibenzyl

and benz?lquinc~lium earths, iron, chmmim,

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

(arsenazo] nitrates selective. Np(Vt)

cyclic

organic

reagent.

to the organic less

the precipitation

is more (c(mpletel but

with

sodium uranyla~~tate. of macro quantities method. of Np is If other these free must from

Prvaipitatwn. seldom cat:lons

Precipitation

used as an analytical that fom first. insoluble When the

or radiochernicul

compounds are ljresent, solution is :r(:latively

be $teparated other ions,

a method such as alpha less health hazard.

cotatting

is usually

mo:re rapid

and offers

A nusber

of Np compounds have indefinite limits

10U solubilities stoichiometry the usefulness

in aqueous or necessity of direct

solution; for

howevlm,

calcination

i:o the oxide

gravimetric

deternunation.

-46-

@ihti&8.

No information it is rapidly

is available oxidized acid

on Np(III)

hydroxide, atmosphere.

probably

because

even in an inert solutions

Np(IV] is precipitated potassium, hydrous filter; volubility lM NaOH is

from mineral

by sodium, hydroxide is difficult No formal in lM NaNOJ or to

and ammonium hydroxides oxide. it The brown-green redissolved are reported,

as tho hydrated

gelatinous solid in mineral but the acids.

is easily studies <1 mg/1.

volubility

Np (V) hydroxide solution

0.014

is green.

The volubility ~!/l;

in dilute

ammonium

is 0.18 g/1.35

g/l;

in lM NaOH, 0.017 was speculation

and in 2.2M NaOH, Iiterature38

There

in tile early

that

Np{V) might precipitate

as NHqNp03-:ti20 or an analogous the exact nature

sodium compound as well of the precipitate as dark brown acid solution;

as NpOz(OH]9HZO; however, Np(VI)

has not been confirmed. with exces:;

is precipitated

(NH4)2NP207H20

ammonia from mineral When reported

the

volubility

is given

a:; 25 mg Np/1. 5

sodium hydroxide co~sition composition tion of the

is the precipitant,

a brown compound with Studies

Na2Np207xH20 is precipitate(i. of the uranates neptunates given leave

on the variable

some question

as to the composi-

above. 137 colored HCl solution Np(III) fluoride is precontaining acid

Fzuotid88. cipitated Rongalite in dilute

Grayish-lilac a dilute

by adding

of Np(III)

to a solution hydrochloric

of ammonium fluo::ide acid while sparging

or hydrofluoric with argon.

The dry hydrate

compound was quite

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-

After bright-green originally

4M

valence

adjustment

to Np(IV) with

ascorbic

acid, ko

Np[C20~)2D6H20 is precipitated containing addition 5 to 50 g of Np(lV), of oxalic acid. of nitric concentrations

from solutions [V), or (VI) in 1 to varies acid as

HN03 by the

T.le volubility i~cid arid oxalic near

a function (Figure bility tion 3).

of the

concentration acid

At oxalic between between all

O.lM, the voluacid concentra-

varies is varied

6 and 10 mg/1 as the nitric 1 and 4M. The solukility in the tetravalent is

is very tlependcnt state, attained. ~3g

on maintaining Significant The salt The soluble

the neptunium

separation

from a number of cations

(~U)Q[~(C20~)~]-(~~)2C20~= aqueous complex was cooled Ethyl yielded alcohol addition

XH20 has be~., isolated. to OC to remove cxccss produced an oily, darkwith

ammonium oxdate. green liquid that

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

of Np(V] in lM HC1 is treat~d in tert-butanol. bl

Neptunyl(VI) crystalline containing

oxalate (Np02C20~3H20),

a grayish-~reen

solid , is precipitated 20 to 40 g Np/1 by adding The volubility

from 2M HV03 - O.OSN KBr03 oxalic zcid until the solution

is IJO.3MH2C20Q.42 increased 20C. from W.5 In lM INOJ at

HZCZ04 in 0.5MHN03 - CI.023M

to v1.5 g Np/1 over 14C, the volubility

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 _

-2.813 : B- 3.7fi 1 I.0

~~

Figure

3.

oxalate

-so-

%0.75 g Np/1 as the oxalic to w. lSBL Pervti&.

acid

concentration

varied

from WI.002M ,

Np(IV) peroxide

is precipit:lted

from solutions addition of

containing Np(IV), hydrogen reduced peroxide.

(V), or (VI) in >3M HNOJ by the ~o The higher valence neptunium through states

are rapidly precipitates. colored,

to Np(lV), and gray-purple does not progress complexes crystalline that

peroxide the highly

The precipitation soluble peroxide. acidity peroxy fio

are characteristic

of plutonium depending is on the reported -%

forms were prepared solution.

of the precipitation

The volubility o: nitric acid

as a function peroxide. solutions not readily Iodate8. reported.

of the concentrations

and hydrogen occurred in were

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

ac;.d concentrations iodate solid, acid

of <2.5M.

of Np(IIl) a tan-brown

has not been is precipitated solution. The when

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

some Np was in higher

Amtate.

Rose-colored

N~@Z(C2H@z)s nitrate solution

a sodim acetate - sodim sulfuric acid solution b-te

is added to a dilute to 90C in the presThe

that

has been heated

NpOZ2+.

ence of potassium M.1

to give

volubility

is

g/1 in 0.5M H2SO* - 0.07M NaNOs - 2MNaCzH~02.38 -sl-

Ccmbo?latea. rqor~al precipitated to a solution ion,~3 Phosphate.

No sinple

carbonates precipitate

of NF(III)

and Np(l V) are

A light-colored by addition

of NF(V), KYpOaCOs, is carbonate (to about iodide pH 7)

of solid

alkali

of Np(V) uade by reduction

of Np(VI) with

A green

gelatinous acid

precipitate,

Np(HPOb)axHaO, in hydrochloric

is formed when phosphoric or nitric acid.

is added to Np(IV)

The volubility

in lM HC1 - O.SMHsPO~ is W56

u g/1,

and the volubility sulfates. Mefodeva complex

in lM HNOJ - lM H#O~ is %134 mg/1.+5 and Gelman32 report precipitation of

Np(lII) Np(III)

as the

sulfates

KsNp(SO+)b und NaNp(SO~)2*nH20. hydrochloric and sparged with the argon

is produced

in dilute

at %SOC using sulfates Np[IV)

Rongalite

mductant.

In the dry form, even at increased

complex

are stable is crystallized

to oxidation from hot presumably acid

teqenture.32 acid as a

concentrated

sulfuric

bright-gnen is %16 g Np/1. been reported, not reported,

compound, Sulfuric

Np(SOk)2*:cH20.

The volubility

solutions

of Np(V) and Np(VI) have on volubility.3S Although analogous to

but no data it is expected could alkali

are given that

Np(IV) colpounds

Pu(IV) sulfate

co~ounds salts, Other

be precipitated metal ions,

fmm a solution

containing

and Np(IVj. coaplex salts have solutions

Conpounda.

Several

Np(IV) chlorLde

been prepared.

Yellow CszNpCls was precipitated

by uixing

of Np(IV) and CSC1 in 2 to llM HC1 and saturating the rwsulting

-52-

solution <0.DIM ~d

with hydrogen increases

chloride.

19N3volubility

in ~lOM HC1 is A similar compound,

to w1.4M in %lM lIC1. ~ by adding

[( C2HS)~N]zNpC16, was precipitated chloride in 12M HC1 to Np(IV)

tetraethylammoniwn Several other

in 8 tc) 12M HC1.12

complex salts

of Np(V) and Np(VI) have been by the

reportecl.

Yellow used (Ph4As)2NpOC15 yellow)

[(C2~5]4N]2Np02C14 was precipitated for the Np(IV) salt,13 (bright yellow),

same procedure yellow),

and Cs2NpOC15 (bright

CsSNpOC14 (turquoise),

and CszNpOzClk (dark q have been

were made by variations The phenylarsonate reported.32 dry.

of the same pr>cedure. and salicylate stable

of Np(III) at :unbient

They are quite

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

extraction the effiother

of Np is usually ciency

uade from nitrate

and specificity as fluoride,

are decreased sulfate,

from chloride

systems;

systems,such with

and phosphate,form complex ions

neptunium,and There

extraction of bath

is inhibited. ion association extrac:ion extraction systems for and Np.1bbD15

are examples

chelate

extraction systems,

among the solvent compounds replace almost

In chelate

such as lTAp cupferron, coordinated covalent, water cheiate

acetylacetone,

and 8-hydroxyquinoline ions and form neutral, in such organic several

from neptunium compounds that are

soluble tion

compounds as hydroc~rbons.
uechanisms

In ion associa-

systems,

are possible

by which uncharged, attraction association system, is coordinated nitrate ions solvents

extractable between

compounds are oppositely charged

formed by electrostatic ions. In one ion

an oxygen-containing to Np(IV), to give conmonly isoamyl and the

organic complex

compound cation

such as ether with

is associated species. include

an uncharged used for alcohol,

extractable

Ion association TBP, hexoneo carbinol.

Np extraction pentaether,

diethylether, For solvents complexes

and dibutyl

such as hexone with actinide

and diethylether, nitrates, the order

which fom
of

coordination

extractability

of the various

-s4-

oxidation last

states

is usually generally state hexone

(VI) > (IV) >> (111) considered

nd

(V)~ with The but is

the

two states

to bm nonextractable. by diethylether

(IV) oxidation extracted agents, the into

is poorly and dibutyl

extracted carbinol.. complexes the

For TBP and chelating with the uetal complex nitrates, is usually to

which fom oxidation

coordination state giving

stable

strongest

extracted

most efficiently. is

The tendencies

of the

actinides

form complexes and other effectively. exceptions state

(IV) > (VI) > (111) agents usually (Table

and (V). the

Thus,

TBP, TTA, most these

conrplexing

extract

(IV) state

An exception may be the result

17) is lJp(IV]-TBP; instability

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

C71ezute s~atema. A large that form strong coordination

number of ~i-functional complexes tiith metal

been investigated. organic phase. solvents-such Of these

These complexes as benzene the

are mme soluble

in nonpolar

or CCl~rthan fluorinated

in the aqueous B-diketone, used 2for extrac-

compounds,

thenoyltrifluoroacetone tion of ?+@ radiochemical in include before states.

(TIA) has been most widely and analytical

appl:lcations. of the

17~*a total

Many variations separation of its schek

TIA extraction the analysis i27~]92#*9D10

as a part

of Np or the determination

oxidation

-55-

TAUE 17 VAAIATIOUW ESTRACTIOII COEFPICIU(TS MITMOXIlhTIOR STATE

QElmkk ll##t
1* TW-korosem m O.sm nA-xylOm Di*thyl

Aewau Imi)*

Pmula

!QQw_&MM_ 3.0 ,.-6 10

YFXQ__!Mw_ 0.13 ~o-. 11.0 10 4.6

.!Mw_&Qv_wQ 0.014 ,.-8 :!l. s ~@ z.~, 0.(104 ..31 1.:!

-(III) O.m 10-0

1J4 HloB edk tNoB lM MEb-sat m,mo,

q Clwr

0.1

0.3

Ibx$nw

Ossm tmm-11.lm m8N08 C* H40,

0.14

l.

9.e

0.3

1.

,a.5

~lw

-56-

Some data
0.5M TTA

for

the extraction for a range

of Np and other of nitric

cations

into are
1

in xylene 18.

a,cid concentrations

given

in Table Shepard

and Meinke have compilti showing extraction The data

a useful

set

of TTA extraca number ?TA

tion

cunres

as a function

of pi-l for

of elements.lso extraction elements. Basically, of Np to the fering ions

show that

by judicious

pH control,

is useful

to separate

neptunium

from many other

the lTA method depends highly extractable

on quantitative state while

reduction interstates.

tetravalent

are

stabilized

in inextractable

oxidation

(Procedures IKl is rapidly hydro~lamine

1 and 2, p 138 and 141], and co~letely reduced

Neptunium with iodide,

in lM HNOs or lM sulfamate,

femous

hydrochloride-potassium chloride.

or hydroxylamine the ITA,

hydrochloride-ferrous and Pu(III] fering directly alpha Fe(III), and U(W)

NplIV)

is eXtrdCted into phase,

remain in the aqueous the extract

If no inter-

cations for emitters Zr(IVl,

are present, Cotmting. 1s verified

can be evaporated of separation

from

The efficiency by alpha

other

pulse

height extracted

analysis.
ffrom

and Pa(V) are strongly is attained 8M Ii?#3s. Sulfate, by stripping Trivalent

lM HN03, the

but separation lTA-xylene do not

if

the Np(IV)

into

actinides oxmlate,

and lanthanides and chloride, with Al+ before

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

.. Ion NP(III) @(IV) Np(V) f@@I) Pu(III) Pu(IV) F%(V) Pu(VI)

!!!Qd?Q 1.0 1,0

8.0 0.8 0.8

Extraction at . <3 )(

Coeft:lcient 25*C Jo-s

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

<l x 10-3 375! 1 x 10-5 1 x Los 1 x 107

25D

1 x 10-9 1 x 10-20 1 x 10-20

4 x 3.1

10-~

-S8-

The relative The nominal 10 M 151 .

#152

standard

deviation attained

for a:he analysis from plutonium

of

is 22%. is 10g to and and

decontamination Some data systems

on the extraction

Np from sulfate by Sullivan

perchlorate Hindman.93

with TTA have been giren

ITA extraction also

preceded

by a LaFs coprecipitation Np has been separated

of

cycle

has

been described.153-L56 materials

from numerous
lTA

special extraction separating

where a combination

method:J including m method including for

was used.

Holcomb157 has described radionuclides,

17 gamua-emitting mderator nuclides

23gNp, from exchange. and

heavy water The individual

by ITAsolvent

extraction

and anion

were determined

ty gamma counting

gamma spectrometry. 8-Hydroxyquinoline Np(CSHGNO)~with tion

of

forms the following

chelates

with Np: Np(V]. Extrac-

Np(IV) and H[N@*(C9HGN(~)~] with as a function ofpH

4.

a number of elements

into

O.lM

8-hydroxyquinoline actinides hydrolysis extracted extract

in CHCIZ is shown in Figure only at pH 4-6, cation and at this

The trivalent

@i appreciable
is

of the metal almst

occurs. into

~] Np(IV) cupferron chlomfom

quantitatively in 8H HC1. i50a with

from lM HCl and

is back extracted Separation Pu and probably

acetylacetonate

has been reported

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.

/CHC13 [Na, NH*,

Cf(III), N (IV), and of Ra(II ! with

H)CIO~,

?, 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

so Pu and U, which form extractable 59!S1 PuIIV)

Chmutova et CZZ.extracted solution and fission

from 3M HNCSwith

a chloroform (V),

of N-benzoylphenylhydroxylamine; products (except

IJOZ2+, Am(IIX],,

Zr and I%) do not extract.~62 from 1 tcl 4M HNDa and 1 to under

Np is ex-

Np(IV] is strongly 6M HCl with

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

same conditions, tracted

at pH 9 to 10 with and is separated

in n-butanol

and

isopentanol

Ion A880CiatiOrI sYStm for large-scale

@8t4w18. processing

is a useful used

for quantitative soluble the type adding that free

analyti~al

separation.

TB~ forms an organicnitrate, generally of concentration Other reagent by

coordination

complex with

the metal

M(N03)149ZTBP.lb> salts

Increasing

the nti,trate ext::action. ions,

nitrate affect

of Al or Ca favors include temperature,

factors puritY,

the extraction

complexirlg

TBP concentration,

and mi],ing time.

A S_rY The a,gent f

of the early physical

work with TBP has been given by Geary,lsG properties of TBP as an extracting

and chemical

have been summarized

by McKay and Healy. *G7 Other discussions 168-170 xtract~on Coefficimts

the use of TBP are in References -61-

for many elements concentrations data

for

a variety

of aqueous

solutions

anJ TBP 149

have been reported 19.

by Schneider

and Harmon;

are shown in Table Np(VI) is almost

completely Na(I),

separated Zn(II), Separation

from Al(III), and many other

Am(III), cations

Cr[III),

Fe[II),

Fe(III),

in one stage involves

of TBP extraction. oxidation stripping

of Np from Pu and U for extraction of inextract-

either

of Np to the

(VI) stat{!

and subsequent able

of Np(V), or stabilizat:.on of Pu and U. ha:

Np(V) followed The following

by extraction sequence

of extractability actinides: actinides while

been found for

the

various

oxidation

states of the tetravalent

PI(IV) > M(VI) ~~ tht sequence is

M(III) Pu(IV) actinides n-or:

> M(V).

For the

> Np(IV) > U(IV) > Th(IV], the extractability

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

(Figures actinides distribution

HCl solutions from nitric ficients because

with acid

but

no maxima.

Lower d:.stribution acid Strong

are observed

for extraction

from perchloric ion.

of weak coqlexing

by the perchlorate

agent% such asOSOb2-, all quite actinides stable

P@k3-, and F-, reduce however, these cations anions

the extractability such as Al that negate

appreciably; complexes effect with

partially

deleterious

on actinide

extraction.

Distributicm

-62-

TABLE 19 EXTRACTION Coefficient DATA FOR TBP1bg

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

TEP (%) 30 15 15 60 100 100 15 12.5 15 12.5 100 30 30 30 50 12.5 30 30 30 30 20 2G 20 25 25 30

Extraction Coefficient At 25c 0.013 0.0003 0.0003 0.002 0.0001 0.0004

0.005

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).

Dlstrlbutlnn of Tetravalent TBP.-Kerosene

Coefficients Actinfdes from Nftric

for tte Extractlm by 19 ~ol % Acid S~lutforl. l&5

-64-

~lgure! 6.

Dlstrfbution of Hexavalent lBP-Uerosene

Coefficients Actinlde% from Nitric

for the Extraction by 19 vol Z Acid Solutlon.G:

-6S

coefficients lower171 than

for Np(V] and trivalent for tetravalent

actinides are appreciably actinides,

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

good mixing. cmganophosphorus methods the butyl for series

The extraction

properties

of many >ther however,

compounds have been studied; Np have been defined. found the order Higgins

F:w separation

et aZ. wm:king with

to be phosphate

((RO)SFY1) < phosphonate ox:~de (RsPO).i72 for I.he extraction wilh various

(R(RO)2PO)

< phosphinate

(Rz(RO)PO) < phosphine coefficients actinides 20.

The distribution tetravalent phosphates

of some

and hexavalent are given

trialkyl

in Table

and Petrov Burger t7b*175

SUb!3t~ltUUIItS in

et a2~76 found that

electronegative and phenyl,

the alkyl

chain, such as, chloride Sidda1173

strongly the length

depressed

the extraction. chain

found that series

increasing

of the alkyl

in the phosphate

made little and chain is

difference hexavalent to increase extraction generally

for up to eight actinides.

carbon

atoms for tetravalent of branching the alkyl

The effect

the extraction of Th. the

of U, Np, and Pu, but to strongly mechan~sm of these

but the Solvstion

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

Th 2.9 2.4 2.9 4.2 3.0 2.4

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 -

necessarily the same for all

elements.1

A method with mono[2-ethylhexyl]orthophosphoric acid in

contact with 12M N(21+ O.lM hydroquinone separating trivalent the other contact Np(I!/) from U(VI), rare earths. Pu(III),

has been effective Am(I[I), Cnl(lII), and

for

The K value

for Np([V) is V103,and for

i:5 attained

cations,mlO-l; followed

thus, separation scrubbing the acid

by a single pha:$e.~~

by multiple

of tl~e organic

K. Kimura178 has determined tion coefficients

depend{mcy of the distribuextract~ti by SO vol%

for many elements

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

cJf Np(V) into than

Np(V).

Np[IV] and Np(V[),

both of which are more extractable Np(V)Iin dilute Pu(IV), that nitric acid

has been separated however,

from U(VI), there was evidence

and Th(IV) by HDEHPextraction;

a few percent

of the Np(V) was reduced extraction. 180

to Np(lV) and not

separated

by a single

Kosyakw et C[ZjT9 used

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

of Elements frcm as a Function cf

HC1 Solution by 50% HOEHP Acid Concentration.17*

-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

sodium nitrite. with

I@(V) was then

oxidized to HP(V)

to Np(VI) and extracted and recovered

HDEHP. Np(VI) was reduced phase by washing with

from the organic f-

O.lM HNOs.

Am was back-extracted reduced to Pu(III)

the HDEHPwith

W HNOs and Pu was with 3M H?U)9*

and recovered

by back extraction

U(VI) was recovered Chudinov

and

by back extraction Yako*~lati-o step extracted

w:.th lU (NH~)z COs. IJ and Pu from Np(V) with determination of

HDEHPas a preliminary Np(IV) with Arsenazo(IJI). Peppard

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

the non- :etravalent

et UZ.B2 used this

method to puvify

2GPu for

The Np(IV) can be returned of TBP to the organic in the distribution phase,

to the aqueous re:;ulting

phase

in a great

coefficien-:. the d:Lstribution coefficients acid

Kosyakov et U2. *79 dete~ned of Am(III), (Figure conditions 10). Np(V), ~ey than Pu(IV),

and U(VI) in I{zMEHPfrom nitric higher :For the same aqueous

are generally for HOEHP.

those
ROSS183

White and extractive

have written

a general

review

of the

properties

of tri-n-octylphosphine

c~xide ~m).

-71-

R17

-1

Figure

9.

ExtractIon H2MEHP in

of some Actinide Cations Toluene as a Functon of

into 0,48M HCl Concentration.177

-. 72 -

6.a

5.0 4.0 30 $3 ~ 2,,0 d

I !,0

o -1.0 -2.c)~.L--J_. -1.0 -0.5

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

compositionsare shown in Table 21,

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~-

(M) 4.0 3.9 6.1 6.1 4.4 6.3s $.4 S.O

!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

INTO VARIOUS SOLVEWS

\ Extrm:ted

!ko2.
17 6S 23 48

!P.u!l
12 !2 )1 19

!!LQIQ

w
a
70 89 8: 95

WQ!!l

100

DBBP,= .Jot D~,d 85$

dlM HND, % 2.4M Hm,

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),

strongly Hg(ll), After

are Ce(IV), T1[III.1,

III(W),

Au(III),

and

SC{III);

P, Cr(V1],

and Bi[III)

are partially ferrous

extracted.

back-extraction

with

dilute

acid,

ion and urea

orhydrazine

are added to reduce A second extraction

Np(VI) to with

Np[Vl; IWNOS is added for salting. diethylether further separates data

Np(IV) fron of the acid

U(VI).127~i@ actinides, including into dibutyl

Distribution neptunium,as carbitol

for

several

a function

of nitric

concentration

are reported.loloo including mines, long-chmin and quaternary alkyl or aryl primary, react in

Amine extractants, secondary,and with acids the organic amine: 3N(org)

Amay

tertiary

amine salts

to form an ion-association phase. The mechanism

complex which is soluble is illu:itrated with a tertiary

+ (aq)

+ A (aq] anion

+ R3NH ---- A-

(org)

be either

a simple

or the an:.on of a complex metal

acid. anion

The complex may undergo a further reaction with another in a

u anner

analogous

to anion

exchnnge. + A {aq) PuIIV], ccqounds in radioactive is

R3NH+ .-. The higher and U.

A (erg)

+ B (aq)

+ 9NH+ .- B (erg) extractanl:s

over

araines are excellent of amines to radiation

for Np(IV),

The advantage stability The amines

orgamphosphoms and hydrolysis dissolved

the greater solutions.

are usually

in an organic

-77-

solvent separation

(xylene,

benzene,

or chloroform).

TCI

qchieve rapidl phase

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

is added to the organic solution

extractztiility the

of Np in nitrate selectivity tion nitrate ~nium

is Np(IV) > Np(VI) > Np(V), although

depends

on the structure phase. solutions > secondary

of the umine and the composipfwer of the asdncs order Quarternary in

of the aqueous and chloride > tertiary

The extrsctive varies

in the

> primaryJ$i

from H2SOS solutions, l:oefficient of tetra-

the squence valent

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

(more than one oxitiation tri-n-octylamine

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 Np(IV)mIci Np{V[) with acid with is reported. 1]*1$2 A

(TLA) from nitric extraction

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.

of tktlcxavalent Actfnfdk The Extraction Nitrates by 10 vol Z TOA in Xylene. ~g

-80-

Ioo#

w-

-1
AQtJoan Hrws, M

-81-

(TIOA) in xylene ferrous wlfamste.

from aqueous For further

SM nitric separation, with

acid

solution

containing

the neptunium-bearing ferrous a TTA

organic solution was scrubbed Sul.famate. extraction. extraction Final 19~s with purification

SM HMO$containing with

of Np was qchieved frm

239Np has been separated Np(IV) was extracted ~ni~ O~stributilm

2*~AJSby

TIOA.*g

[i# > 20] froa 0.1 in xyltme. for a large fron for various

to IOM HPKlgwith Ihe ~was ntaber

O.lM tetraheptyl

:litrata data

~2000 in lMNNO1. l$ in quaternary

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

- and hexavalcnt 14 qnd 1S). the

Np, Pu, and U from HICl solutions Pu(lV) is much more extractable and the hemnmlent :\ystem.

(Figures

and U(IV) under are umc

same conditions, than the

actinides

extractable

tetravalent in this ext?actsd

Np(IV) qnd Pu(lV)

qcid

were strongly

from sulfuric In guneral, solution

Proce

by the

primary

amine Primene*

JH-T in XYlonc.

the order W8S primary durcs these

of extraction >> secmdsry

of Np(IV) and Pu(lV)

~ tertiary ~Jne*20Q

from mlfate
*n) ~re

for aciinuextraction methods also offer

have been reported potential (ditwntaj.

for U and Pu,

sndi

for Np separmtic}n.esi]~ze The torn extraction synergism of metaks is iusod by mixed

Mixed &xtruotunt8 to denote extract~nts ~gfstered enhanced (diluents) tradcnamc

(or depressed) as c~ared

of

to extraction Mas Co.

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-

(diluent) under the

taken

separately.

The rangl~ of phenomena is diverse, subject l:omplex,and is given

described

term synergism A reviw the subject sre

not completely by Marcus.* attention, only have

understood. Although

of this

has received reported

con~iderable

a few examples reported product

for Np.

Lebedev et a2.202 its

a procedure

to determine

23Am through large

daughter of curium

2Y9Mp in solutions products.

containing

quantities

and fission

O.lM l-phenyl-

3-methyl-.4-benzoyl-pyrazolon-S (TEP) in benzene were used to

(PMBP) and 0.2SM tributylphosphate separate lM HIP04. other gm Np(IV~ from Zr, More than

Mb, Cs, Ce, h

and Cm in O.SMHNO, and with zO.1% of of the

99% of the

Np wa~ extracted

elements. activity Taubezog

The AR was determined of the extracted has d~scussed

qixtues

by measurement

239Np, inflwunce of polarity benzene in two-

the

component tetrachloride several preted

diluent

of chlorofl}rm,

and carbon with

on the

extraction

of Np(IV) qnd Np(VI) cooplexes The results npucies, are inter-

phosphate in terms dipole

and amine extractants. of the size of the complex

the diluent and

structure,, other

interaction Figures

between

complex

and diluent,

factors.

16 and 17 show t~~e effects dis+ributicm nitrate frm

of variation

of diluent

mixtures

on the

of Hp(IV) and (VI) into nitric

qcid.

TBP and tetrabutyl~nium

-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.

with TBP from Mxtures.2ss

-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}*

such as sulfonated to be sorbed charge

polystyrene. on cation

In general, the ability increases Thus, with the order

exchangers hydrattd for

and decreasing

radius. .Np is

on cation

exchangers

Np(IV) ~>Np(III) >

All Np species are sorted at low acid concentra-

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

applications. Anion exchange

is one of the techniques

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

are good references Other reviews

to the

theory

end applications include

of

ion exchangers. Korkisch,20s2il

of ion exchange

Massart,20e

and Faris

and 8uchanan. :10 forms anionic sorbed by anion nitrate resins; and chloride the anionic elements. sorbed

Anion Erohunge. complexes species that provide are

Np(IV) strongly

separation state of the

from the cations actinides Greater al:;o

of many other fozm strongly

The hexavalent anionic chloride

complexes. elements

sep:ltation

of Np is attained in the chloride over a

from most other system.

in the nitrate coefficients and nitrate in Figure cycle,

:;ystem than

The distribution
of nitric

of many elements concentrations 111. :~ sample

wide range reported.212

acid

have been

Data are anion

given

In a typical is adjusted

exchange

containing

Np

to 7 to 8M HNOs for to 0.05M ferrous is reduced or treated

optimum :\orption sulfamatc to Np(IV1. with

of Np(W~)G2-

ions, all

and 0.01

is added to ensure The solution

that

Np[V) and Np(VI] 30 minutes the

is heated

to 55*C for to react this resin Zr, all

sufficient e.rcess

sodium nitrite Fe(II)

to

sultlmate

and oxidize to prevent

Fe(III); in the to remove and

treatment bed. Ru, Pa,

is necessary The resin Fe, Al,

e.~cessive strong nitric

gassing acid

is washed with rare earths,

U, transplutonium lh(IV) and Pu(IV) 5 to 15 bed volmes hydrazine

elements, are not of 5 to Pu(IV)

most other separmted; 6UW3-O.05M

cationic howevez,
femous

contaminants.
washing with

sulfamate-0.05M

reduces

to

-09-

Figure

18.

Sorption of by Strongly

the
Basic

Elements Anion

from Nitric Acid Exchange Resins.212

Solutions

Pu(III),

which Th.

is removed from the The Np is eluted of the as well resin is resin

column. with

Washing with

HCl removes and particle from other Macroporous separation variations

0.3M HNOg. Cross-linking influences ofthc the separation

size cations anion

greatly

as elution superior

Np. i52zi3-215 anion resin for with

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

or aminoguanidine The separation and Pu!IV) in nitric

of tracer acid

Th(IV),

Am(III),

by anion

exchznge

has been reported.21G

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

column was washed with then with

7.2M HNOg to elute Th(IV),

Am(III)

4M HN03 to elute Pu(IV). Other

and Finally macro quantities

with

to elute cations

work with

has shown incomplete to Np(IV].

separation Also,

of Np probably

of some reduction completely

Th([V]

and I%(IV) were not products by

separated.

The separation ascorbic acid

o:: Np from fission is reported

in 7.SMHNOY using Ichikawa.217 Radiochemically high purity chloride metal

reductmnt

pure with

Np has been p::epared anion

for

production cycle

of

one nitr~te cycles coefficients acid

exchange

and two

anion

exchange

successillely.zie of mnny elements over a wide

The distribution range of hydrochloric

concentrations -91-

have been reported.

These data
exchange

are used
(Figure

to design

separation

systems

:forchloride :}eparated by

anion

19).*2*zi9

Np, Th, and PU are by sorbing the anionic

chloride

anion

exchange

chl~oro-complexes

of Np(IV) and Pu(IV) in 8 to J2M HC1.

Pu(III) is eluted with

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

separations including U and Np are

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,

equilibrium was not reached even after 40 hours of mixing.

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

Registered Trademark of Dow Chemical Co. -92-

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

l:+ .;, ,[.

~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

EIMlllEll El ~. E3fll Eilll fill * km . -.Bil Kit!!kill Eil Eliil

NM %

-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

Elu@nt W&moo column

VdUCWB9

Figure

211.

Uraniun-Neptuni uwPlutonlwn Exchange (bwex 1-X1O, x 3 cm Column). **s

400

Sel~aration b y Anion Nesh, 0.25 cm2

-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,

PU, II. Pa, WJ Zr in 1~1,

anion resin. EquiIibri~ and

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

to WN NtPO. with attained,

lbuu#-2 hut data

Separation erratic.~a

andleuas

Sp ukth

has hem

separated first. frm

fmm

Pa by elution
has also

uith hem

1231 K1-O.5N achieved

Pa elut{ng u~th

Separation

by

clution f~rst.zz*

S!UIUl

an~on resin, in which

case Sp elutes

!JJ(IV)
Sa2CD1

haz been sorbad

uith W*CI

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

s01ution9 exchange for

as sk behavlw

:+OSof

Ion.
this

a: (x:.z
complex

as a

poss~ble

has~s

separation for all

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

use in nitric are thought resin,

or strong

~olutions.233 skeleton in the

Tlw!se qccidents of the exchange presence should carefully The nitric col,un
of

to be due to nitration to the resin spontaneous!

of the reaction

leading

heat.

Anion exchange

in the nitrate and temperature in stronji nitric

form should be acid.

not be stored controlled acid

in the dry state,

qt

<60*C when used should

concentration

be <8.SM, a~~d flow to the wlmn high levels

should

not be interrupted, are in the col~.

particularly

of radioactivity

cation &Ywhf.znge. Sulfonic

acid

type

resins

have had limited and Np(V) are hove been and

applications
reduced

for

Np separations resin.:Sh

because Several state

both Np(uI) separations

S1OU1Y by the

reported

for the pentavalent reported the

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

in the hydrogen with

di:tedto the hexavalent state dqpended exchange lh(lV), on reduction

has been

to Np(V) by the resin. for partial separation

cation

used

of Np from Pu(IV), nitric

and Zr(lV).

Np was

ox~d~zed

to Np(V) in dilute

-97.

acid

before

sorption

on the resin,

but a fe~r percent of the Np(V) and was not

was reduced to hlp(IV) by the Dowex-5OWrosin separated from the other cations.23G

The distribution detmmined for

coefficients

for many of the Dowe~-5G resin.

elements

were

in 0.1 to 12M HBr with

Conditions

separation

of U(VI) and Np(IV) and separation of Np(IJ) and (Figures 22 and 23), Mary other separation

Pu(III) were given methods fcm Np could

be devised

from the distribution data

(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

Pressurized at for tory

elution

development

chromat~graphy acid elements

on cation

resin

70 to 90*C with a-hydroxyisobutyric separation and with of trivalent macroscopic type actinide quantities,z~~ for

has been very useful both in the labora-

Although

no specific

separations for highly

of this radioactive

Np are reported,

the m~ethod is useful

solutions. for many of the eleme~ts acid concentrations on Dowe3@,-50resin and also over a

Distribution over range a range

data

of hydrochloric acid

of perchloric

concentrations

have been reported (Figures

2S and 26).1$ -98-

a-

Smp18

9M WI 9M HBr ,,, .,,.

C)-2

.44J-.-JQ 6 8

Column Volumos

Figure

22.

Separation
(Oowex

!iO-X4

of U(VI) and NP(IV;) bY Cation Excllan9@ 0.2 cmz x 2 cm Column@ 25 }?37

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 25. Sorption of the Elemen:;8from HC1 Solutions by a

Cation Exchange Resin.

Figure 26,

Sorption of the Elements from HC104 Solutions by a Cation Exchange Resin.23@

i!no~anio largely higher

Ion ticdzangera. by synthetic

Inorganic resins

exchangers

have been because of

superseded capacities

principally

and more useful physical characteristicsof

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

zirconium tungstate, and Shafiev et al.2k3

easured.zbz zirconium molybdate have been u have studied the separation

of Np, Pu, and Pm on 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

does not change

the oxidation

The sorption on amonium

of Np, Th, and U from HN03, HzSOb, and molybdophosphale of so~ltion (AMP) colunns has been

dete~ined.2b~2s U(VI) ~> Np(VI) separation Tsuboya separating

The sequence > Np(V). These

is Np(IV] > Th[IV) >> the

same woy.kers demonstrated columns loaded

of Th, U, and Np using et aZ.247 demonstrated

with AMP.24G for Np(IV)

conditions

in a HNOJ system acid exchanger;

Np(IV) and U(VI] with a tung:;tic retained than

is much nmre strongly

U{VI) from 0.S to 2N HNOS.

103

D.

CHRWATMRAPHY
Emhwction

C?w0watog3up@. separation

Extrac::ion

chromatography

has 100%
was

been applied TBP sorbed initially

to the

of Np, PUB Am, and U with The diatomaceous vapor, Nitric then acid, :~hase.zho
of NF

on diatomaceous exposed

silica.

silica

to dimethylsilane stationary phase.

treated with

with TBP, and without workers2b9

and used as the reducing used this modifications agents, system

was used as the mobile for a similar separation

Other

and found that of Np(VI] to products.

oxidation states

were required

to prevent

reduction

Np(V) and to improve Eschrich250

used the

separation
same system

from some fission to determine the

of Np by eluting Np(V), Np[IV),

with

0.5 to 2M HN03.

The order that

of elution some reduction

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 -

The chzomn.~a~raphic batch extraction;

much more effective adequate

two

separation isotopic

so that

dilution

was not necessary. to separate separ;ltion

column separations

were necessary reported

Np frm

Wehner et aZ. fission

252 have also

cf ~3gNp from wi~h

and activation

products

on Poropak..Q impregnated

lTA-o-xylene. Some workers wkth an organic

q

have used Kel-F* extractant ofM. as the

or ~eflon** phase

powders coated for extraction

stationary Co.

Registered

tradename tradename

K. Kellogg

q *Registered

of Ou Pent. - 104 -

chromatography nitrate products.

separations.

Kel-F

powder

:oated

with

trilaurylamine

has !]een used to separate The feed was adjusted After

Np from U, Pu, and fission to 2M HN03 - O.lM Fe(SO~N}12)2 and

passed through the bed. containing

Fe(S03NH2)2,

the column wa:i washed with

.lMHN03

thu Kp was eluted with

HzS04 - HN03.

The method is very

selective

for Np(IV) and has yielded chemically ratio of U to Np was >1010 in the feed?s3

pure 23gNp when the weight

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

tCV03 or HC1 by [IV)

methanol,

ethanol,

have been determined Np(VI) to Np(V) or Np(VI) is slowly of the bi~nds. with

Keller.zss before

It was necessary the separation

to reduce because

starting

reduced

in the column resulting Neptunium(IV)

in poor

separation

was separated mixtures. with

from III(IV) Also,

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;

Np(V) was separated

2M HC1-ethanol measured the

as developer. for ele:~ents with atomic alcohols

Rf values

90 through

96 in mixtures

of mineral

.~cids with

and discussed Rf values paper treated

analytical for Np(IV), with

applications. (V), and (VI) have been reported 0.5M HN03 developer solutions for

TOA using

105

- . .... ... ,,. . ............ .

containing separated different treated

water

LiNOS, NN~NOS, or Al(~s)3. for the different oxidation Rf values

The valuss states

are well

of .Npand for the obtained for paper

actinides.zs with
(20:1)

were also

solutions
using

of tetrabutylhypophosphate solutions of nitric

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

of Np from each other layer chromatography

O.lM tetrabutylhypophosphate e

demonstrated.2

Gza Chrcwfatogq?ly. Effective elements by gas chromatography 60 The volatile

separation of the chloriies comploxes the carrier capillaxy

transuranium

of their chloride into

has been were synthesized gas. colums The maintained Cm, Am,

demonstrated.z

at %SOOCby adding experiments

were

A12C16 vapors

carried than

out in glass one microgram

at %2500C with

less

of each actinide. ator~ic elements

and Pu were eluted the snme position

in order as lighter

of decreasing Ianthanide times of W,

number in about in a similar

experiment.

The retention

U, and Pa are much

- 106 -

shorter; it is postulated that the tetra{:hloridesf these elements o

i~re

produced. The chromctogram is measu]ed collecting fractions by

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.

Separation of more-volatile Np(IV} chloride

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

Although electrodqlositionhas been used

for radiometric measuremc!r~t, electrolys~ls has

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 is completely delmsited at pH :* 9, and deposited at pkl C6 ~md pH <3, respectively.2*

have been Other workers using different media for ele~:trolysis

unsuccessful in separating partial separation

Np from other

ac-:inicles. l:ations

Although has been attained,

from a number of comon

no useful separation

method has been reportlxi. An analytical separation of the

q

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

products abundance exchange,

were separated by -ss extraction

for determination solvent

and

spectrometry

using

extra~ction,

chromatography,

prccipitution

108 -

VIII. ANALYTICAL METHODS

A. SOURCE PREPARATION AND RADIOMETRIC METHODS

Counting.

Because

counting methods are more :}e:lsitive than primary methods

chemical or spectrochemicalmethods, they ara the

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,

If 237Np has decayed

can be dete~ined

by gama

ray spectroscopy

2y]Pa

daughter. gam

[f 2:Np is separated 2~7Np 86.6-keV by gg-

from 233Pa lthich

h~as an 86.6-keV dimectly. at

:?ay, the

ray can I>e counted its gains

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

counts attlibutable 2:17Np. to can be uwd to determina gross can

scintillationcounting with
qlmost

q lpha activity

100$ q fficiency
presence

ard in many cases

d

be used to determine nuclides. l%- energy

237Np in the resolution

other

alpha-omitting if~ MOO KeV

in giquid

%C!intillmtion

-1o9-

as

coward

to

1S KeV for spectrmetry

surface with

barrier either

(Ietectors. a !la I scintillation 1:0 determine 2s9Np.

--ray detector

or a Ge(Li)

detector (228,

may be used 278 KeV), (about

The

For 23$Np gamma rays typical coaxial Ge(Li)

the

tw]ergyresolution of a

detector

1.0 KeV) is much better such Ge(Li) is 3 to 1S% for the (LEP)

than for NaI (about 20 KeV). detectors relative ray.

efficien:yof NaI dete~tor photon

to a 3 x 3 in. Ge(Li)

1.33-MeV ghave an energy

low-energy

detectors efficiency.

resolution

of 0.S KeV with method for

lower

An o-y coincidence developed the which increased system

determinating

237Np was

selectivity.2s was taken

The resolving time of

coincidence

as 8 x lC-6 sec. to increase the

A radioactivation sensitivity for

method was developfd 237Np.2G5

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

and after A sunssary

neutron of tho

sensitivity

and radioactivation Table for 23.

methods alpha

for determini~g Np is presented in counting is the ~!;t convenient method

In summary,

237Np, and gamma spectrometric methods are preferred for 238Np

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

(>1) (>1] (>IM) . .

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 -

improved with available advanced instrumentatim.

Scurce

Preparation.

Direct

evaporation ig the simplest for counting. is the The thickness

uethod

for preparing for alpha

sample pulse

aliquots height in self

disadvantage of the deposit, particles. (S0 pg/cm2) evaporated homogeneous and bums a suitable evaporated flamed collodion

analysis

which results If a surfactant

absorption

of the alpha

such as tetraettlyleneglycol solution, the NIP solution in a more on heating to is

is added to the aqueous from a film deposit.zcz~ rather than

a drop resu,~ting

The surfactant The diluted e.g. stainless spattering. and coated

polymerizes

up when ignited. counting to dryness plate,

sample steel

is transferred disk,

and slowly munt layer is of

to prevent cooled,

The direct with a thin

to dull

red heat,

solution,

and the Np is counted. has been widely alpha counting.

of

ElectrodePosition sample useful

used to prepare The procedure alpha emitters

high-quality is extremely that need

mounts for precise when samples contain

a mixture

to be resolved.

Electrodepositionresults in excellent sample solutions that evaporate very slowly that or leave contain

mounts fmm organic large large amounts a-nts

of residue of dissolved actinides

and fmm qqueous solids. can be deposited

conditions.

solutions

Np and other electrolytes

from

a vmriety

of

qnd under

sewral

Gravessgg

described

112 -

a semiquantitativemethod

for

depositing

237Np from Li onto Pt.

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

md alcohol from sulfuric, by Palei.20+ deposition by other

saturated hydrochloric,

ammonium chloride.201-2B3 and oxalic of variables elements acid

perchloric, The effect other

has been reported

on the quantitative has been reported

on Np and

actinide Other

authors.:1e52aG but yield sources

methods

which have a lower efficiency include

with

excellent

resolution

vacuum sublimation

and electrohave

spraying.28b-2g1 several

Both electrodeposition These uethods special cell take

and (!lectrospraying a longer including time than a specially high electrode voltage for

disadvantages. and require electrolytic and special

evaporation designed equipment, electrostatic

B.

equipment

for electrodeposition, with a needle

capillary

spraying.zGG

SPECTROPHOTWHRY Although different oxidation states of NF have sharp absorption

bands,

spectrophotometric

analysis

has had liuited Further,

use because alpha containwithin

rmdiometric

procedures

are mme sensitive. spectmphotometer, Generally,

ment is required for the a glove actinides

q

anu opermtion

box is tedious. can be applied oxidation state,

procedures

used for other Np i:~ adjusted is calculated absorption of the to

to the determination. and the concentration coefficient and the

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

absorption bands and molar

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

use for analysis of Np(III) is at 786 mp kecause this band

Beers

Law.

The strongest bands for Np(I\)(960 mp, Law, but they slit can be used with The strongest

723 mp)

do not obey Beers calibration

appropriate band for

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

method for determining

Np in irradiated

by measuring by

the Np(V) band in lM HN03.

adding

The pentavalent
uixture

is produced after for

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

band for Np(VI) :1s at this method, bichromate,

1.23 urn; in

band for measurements Np is oxidized and thm to the

hexavmlent

the acidity at 1.23 urn

is

q djusted

to 1 to 2U.

The qbsorbance

is measured

- 115 -

TABLE24
IMPORTANT ABSORPTION PEAKSOF NEPlUNIltN2g-2s

Np(II1)

Absorption 8and [w) 55P 60~#d

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

a. lM lCIOq. ~1. ~lo,. ~ c. IM HNOJ. d. Obeys8eer*s Law. e. KOH Solution.

- 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

Pu, do not interfere A study on heavy

when present water solutions

in amounts

o:: the Np.

of neptunium region

in wh:.ch numerous

well-defined by

bands were found in the

Waggener.sOO
color cmph?xe8.

1.2 to 1,11 Um is reported

Spectrophotometric the position by some anions are pafi.ially

methods

for Np lack

sensitivity. coefficients tration. complexes used.

Furthermore, are affected

of the band extinction and by the overcome Np concenwhen color are

These disadvantages that

have very high mlar with arsenazo 7-bis(azo-1) III

extinction [1,

coefficients

A uethod

8-dihydrcxynapthalene-3, -2-arsenic acid] complex The color over is

6-disulfonic reported.301-303

acid-2,

benzenn

The intensity III

of the s~:able green al: 665 mu. is constant

of Np(IV] snd arsenazo forms instantaneously, the concentration range

is measured intensity

and its

4 to 6M HN03.

The molar extinction

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.

Np is reduced lirlit of detection

and arsenazo 0.04 vg/ml,

III

and the relative

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.)

Novikolr et aZ. have

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

Fu interferences. The thorin method has also been automated307

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

is that uranyl ions do not interfere.

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

This method requires an extensive purification

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

l-(2-pyridylazo) 111. With PAR,

(PAR), arsenazo

111, and chlorophosphonazo

the molar extinction coefficient is M.3

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

was O.1% (n = 8) applicationof Stromatts method, the prot:ision for 9 mg of Np.

a 31s demo]lstrated coefficient Also, 3uckingham

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 -

Determination the (IV), (V),

of Ozidat ion States.

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)

electrolyticallyreduced to Ce(III) and Np(V); ard [S) Np(V)

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

Step 2 corresponds to Np(IV).

L&termination

of &idation-l?e&ction

Pot.e~tia2.

The potential

for the Np(V)/(VI)

couple was ueasured in sulf~ric, perchloric, and

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

The potential a mercury electrode.

for

was obtained

or pulse

polarographshas been applied to detemine

small

concentrations

- 121 -

of Np+) Slec with

and othurs J* have reported polamgraphy

from

an analytical

method pre-

square-wave
separation

to determine

%@in Pu after

liminary extracted tions with

Pu by 77X extraction.

!tp is Ihack-

froa nitric

the ITA into acid acid

(to

IOM HMI1. ashing

organic

After

sewer41 evapora-

and uet
oxidize

with mixrd nitric asterixl], the final per-

and perchloric chlorate

amine

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

0.S id of IM EDTAis added;

to

solution is adjusted and diluted

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

on the square-wave aliqwt of a standard

polarograph. Np soiutin

Then an accurately prepared in EDTA is

the cell, and the !Wpconcentration in the ori,ginal is calculated from the
EUrA

solution Interference by adding

from the oxidation

increase of chloride

in peak height. ions is decreased

to shift the half-wave potential. the Np peak. of for the reduction than for of the the well defined. EDTAcomplex
of

The patential

is about ions; oxidation

700 mV more negative therefore,

reduction

neptunium

the peak is shifted and is well

away from the anodic T~e authors report

of chloride ions

precision of f2$ and $10% for concentrationrarlges 500 and of 25 ppm, respectively.

122 -

Caucheeler the Xp(lV)-Xp(lll)

irradiated

ut al,**O couplo
fuels

reported
for

a method whi~ch makes use of Np :iIt solutions !ip is reduced

is taksm. An is of

determining

nuclear

qnd 2Xp

targets.

wlactmiyticaliy to Np(lV), and the polarograa

iali~wt

of .

standard

Sp is added to the cell,

was used
Pu,

utd the procethm with a NIp

repeated content

The method

to U,

analyze Fa, !di,

solutions
Cr,

>20 mg/t

coatainigq

and fission

[products, with 8 precision FWmography chemistry

of U,

of~2%. methods were used

at

and other

to coq~re Jenkins

the umd a

?/p, and Pu by Kraus,

aZ.)2*
and

mgraph manual, po q complexes $tudied with

to study

the

nature

stability

of EMA,
wem

Np(II1)

and Np(IV).a

Np(IIl)

and ([V) and

in chloride *

and perchlorate

media by Hiwken

Kritchevsky,8*

Np was included
qctinides
studid

in a review

of

eiectroch,aistry
complexai of

of the Np(XV) were

by Milner.2* polarographically

The sulfate by hsikm.a

E.

TITRATIW
Potenthmetfia.

10- to 100-mg quantities $2S

cf

Np were

detomined

by redox

titration.

CC(IV) iS used to titrste was used to titrate on the required

?/p(v) to N@(VI), to W(V)* fie of sasple potential]

and iron(II) methods if WI

perchlorate

llp(VI)

can be used successively is present (to give the

(it

same ~lliquot

ceri~: oxidation

and chloride

ion is absent

would be oxidi:~ed

to chlorine).

123 -

..--!...

.,

.!-...

.. . .

.. . .

. . . . .

Stoppered

weight

burets

were used for

adding

reagents,

and a Relative for

plmtinu-cal~l
standmd deviations

~ystem was used to detect for a single for eerie

the end points. were 0.15#

determination titers.

fezmus

titers and 0.S9S

Colnpbttiu

Tftzution.

Np(IV) xylenol

is titrated

with

a solution The color concentrations. Np(IV) is Fe3+, large

of EDTAat pH 1.3 to 2.0 with

orsngw as in.iicator. and the at equal

i:~

reactim changas The error

produced

of Np(IV) with from bright

fordetemining

EDTA is stoichl~tric to light

1 to 4 q

rose

yellofNp

molar

1 to 2%.

in 0.01
Th+,

to 0.05MHC1 with hydroxyl,smine

and q scorbic

reductant. Reasonably

Zrh+, -Unts Cdz,

Pu+,

acid

interfere.
rare

of alkali, CO*+, Cr+,

alkaline-earth, Mn2+, Ni2+,

earth
do

elements,

Zn2+,

and U022+

not interfere.32G analytical results

(%Wopotentirntric. chemistry done in molten

There salts

hJ~ been little

, and so c~r the only useful methods. LiC1-KCl eutectic

have been obtained dete-ined SOOC with

from electmanalytical in molten of t4S.327

31p(IV] was at 400 to

quantitatively an qccuracy

F.

EMISS1(M

SPECTROMETRY

Np has a line-rich lineS at 4~54.5, 4098.8,

emission 3999.5,

spectra

with the more-sensitive Other methods the analyses

and 3829 ;1.32S329 determination

are more useful spectrochemical of imprity spectral carrier

for quantitative method,

of Np than for

which is generally To prevent

used only

elements. lines

interferenceby the

numerous
or

of Np, a chemical method with

sepamtion is usually made, galliw sesquioxide is used.

the

distillation

- 124 -

A quantitative

method

for determinaticw

of impurities

in Np

is reported a modification

by Wheat 232 (Procedure23, page 200). of one reported by Ko for Pui.s30

The method is The neptunium

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

The residue to dr~ess,

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

relatively free from other ions, alpha counting or some other

method is usually

more rapid and offers less health hazard. A

number of Np compounds have low solubilities in aqueous sc~lution; however, indefinite stoichiometryor necessity for calcination
to

the oxide limits the usefulness of direct gravimetric

determination. Often the small quantity orlow concentrationof neptunium precludes the use of gravimeery.
- 125 -

ffycbwidr. acid solution oxide.

Np(IV)

is cqletoly

precipitated

from minaral hydroxida that fores 3%. or is

by Na, K, or MibOH as the hydrated The broun-green but asily is q gelatinous redissalvd solid

hydrous difficult volubility i:~ green; hydroxide

to filter

in qcids.

in lM NaNOl - lM NaOH is ~0.1 rig/L. it is somewha~ mora soluble

Np(VI) is

!Up(V] %ydruxid.

in a sodiuw nitrate-sodiuu
qs

solution.

precipitated

dark scid

brown solution.) ac:~d solution

(NH~)2NpaOt~HaOwith Flwrid%a. as green readily boric hydrated

excess

NH*OHfrom minaral

Np(IV)

is precipitated excess

f;rom mineral iii:.

NpFh by adding

The compound dissolves ion, such as AIJ+ or

in rewgents which complex acid.

fluoridl~

Wlwn K or NH~F in usad as tlh(l precipitant, tha green

double salt KBIp2F3or NHklUpFs is produced. Pertmide,~. large excess Purple Np(lV) peroxide iS precipitated when a

of H202 is added to a strongly because peroxide

acidic solution of rapidly reduces in dilute

Nip(IV),, NP(V), or Np(V1), Np to the tetravalent mineral

i~ion

state.

Reduction always

is much slower irtcorporates

acid.

Np(lV) peroxide

SOW! of the

into the crystal and may have diffcrent crystalline forms Np iS

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

Llxalatefl. from dilute precipitation acid

is prl~cipitated quantitative

Because

is not attained

for Np(V) Jr Np(\I]P

a reducing

- 126 -

q gent,

such as ascorbic
A

acid,

is usul to ensure complete reduction precipitate is produced

and N@12HC20~

to Np(Iv]. under

granular,

easily-filtered

controlled

conditions.o

(Nli~)4Np(C20~)k

have qlso been precipitated

Ioti.

from P@(IV) and Np(V) solution. icxiate potassium is precipitated iodate.s KNp02C03, is acid solution
from

Light tan Np(IV) by adding . excess

dilute

mineral

acid

Cdwnata produced

The double carbonate of Np(V), potassium bicarbonate

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

in bicarbonate. to produce the

tan double Aaotute.

NaNp02(C2H~02)~, reflected light.

by transmitted

and pale with

green KBrOs at

by

Np is oxidized

in dilute

90*C to Npo22+. an equal voltme

Sodium neptunylacetate

is precipitated

by adding

of 4M NaNOS - 4M NaCzHS02 solution.38 Np(IV) di(monohydrogenphosphate) hydrate

%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

in paper chromatography. 331 The tests we::emade on Whatman No. 1

- 127 -

paper for

which was treated 12 hours with

to remove

with
traces

2M HC1 in descending of Fe, Mg, and C=, 24-hour washings

chromatography

The paper

WBS

treated

two successive uater. sensitivity tests with

sy migration of these alpha very of less

with emitters

twice-distilled and the high sensitive

Because

of hazamis

of radioactive an identification

measurement, limit

spot

than

1 ug of actinide and ultraviolet reagent.

were selected. light for both

Observations acidic and basic

were made in white mclia dry; with then each ~nia

First the acidic media was allowed A standafi scale

to

was added and evaporated.

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

of Pu and Np; kojic

only with

The oxidation states of Np and Pu were characterized color reactions on chromatograms and electrclpherograms.

- 128 -

The tetravalent arsenazo-1, the hexavalent I.

states and thorin-I; state.

give

characteristic

colors

with

alizarin,

however,

diphenylcarbaxide

was used for

MASS SPECTRCB4ETRY Subnanogram quantities of 237Np were determined with a mass

spectrometerby Landrum, et al.sgz The instrumentwas a doublefocusing, 60-degree source sector type, with a 12-inch radius. The

chamber contained

a tantalum and a rhenium

filament filament

(from which the (on which gaseous the ionized Np atoms

sample was volatilized)

species were ionized]. After

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

neutron activation, and the sensitivity is at least ten

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

produced for elements

- 129 -

actinides considerable s~les Mixtures 1:1:1;

to be analyzed precision

by X-ray fluorescenc,~ and accuracy. by the intenal Either

spectrometry .~olid er liquid technique. as high as

with

can be analyzed

stsnd,mi at ra:ios

of U, Np, and I% were analyzed results were comparable

to standard

counting.

U, Np, and at ratios However, for the at

Pu in any combination as high ratios element

as

of two elements seriously

were ani~lyzed accuracy.

1:8 without

affecting

of 1:10, present

low results at lower lines

of 5 to 7% were ojtained concentration. with The principal atomic

L series

X-ray emission 96 are given

of elements

nwnbers 32 through X-ray

by Kofocxi.s35 to determine

Novikov et CZZ.36 used microgram containing

fluorescence solutions

amounts of Np in pme Pu. standard including The sensitivity error s~ple was

or in solutions

0.2 to 0.3 pg ofNp. 1 Dg Np was 5%, ~d required

The relative the analysis,

in determining preparation, for

30 to 40 minutes.

The Kal and Kaz X-ray energies by Nelson, et al.337

Np, PUB and Am were measured

K.

NEUTRON ACTIVATION Neutron activation

The

was used to determin~!

subnanogram with

quantities Np

of

237NP.332

unknown sample was i~adiated and comparable flux. weight

another same

sample avemge

of known Np content time-integrated

in the

neutron

After

irradiation,

- 130 -

the 23BNp was determined

radiochemical with separation of

by gamma spec:rometry. methods were ?Ised.

Conventional Isotopic dilution

mass quantities

237Np ser~ed t,)determine chemical

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

preparation, and gamma counting3bofa? analyses. measured

Characteristic isomer st,ift ranges have bem fcr

several valence states of Np using l&sbaue? resonance

59.54-keV gamma ray of 237t-ip. They

of the

exteld from about

-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

3kla significant contributions.

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

intestinalabsorption, and short-term retention of

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

due to the of its

low specific Table

activity of 237!Jp and the 25 lists body burdens

SF

low energy

gamma radiation.

and maximum permissible concentrationsof

occupational exposure.b In and 23Sp for continuotis

- 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

TABLE 25 HEALTH HAZARD OATA FOR NEPTUNIUM [SOTOPE:S3

Isotope
2sNp (s01.:)

Organ
Bone

Max Permissible Body Burden (uC:~L, 0.06 0.1

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

9 x 10-b 4 x 10-3 30 40 70 100 100 200 300 Soo 4 x 103

;! x 10- 8 x 10-7 41x 10-6 7 x 10-6 ]*-S 2! x 10-5 7 x 10-7 2 x 10-6

- 133 -

x. A. INTRODUCTION

COLLECTION OF PROCWLJRE!i

The procedures o Procedures exchange, these

uethods

are divided

into

three

cal;egories: chromatography, or :wme combination swnples. pulse dilution. ion of

for extraction, and carrier with highly

extraction radioactive (alpha isotopic

precipitation counting or possibly

n.athods utilize

Most of these analysis), The

alpha

height

gaxna

spectroscopy,

method of determination e o Procedures

is not detailed

for all. procedures.

used for environmentaland biological samples.

Miscellaneous procedures for quantitativedetermination, including absorption spectrometryof color complexes, coulometry, and gamma spectrometry.

B.

1.ISTING OF CONTENTS Author Moore*e Title cr Method . .

Separation c~ i4p b:yTTA *

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

Determinationof Np in Samples of U and Fission Products 161

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*

An Analytical Method far 237Np Usjng Anion ExchaLnge 167

Nelson et 220223

Separati.cn U, Np, and of Pu (Jsing Anion Exchange! ~69

12

Holloway et aZ.*2 !3eparaticn Zr, Np, amd of Nb Using Ar,ionExchange 171

13

Jackson et al,kg

Separatism of Np and Pu by Anion Exchange 173

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

Radiochemjcal the Separation

ADounts of

Reactor 18 8utler35~

Effluent

184

Detemina:ion Urine

186

~pe 19

III Granadelsz Dete2minacion by G~ of 2B7Np 189 Ray Spectrometry

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

Microvolmetric a2.32G metric EDTA Mdwd

22

Novikov et al. B53

Photometric Complex

of Np as the Peroxide

23

Uheat 2 2

Separatim of Impurities

Spectrographic

24

Ermoloev

et aZ.30s

Photometric

of Np as the X~lenol Orange Co~lex

- 136 -

Procedure 2s

Author Stromatt31

.Title or Method Analysis for Np by Controlled Potential] Coulcmetry 206

- 137 -

Procedure

1.

Separation of Np by HA F. L. Fbore*o

Extraction

i?utl~~

of Mt?tlwd from fission products, U, Pu, transplutonium into an aliquot is

Np is separated elements,

and nonradioactive

elements After

by extraction separal:ion,

thenoyltrifluoroacetone suitably counting prepared of 23qNp.

(C.F.

(TTA). for either

alpha

counting

of 237Np or gamma

Reagent8
q q q

Chemica28)

HC1,

lM

HN03, 10M Hydroxylamine Dissolve hydrochloride (NH20HHC1) solution, v5M. water

69.5 g of reagent in 200 ml of distilled for dissolution. 40 g of reagent-grade Store

and warm if necessary

q

FeCl , w2M. tetrahydrate glass

Dissolve

FeC12*4Hz0 in a dark

in 100 ml of 0.2M H(H.

stoppered bottle.

2-Thenoyltrifluoroacetone-xylene;olution, : W.SM. Dissolve grade 111 g of compound in one liter of reagentxylene.

E@@n3ent
q q q q q q

Extraction Hot place Micropipets Stainless Counting

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)

l%etreatment If interferencesmay be present in salution tracer, Np is adjusted with the Np

to Np(IV) and carried on ~1ug of La pre-

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

in a few drops :Frm

of 2M A1(NOS)S HNOI
iB

and dilute

While the extraction of Np(IV)

usually very effective, HC1 should because there is a greater tendency

be used whenever to form extractable

possible Fe(III)

ion in the HNOSsystem. It is desirable chemistty is employed. to

u easure

the chemicrnl yield is useful

if

wch

A 237Np spike

for determining 237Np yield.

23gNp recovery; Procedure

239Np uay be used for dete:nuining

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

remove the aqueous

6.

Mash the organic IM HCl for 3 nin. discard

the

phase

by mixing

k)ith an equal

volume of

AI1ow the phases wash. phase

to s,~patte and

aqueous

T t.

Strip equal strip the

the Np from the organic

by mixing

with an

volume of 1CB4 HIWs foL 2 min., is too high last traces in g~ activity

(If the aqueous for alpha measurement,

of radioactive of the

Zr and Pa may be removed 10M HNOs strip solution

by a S qin re-extraction with an equal Ordinarily, negligible extract

Fe is a

volume of ITA. the small amount of Fe in the ITA causes in counting, and the plate. by TTA If

self

absorption

is mounted directly problem , excellent the Np into aliquot for

on the counting separation

is attained

stripping 8. A suitable strip alpha

10M HNOs. or the 10M HNOS either 39Np.

of the ITA extr;lct by conventional

is prepared counting

lrnethods for for

237Np or gaiuna ,:ountinlg

- 140 -

Procedure

2.

Separation of R. S. Dorsett15

by llA

Extraction

OutZine

ofllethod of Pu, U, fission into products, thenoyltrifluorol-he analysis

Np is determined in the presence and other acetone alpha-emitting (TTA) followed nuclides by alpha

by extraction counting

of- the TTA.

consists of three parts:

(1) the pre-extractionstep in which

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

of the TTA extract. Np is stripped

cation is required, the

oxidation state are adjusted, and a second

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)?

coefficient of variation of 2% is solutions.

Reagenta
q

Hydroxylamine by dissolving to one liter.

hydrochloride 69.5 g of C.P.

(NH20HoHC1), lM, is prepared grade compound and diluting

(NaN02),

lM, is prepared

by dissolving

69 g of C.P.

grade

compaund and diluting s

to one litl~r. 0.5M, is prepared with by

2-Thenoyltrifluoroacetone-xylene, dissolving C. P. xylene.

111 g of the compound in one liter

- 141 -

Ferrous solving solution.

sulfamate iron

[Fe(NH2SO~)2], The solution

2M, is prepared of sulfamic is filtered acid after

by diswith dis-

powder in an excess

minimum heating.

Aluminum nitrate [Al(NOg)s), solving one liter. 750 g of C.P. grade

2M, is prepared

by disto

coml)ound and diluting

(tlNOs) nitric from C.P.

acid

solutions

arl? prepared

as required

grade

stock. 0.5 mg/ml, LS preFlared by dissolving

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

Micropipets Stainless Counting steel plate counting

heater

plate:;

Meeker burner
Asbestos

s
q

board

Sample carrier Alpha proportional counter Alpha pulse height analyser

o o

Pretreatment FZuotide present La(OH)J. in the method. solution, When it is not knc}tin what impurities
Np(Pu)

are with

can be caxrier precipitated in HNos, and La is

The hydroxide

is dissolved - 142 -

reprecipitated

as the fluoride.

The fluoride precipitate con-

taining the actinides and lanthanidesis dissolved in A1(NOS)3

and dilute HN03, and this solution

is extra:ted with 77A.

@ in Mbut~Zpho@uzte

(TBP).

If Np :.s present

in TBP or

other organic extractants, it is stripped w:.thdilute HN03(%0.1M)

and then analyzed by the procedure.

Sepamtion

ofNp

and U.

Acid control is very important for

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

of U content of the final lTA

extract.

.%oaedme 1. Pipet 103 to 104 dis/min alpha of 29;Np into centrifuge cone.
7

a lS-ml

.. Add sufficient water or HN03 so that the acid is lM. Mix.

at the end of Step 3

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.

Allow the phases phase phase, and discard

remove the aqueous mixer.

Add 4 ml of lM HIXls to the organic

and mix for

2 min in the vortex - 143 -

6.

If the alpha proceed proceed

activity

due to F% and U is <103 dis/min, If the alpha activity is >lOs,

to Step 9. to Step 7.
aqueous

7.

Remove the

phase

from Step S and discard organic phase,

it.

Add 1 ml of 8M HW3 to the

and mix for

5 min in the vortex 8. Discard the organic

uixer.

phase. plate

Repe~t~Steps heater, steel heat

2 through

5.

9. WITI on the counting Id place heater. 10. Pipet an aliquot twice a clean

to 175 to 190C, plate on the

stainless

counting

from the organi.: with xylene, until

phase

that

contains Rinse to the

%103 dis/min the pipet plate. 11.

Heat the

Np, and add it

droptiise dry.

to the plate. rinses

and add both

Heat the plate

plate

over

a Meeker hurler Place the :~late

flame until

the plate

is a dull board 12.

red color.

on an asbestos

to cool. is cool, add 1 dr.)p of coilodion to dry several to cover

minutes

Uhen the plate the surface.

before
counting.

Allow the plate

- 144 -

Procedure

3.

Detenninatlon of 23gNp fn Sanples U, Pu, and Fission Products

H. L.

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,

If the sample is a dissolved U foil, HN03 must be added

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

La cnrrier: 5 mg La/ml, added as La0J0J)3.

6H20

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:

237Np standard solution: S,000 ta 10,000 in 2 to 4M HC1 or HN03 - 145 -

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

1:1 H20 and concentrated

HI-HC1: 1 ml 47% HI + 9 ml concentratedHC1

HF-HN03:

equal

parts

by volume of 2M solutions

NH20H*HC1: SM (or saturated) KMnOk: 10% solution

NHbOH: Dowex

concentrated 1-X1O anion exchange resin:

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

erlenmeyer flask, and then

in the samrle. Wash down the

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

The resin is supplied by the

Calif., who purify and grade

Bio-Rad Laboratories, Richmond, the resins manufactured by the

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.

volume of solution shou:.d 5 to 10 ml. be

(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,

Dissolve the precipitate by slu:rrying with 3 drops (Ignore

of saturated H3B03 and adding 3 drops of concentrated HC1.

any small residue.) Add 3 ml of 2M HC1 and precipitate La(OH)g by adding about discard with the
1 ml of concentratedNH40H.

Centrifuge, t)y boiling

and it briefly

supemate. milliliters

Wash the precipitate of H20. Centrifuge

several

and discard the

supernate. step 5. Dissolve the precipitate in about 5 ml of 2M HC1.

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

thwn 0.2 ml, repeat the

hydroxide and fluoride precipitationsuntil the volume of LaF9 precipitate does not exceed 0.2 ml.

- 147 -

Step saturated and allow

6.

Dissolve

the

fluoride

precipitate

in 1 drclp each c:f of KMn(lq,

H3803 and concentrated to stand for S min.

HNOg. Add 10 drops Add 2 drops

of HF, and allow the

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.

Add 2 drops of La carrier to the sclution, stir.

centrifuge, and transfer the supernate to :1clean centrifuge tube. Wash the
precipitate with

1 ml of 1{1:-HN03, the add

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.

Add 5 drops of NH20H-HC1 ard 2 drops of Sr hold-

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.

Dissolve the precipitatewith 1 drop of saturated

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

up the solution in a transfer pipet and evaporate

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

Outline After evaporation.

of Method the sample is dissolved, the vo~,ume is reduced by

Np and other hydroxides are precipitatedwith SO%

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-

tracer. to about bath,

Add W2 mg of La3+ carrier and boil 10 ml. centrifuge, the sclution until Transfer

and 2 ml S5% HI the volume has been Add suffiHeat

(no inhibitor),

to a 40-ml cone.
may be present.

SO%NaOH to dissolve any Al that and discard

in a water

the

supematant

10 ml of 10M NaOH. Wash the precipitate

Again heat, thoroughly

centrifuge, with centrifuge, 3. Dissolve

and decant. and decant. the precipitate

30 ml of H20 (to remove most of the Na+ salts),

in 10 ml of concentrated

HC1.

Add 2 drops
4.

of 55% HI (no inhibitor). the solution with

HC1

Cool and saturate salts the column, precipitate, solution

gas.

(If

white Pass

centrifuge

them and decant.)

through

a Dowex l-X8, the effluent. effluent

50 to 100 mesh If 23tPu is to the time of Np-Pu

6 ma I.D.

by 11 cm, pretreated with concentrated Discard and note

HC1 - O.SM HI. be measured, separation.

5.

save the

Wash the column with

15 ml of IOM HCl - 0.5M HI, and

collect the wash with the effluent.

6.

Elute the Np with allow eluate a minute

three

S-ml portions elutions. flask.

of 5M HC1, and Collect the

or so between

in a 125-ml Erlenmeyer HI , and boil lM HC1.

7.

Add 2 drops 15 ml.

to ne~.r drfless.

Transfer

to

a 40-ml cone with

Add lM HCl to uake approximately

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.

toluene, the layer

or xylene, layers into with by a

,Soparate the organic the extraction

5 ml of

Combine I:heorganic fractions.

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

Back-extract of 9M HC1 for and transfer extraction

aqueous phases.

the Np by equilibrating 10 min. the aqueous with Separate the to a clean

as before, Combine the

1 ml of 9M HC1 for

11.

To the Discard repeat step

combined

aqueous

phases, layer).

add 2 drops Equilibrate

of 6% for 30 sec. This

cupferron

and 5 ml of CHC13. the CHC13 (lower

Add S ml of CHC13 and Nb activity. flask, (CA~ION: until add 1 ml The if too

the extraction. is designed the

Again discard the CHCIZ.

to remove trou~lesome

12. Transfer

solution

to a 125-:nl Erlwuneyer fo:nnic acid acid.

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

Warm th(g solution oxid:.zes

the HN03 has

U(VI) and reduces

be >1OM, use HCl gas if x 5 cm column,

50 to 100 mesh, the effluent

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.

Examine on a NaI detector

the sample

for ganm pure,

is radiochemically

Electroplating 8oil saturated

acidity

the solution

from Step

10 to near

dryness.

Add 1 ml of and adjust the

ethyl NHtiCl and one drop of u

with
NH40H and

red indicator,

lM HC1 so that

one drop of lM HCl turns Transfer the

solution

red.

(Volume should cell cathode. fitted

be 3 to 4 ml,] with a Pt hire

solution

to an electroplating diameter
the

anode and a l-in.1.5 amps through

Pt disc for

Pass approximately

cell

15 min. NHkOHto the cell for another while electrolysis

Remove

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

the addition cell,

Dismantle alpha count

flame the yield.

for chemical

Gamma and beta

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

and 23gNp, showed no activities Other than 23ehp

- 1s3

2. 3.

10 to 12 hours The yield for

is required this procedure

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-

parated from Pu by 7TA extraction ve polarograph, Retzgenta

q q q q

Distilled

water gradt (NFzOHOHC1)solution, Dissolve 5M

HN09, analytical-reagent Hydroxyamine lTA solution, filter, hydrochloride

0.5M in xylene: with (FeCIZ) Dissolve xylene

28 g of 2xylene,

thenoyltrifluoroacetone and dilute chloride

(lTA) in 200 ml of pure to 250 ml.

q q

Ferrous

EDTA solution: tetraacetate with

37 g of discldiu.m ethylenediaminewater, adjust to pH 7 and dilllte to 100 ml.

(EDTA) in distilllsd

ananonia solution,

Piwoduw

1. 2.

Weigh %300 mg of Pu uetal Add S ml of distilled 1(M Hcl.

and 2 ul of

accur~.tely. and then subsides, slowly

solution.

water

add 0.5 ml of

When the reaction

add 1 ml of ICR14 Cl H

5M NH20H*HCIand warm the

3.

Dilute allow

to 10 ml with

distilled
state

writer,

mdd 2S0 mg of FeC12,

5 min for oxidation quantitatively Stir

djustmnt.

4.

Transfer

to an extracticm vessel, and add for 10 minutes, allow the phases

5 ul of O.SMTlA.

to separate, and remove the organic phase.

1s5 -

5.

Repeat

the

extraction

with phases

S ml of (),SM TTA. in the extraction vessel, add

15. Combine the organic

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.

Heat until solid perchlorates remain but do not

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.

Determination of Np in Sample Containing Products, U, and Other Actinfdes A. Schneiderlgk

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

5M HN03 3M [Ferrous Sulfamate], Fe[NH2SO:)2 5.5M [hydrazine], N2H4 [TIOA) in xylene

.
q

.
q q q

10 Vol% tri-isooctylamine lM HCl

5M [hydroxylaminehydrochloride] (NHzOH=HC1) 0.5M TTA in xylene

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

1 drop of 5.5M N2H4.

Stir 4.

and allow

to stand

for

.5 min at room temperature. for 3 min to

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.

the aq~eous. original vial

to

s.

Transfer clean allow

phase.

from the

vial

1.5 ml of SM ~03,
Stir

3 drops
the

of

Fe@H2S03)2,

and 1 drop of N:H4. to separate,

for two minutes,

aqueous

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

2.0 ml of the aqueous Stir and let and heat stand

at 65C

HC1

phase 3 min.

to a of Remove

vial.

Add 3 drops

of 5M NH20HHC1and 3 drops for for 3 min. Stir for

2M Fe(NH2SOs]z. from the bath, 8.

Add 1.0 ml of 0.5M ITA in xylene. a complete organic

uounted

4 min to give The

emulsion. alpha

Allow the phases

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

ion does not anions

The deleterious

is circumventl:d Al ion.

the sample

or by adding

- 159 -

!,

For U-tree samples,

the combined system yields 96 t2%

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

(Cc, Ru, Nb,

1 x 106 and :aPu separation

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

U ond Fission Elliott, and

W. J. Maeck G. l.. Booman, E. ReinJ

Introduction This procedure determination methyl isobutyl describes a method for separation and using

of Np in solutions ketone

of U and fission

products

and thenoyltrifluorom:etone state

(TTA) e,xtractants.

Np is oxidized

to the hexavalent

and qllantitmtively xtracted e

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

from the ketone

extracted

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,

add 13S ml of conccrltrated hydroxide reagent,

Md SO nii of 10% is dissolked.

itetrapropylanmnonium to one liter

with water. IM HI - C,,5M NH@HHCl and

Reducing-strip

solution:

().25M FeCIZ solution. 0,>2SMKMn04 Methyl isobutyl ketone (),5M lTAin xylene Ethylenediamine

161 -

Pmuedure 1,, Add 6 ad of A1(N03)s salting :}f~lution to a tube containing

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

and mix for

3 minutes.

Remove 2 ml of the organic for 10 uin and allow

ph~a:se, and transf(m to another to separate.

tube containing 4 ml of the rmlucing strip solution. MiX the phase~

5,,

Transfer funnel; 10 min.

3 ml of the aqueous

lp!lase tcl a 30-ml separator vigorously for

add 3 ml of 0.5M TTA, md stir

6.

Let the phases separate, and discard the aqueous minutes,

phase.

Add 3 ml of reducing-stripsol~tion, and scrub far 5

7.

Remove an aliquot counting plate

of the organic

phase,

and dry it

on a

under

a heat lamp. Cover the residue with

2 to 3 drops of ethylenediamine,evaporate to dryness, ignite, and count.

1,

Extraction isobutyl extraction Ru and Zr, follow

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

very good separation

The extraction Np, are

of U and Pu is separated

cO.1 and 0.01%,

by >10. counter is used for gross analyzer counting, system is

2.

An alpha used

scintillation height

and a Frisch-grid for pulse

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

extraction and activation

chr~tographic prtiucts after

separaneutron with

tion

Of sNp from fisAion The system It

irradiation. lTA-xylene. easily

is Poropak-Q that

resin

impregnated

is suggested with extraction

radioactive chromatography

samplles are more than with lTA

analyzed

extraction. ReagentB
q q q q q q

Poropak-Q

resin,

100 to 120 mesh (~mall amount of n-pentane added)

0.4PI ITA in xylene 2M W1 lM FeC12 3M NHzOHHC1 10M HIW3s

P2wmchlw? 1. Dissolve HCl . 2. Md 3 ml of freshly

ix, NH20HoHC1s

sample

in 2M WI or convext

to c~hloride

with

prepared let stand

lM FeC:lZ and 4 ul of 3M for 1!, min. (S cm long and lTA-xylene

and

3. Transfer the adjusted

solution to a column
Q impregnated with

0.6 cm I.D.) of Poropak l/(-2.min)C nt W1 s

- 163 -

4.

When the feed has passed 2 ul of lM HCl and then Discard the effluents.

througlh

the column,

wlzsh with water.

a few dr~~ps of distilled

5. 6.

Pass

S ml of 10M HNOSthrough

tlw! column to strip the

the Np.

Count the HN03 solution after nected separation with to a S12-channel

containiltg a 3 x 3 in pulse-he:!ght

23gNp immediately detector conmd evaluate

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

of 1 pg of U was determined at a thermal neutron flux

irradiation, with a

of 2 IC 10]3 n/cm2-sec
WilUh

cooling period of K!Ohours.

a longer imadiation,

a detection limit of 0.S ug is sllggested.

- 164 -

Procedure

9.

Separation of Phase Partition

U,

Np, Pu, and Am by Reversed Chranatogruphy

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

(diatomaceous and aqueous Reagente

q

H?#lg solutions and MateriaL3 Super-Cel tributyl

actinidos.

Hyflo Purified HN03

q q q q q

phosphate

(TBF)

Sodium bichromate Dichloro-dimethylsilane Glass column

solution

[NazCrzOT]

Rwceduw 1.
Add Na2CrzOT to

1 to 2M HNOs containing five hours t~ yield

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.

to remove any air

volume per

(not greater

than

1/10 of the total Hyflo Super-Ccl)

column volume and containing species

a ma(imum c,f 1 mg TBP-

100 mg of silaned

l/(min-cn2). at a flow of 0.4 to 0.8 u

- 16S -

4.

Wash the columm with Am(III), Cr(VI),

1.7M H?U)3to remove (in order)

and Pu(VI). switch to 1.7M HNOSI O.lM NzH4 immediately,

s.

After wash.

Pu(VI)

elution,

(Np 1s reduced

to Np[V) and elutes

and U(VI) is remved.)

Nota

If U, Np, and Pu are present The feed NP(IV), The order is adjusted 0.7M HNO, -

, no oxidation
0.02M

step
to

is required. yield Pu(III), is used.

Fe(S03NH2):1

and UCVI), and the of elution

same composition Np(IV),

wash !Jolution and U(VI).

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

by gaama spectrometry. yield corrections

is :;piked with onto a small

to permit

colum

of Oowex l-X4

(100 to 200 mesh) resin After

from 8M HIW13 containing washing with

and

Fe(NH2SO~)2 and sem.icarbazide. volumes

Np is

30 to 40 column
the

of 4.5M HN03 containing with dilute

Fe(NH2SOy)Z

semicarbazide,

eluted

HNOs containing

0, 00SM Ce(SO~)z, factor

Np

recovery

is @5# with factors

a Pu decontamination

of 5 x 10. fission products feed

Decontamination are all does not >104.

from U, Am, Cm, and gross

Uranium at concentrations The Pu decontamination the HNOgwash with

up to 180 g/1 in the factcm

interfere.

can be increased

10 to 100 by following
Np

12M HC1. - O.lM NH*1. The uethod is appli-

is then eluted with 6.5M HCI - 0.004M HF. to samples Reagenta

q q

cable

containing

high

salt

COnCentratjLOnS.

(C.P.

Chmn%a28) HNOs

Concentrated

w2M Fe(SOsNHz)z Semicarbazide 2agNp tracer

s
q

MtZte2%Uz8
q q

?~~wextf

1.x4,

1oo-2OO mesh

Glass

column,

0.3 cm x 7 cm wit!l 10-ml reservoir - 167 -

Counting equip-n t

PJwf?ed3uw 1. Adjust HFM33.

2.

an aliquot

of sample

to @N HNOs Mith concentrated

Add an equal semicarbazide

volli .e of 8M HNOS - 0.02 Fe[NHzSOq)z - 0.2M and mix.

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

1S to 20 ml of 4.SM HNOS - O.IM semicarbazide - O.OIM

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.

eluate in a 2-ml volumet~ic flask.

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,

of U, Np, and Pu Us-lngAnIon Exchan e D, C, Michelson, qnd J. H. Holloway ?2,

GutZine of Method
This U, Np,

uethod

utilizes

anion

exchange

.n ml

for

separating alkali

and Pu from ~m-adsorbable

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

of the uranides in either

can occur

the +4 or +6 oxidation In this pr,>cedurm,

in the +3 or +5 states. Np and Pu are reduced sorbed

U is sorbed state.

+6, while selectively remain

in the +4 oxidation and elut:d, eluted while

to PuIIII)

UG+ and Np+ portions

sorbed.

The latter

are then

in separate

with HCl - HF uixtures.

Reagenta
q q q q

(C.P.

ChmicaZe)

9M HCl 9M HCl 4M HCl 0.05M NH~I

O.lMHF

0.5MHC1 - lMHF

Matefia2a
q q

Dowex

1-X1O, -400 uesh anion 0.6 cm I.D.

resin with heating

Column, device.

and 12 cm in length,

q q

Resin Plastic

bed, test

0.28 cmz x 3 cm long. tubes

- 169 -

..

e e

Teflon evaporating dishes Pl!astic transfer pipettes

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

bed with 3 colum~ volumes of 9M HCI.

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,

Wash bcd with 3 column volumes cf 0.5M HCl - IM HF (U fraction].

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.

Separation of Zr, Np, and Nb UslngAnion Exchange J. H. Holloway and F. Nelson224

Outline This

of Method

procedure is used to separate trace mounts of Np and It makes use of the fact that Zr(IV)

Nb from micro-amountsof Zr.

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

6MiHC1-lMHF-C12 6~~HC~ - 1~1HF 0.5MHC1 - 1.OM tiF 4M HN03 - lM HC1 - 0.2M HF

Matetiah e o Jlowex 1-XIO,

-400

mesh anicw resin

Column, 0.9 cm I.D. x 12 cm ir length containing 2 ml of resin

e o o a

Teflon evaporating dishes Plastic transfer pipettes Plastic test tubes Chlorine gas

Prccedwe 1, Dissolve the sample, and evapcnate it to near dryness.

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

to the column. (U ml) of 6M HCI the bed. at W.8 cm/min.

Wash the bed with lMHF - Clz. (Control When the

Then

2 column volumes pass the air pressure

sample through wash ~ith

the flow with

sample has passed,

an additional

3.5 column volumes 6. Wash with Np. 7. Wash with to elute 8. Regenerate

of 6M HCl - lM HF - Clz (Zr fraction). of O.SM HC1 - lM HF to elute

3 column volumes

3 column volumes Mb. with

of 4M FNOS - lM HCl - 0.2M HF

3 column volumes

of 6M HCl - IM HF - Clz.

The total time for the column operation is k30min.

-. 172

Procedure 13.

N.

Separation of Np and Pu by AnIon Exchange Jackson and J, F. Short34g

OAtZine of Method This and Np. procedure describes separation of macro umounts of W

It is based on the fact that Pu(III) is not sorbed on

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

purification of 2.3 g of Np237 from approximately 50 mg

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

column 20 cm long and

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

was found in a drop collected

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

this stage. Some 6-Y :m:tivity was detected

wool at the top of the resin cf}lumn and was assumed the daughter of Np237.

- 174 -

,,.,

Procedure

14.

!Separatfon

of

Np and Pu by (hltfon qnd L.

Exchange

V. t). Zagrai Outline

Np(IV9

i.

Se14c1wMcov29

of Method
and Pu(III)
q re

adsorbed qf~er

on tho

cation

resin

KUl or

KU2 from 0.2SM }Kl solution water :eqeratures.

reduction with

with

SOz at boiling and Pu stripped

!#p is eluted

0.0i91HF,

with 0.5M HF.

P2%w31iu2w

1. To 6 tc)8 al
&nd Pu,

C 9.2SN HCl containl,rg the pleyfg!ass

1 to 2 ml of

Dg mounts

c~f Np
x

add a~t half of the resir in the hydrogen fom to fill

and

required !90 2. Pass

cc)]water.

(1 IUSdiameter

high]

S(3Z gas through the solution tigorouBly for 1S to solutions to cool

to the

,20rein, uhile the 3. Allou

ltransfer the top

heatinl

on a boiling

water
mnd Plug

bath.

the

solution
the resin

to room t~rature,
CO]W

with

a pipette.

of the CO1throug% the

with cotton,
CO1-.

s.nd pass

the remaining

solution

4.

Wash the resin Is!i of H20.

with

10 ql of 0.2S PI WI,

follouedl

by 10

5*

IEIute the 40 to 60B1

Np into

s Pt dish

or a *7eflon

beaker

with

of 0.02M HF. 4 to S qi of ().5#1 HF.

6.

iElute the Pu with

- )75 -

Procedure

15.

Separation U and the Sulfate

and Radfochemfcal Iletermfnatfon of Transuranfu Elesmts Usfmg 8arfm

c. w. slll~23012*,125
Intrv&uth Large trivalent and tetravalent
Ea!50t

ions

~re

precipitated

with

uhile mnomlent
procedure outlines

and diwlent the separation

cations are not

precipitated.

This
el-ts

of U and tronsuranium

both from other

of the

elements qnd froa emch other. The

hexavslent state
q re

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

lpb spectmametry. for q

Concentrated C.!P. Kasm

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 -

Prood4r6t 1. Add 3 g of anhydrous 6 drops of 0.45~

solution a 2S0-B1 solution containing Erlenmeyer of

KzSO~ 2 ml of concentrated My
8aC1202H2C) the elements (S /rng of to em) to

HzSO*, ml
the in

each of concentrated

mlkd HCICI~, and 2.00

be precipitated

flask there

md
is

evapo]ate
quc!;tion

until about

fumes

of

HzSO*

appear.

(If

any

removal

of organic 2.

Mtter$

qdd IWO] and/or

tlCiO~ and re-svaporate. swirling

and

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

concentrated H~SO*, melt

and

heat

to boiling

or until

the

pyrosulfate

is dissolved.

00 not volatilize
4.

tsuch HzSO~. KICrzOT,, and mix to ensure Do not

dichronate

Cool and add ~10 IDg of solid

cmplete cxidation
and

of

Np.

heat

becBuse
will

1% Mill

be oxidixed
decomposed
%. t).

the

excess

he the]~nlly

. qnd add ~20 IR1 of water; q nd Mash the precipitate;

Cool

to

v40*C

boil

for
the

I minute.
%p and

Cool,
U are

centrifuge,

in the

supemate. !laClz to the to

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

of H2!~Q appear the

?

may have boiling,

to

folloued cool
for

Np. and qdd

8.

Heat %10 q

minutes,

of

reoxidi:e the l~lJ.

for with 1 that

9.

Add ?0 ml of water and c~bine

the

qnd boil

wilwte;
~rom

cool. Step 6.

centrifuge,

supemate

la.

Add 0.S ml of SO%tilOZ to reduce state, and evaporate

to

Np ~:o the quadrivalent

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.

wash, and mount quantita-

TIN) U remains

procedures

fo]: Np are

given cations. for

when

Np is to be separated 2. Details are given

from one or tl~o other reference steel ~wticle disc

in the

depositing fits into into a profor

the precipitate a specially specially cedure alphs uses

on a stainless designed centrifuge counting

that

holhler

andl also

designed

holder,,

An alternative

electrodeposition

of th~! radianuclides

spectrometry.

- 178-

Procedure 16.

The Low-Level Radiochemical Determfnatiom of 237~p In Environmental Samples

R. W. Taylor3S0

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

viduall}-removed from the TIOA. HCl - O.OSM NH*I. and U is removed

is sl:ripped will

Np is removed next last with O.SM HNO~. contain

4M HCI - O.OSM HF,

Uost environmental that the will Fe will extract with

saaples the froa

large

quantities into TIOA, Np, but

of Fe Much of it is

actinide

elesmts

bu stripped

the TIOA al.cng with ether.

easily

removed

from 8 N HCl by isopropyl no Fe, the

ether

If tho sample step may be

i!~ known to contain

otsitted.
Final

extraction

decontamination ?@ is

of Np is accomplished

by solid

ion
by alpha

emhange. pulse
height

final 1y electrodepositet

for rsdioassmy

analysis. saaple contains large quantities of U, some of 2SU

it

When ths may

foliou

the

Np qnd be elactrodepositccl energy

The

on the

plate.

and

a 9TMp .Mve

the same alpha

one another.

(4. 7S MeIV) and cannot

ba converted to

be distiny~c~ by

guished neutron activity time. result

from

Np can

irradiation is wry Tw-how in 8 2pU

for verification low, conversion

of ~ ~. to 2SPtI will

Also,

whwn the Np the counting

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

activity due to Np.

R6!agt?nt% o o
e

HN03, 16M, lM HCl,

H202,

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

just prior to use. end of the day. o

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

volume OF 0.5M HN03. with distilled

HNOs wash, the

g

and wash finally TIOA in

a glass

cleaned
-

flask.

4M HCl

O.OSMHF

o
*

Isopropyl

ether exchange :rlasin, ~!Od to 400 uesh

Dowex 2-X8 anion

PmudLir8 1 Adjust saaples

evaporated the

sample

to be analy:z(sd directly;
MM HCl; and

to 8M HC1. irlsoluble
aqueous

Soluble materials
may be

may be dissolved with

near hot dryness to

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.

Transfer the sample to a 500-md separator

an amount of 10*

funnel,

Add

TIOA equal to one-fourth the amount of

Shake the funnel for one minute. the original sa~le. Allow the phases to separate, and drain the bottom (aqueous) phase.
4.

Retain for other analyses.

20 ml 8M HCI (according to volume c~foriginal

Add

10 to

sample) and shake one minute.

Allow phases to separate,

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

Shake one minute and then allow phases

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

tl~eaqloous which contains

pmtion of 41.! HCl -

a f:rl!sh

O.OSM HF,

the

two :s:rips. 0.!51d HNOs.)

U can now be

stripped 7.

from the TIOA with

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.

(CAUTION: Vent shaking.) ether ether extraction

Drain

separator
aqueous,

funnel and retain. regulations. portion aqueous at

frequentl:r

while

Disca]*d the Repeal: the

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

sample two or threo

181 -

16M HWS

and

30~ HzOZ.

Md 2 or 3 ml 12M HCl and

Repeat

evaporate 9. Dissolve The resin it the sa@e

10 sl

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

must be pro-conditioned through

5 ul of 8M ICl through
with

the Np from the COIUWI

tD

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

to an dectrodeposition 2 ml of distilled Add 2 ml of water until to the cell.

transfer full.

1.SM NH@H to the is

and add distilled

11.

Electrodeposit
three hours.

the sample qt 10 V and about

Maintain the pH

200 mamp for between

of the solution

1 and 3 during electrodeposithn

for
and

electrodeposition. period,
the cell , rinse

A: the end of the with distilled and flame analysis. it. If 2g7Mp In 2% by conThe
water

qdd 1 ml o:? 12M B21H and plate

1 min.
remove the is

~ty

the plate.
plate by

Dry the plate

height

12.

Count
there

q lpha plse
q ml if

no

U present

there

i!; sufficient directly. little

present, present, version

qbsence

radimssay
of U

ccoqlishd carI be q or when there sensitivity

% is

the presence

is wry

increased
of ZIq) to
of % the ~

can be) qchieved irradiation. initial by 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

long enough pulse

to pemit

decay

of induced Correct the

Pt activities
the

and to allow by alpha if

23 Np to decay height

to 2s Pu.

Recount

plate plate, before

analysis.

amount of on the

gepu now present necessary. irradiation

by any originally the activation

present formula.

Calculate from the

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

one gallon of reactor effluent water, and evaporate to

stir, and let stand S min.

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

ml of concentrated HF, stir, and let stand for

S min. 7. 8. 9. Centrifuge and discard the liquid phase.

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.

Discard the aqueous phase. - 184 ..

12. Wash the organic phase with three 20-ml portions lM HCI for
13.

of

5 min each.

Discard

the aqueous

solutions.

8ack-extract the 2S9N with 10 ml of 8M HN03 for 10 min. P Place ,leat

the aqueous
HC104,

14.

in

a SO-ml beaker

containing to dr:yness

3 ml of under a

concentrated lamp.

and evaporate

15.

Cool the boiling.

beaker,

add %5 ml of 8M HN03, and heat

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.

Detennlnation of Np In Urine E. Butler3s J

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

back extracted, plqnchetting

and and

is

determined

by direct

counting

background

solid-state

counters.

A variation mination

of the procedure in biological

provides

for

sequential

deter-

of actinides

and en~ironmental

samples.

Pu, Np, and U are extracted N HC1 containing

Th,

from EN HC1 to TIOA.

Cf, and

The residual extracted from

Am, Cm, Bk,

Es are

i2M HNOS to DDCP [dibutyl

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

Erlenmeyer flask with concentrated HNOI (201 n!l of acid Acid is

the

added to the

urine

in the

polyethylene

bottle

to renwe The is wet

Np, which may be adsorbed sample is evaporated

on the walls to dryness,

of the ilnd the

container. residue

acidified ashed

with HN03 and HzOZ.

Nitrates are metilthesized chlorides to

by evaporation to prevent interference with Pu (liIj removal.

- 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

(For urine samples

10 ml of 8F!HC1,

of 250 ml or lCSS, rinse

and add the rinses to the funnel.)

4.

Drain and store the aqueous [lower) and Cf analysis.

ls)er

for

Pu, Th, #m, Cm,

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

the funnel and shake

to n

vigorously for 10 sec. Drain the Np strip Discard analysis.

7,

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

to dryness. Wet ash with tLYO1and 1[202.

Rinse sides of breaker with 4M IL%03ond evaporate solution to

8.

Add

1 ml 4M lINOIand transfer solution to stainless steel

planchcts and evaporate to dryness under an infrared lamp.

Complete transfer with 3 rinses of 4M I{NOJ.

9.

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.

Detetmlnatlon of ~:pby W. O. Granade 352

Ganma Ray Spectrometry

Intrcdactiun A gama spectromctric

incthod was develoFed that allows for

the rapid determinationof Np in process solLtions containing fission products. The method is unaffectedky highly salted, corrosive,or organic mcdii3. 237Np is dctcrninedby ,iymma

spectrometryusing a thin lithium-driftedgermanium [Ge(Li)]semiconductor detector to resolve the 86.6-keV

237Np gamma ray.

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
,!

is used for the accumulation

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 -

to the 86.6-)ieV 237Xp photopeak. 233Pa is required. solution

a pure

stancard

solution

of

233Pa is purified

by passing

an equilibrium

a of 33Pa-237Npthrotgh diatomaceoLsearth column which

IIIC 233pa is cluted, and

sorbs 233pan is determined emission). counting determine

the :7Np contaminant

level

by alpha Aliquots

counting

( 233Pa does not decay by alpha into a standard gamma

of 213Pa are pipetted A series of counts

geometry. the ratio

of the

233Pa are made to peak to counts the 213Pa peak.

of gamma counts The ratio counts

at the 8tl.6-keV is used to calculate

at the 311.9-keV contribution me

peak.

to the total

detected

at the 86.6-keV

efficiencyof the Gc(Li) detector for 86.G-heV gamma

rays is determinedby calibrationwith known gamma standards between 43.5 and 511.6-kcV.
tkaly~i

Tnc standards

and sample

arc counted in a holder which ensures

a reproduciblegcomet~ at 2 cm. The deadtime correction (always

<20%) was

found to be accurate to <1%. The gain setting of the

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

f the Conqzton background and the 23spa contril,utionrom the 86.6-keV

- 190 -

total photopeak
bmckgromd average of is the

amm.

The contributia be

of

wdcrlying

Co~con

a~sumed to comts

linear

over

lhc peak area.

An

from 4 channels

on each side

of the peak

is used to determine the backgromd correction. For an analysis

above less the than determination 101 of the limit measured (the value), relative the standard peak area deviation is

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

disintegration the net

per minute value of 77Np

counts per

obtaind by dividing
the gray ahmhince

uinute

(photon/disintegration)

efficiency

at B6.6-keV. of *N,p results agreed ~ithin obtainsd 5%. by ga-a spcctromctfi

A coqarison and TTA extraction alpha

ITA. phase ing

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

the aqueous the

phase.

TIM: resulting extracted

gama

shoued

97% of agreement

237Np had been the

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

media with no adverse

A lower

of detection

of 1 x 10 d/m/ml at a confidence level of 9S1 was

of counts
using a diluted standard 237Sp

detemined fmm a series

solution.

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

R. G. Bryan and G. R. Watwbury302 Outline of Method

spectrophotometricall!r

Np is measured complex after

as the

arsenazo

Ill

separation

from Pu and impul-ity

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

O.lM I{Cl. and the

111 complex is formed at a wavelength

of 665

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

acid-2, 7-his of arsenazo

o Ascorbic

(azo-2) -phenylarsonLc 111 in S00 ml of wate:: 5$. Dissolve

Dissolve

acid,

6 gr:~ms of ascorbic

120ml c o Carbon I!Cl,

of 8t4W1.
tatrachloride, (CClk) reaglmt

grade.

12M, reagent

grade.

o
q

Np stock Phosphoric

solution.

Dissolve

higlh purity

Np metal

in

12M HC1.

acid,

(HJPO*) 1S.9}1, rzagent

grade.

grade.

KOH, pellets,

reagent

- 193 -

Reducing

solution,

5% ascorbic Dissolve

acid

and 0.5% Fe(II] acid and

ion in 4M HC1.

2.5 It of ascorbic

1.75 g of Fe(NH2S03)z
q

in 50 ml of 4hl I{Cl. (TIOA in xylene), 5%. xylene.

Tri(iso-octyl)amine-xylenc

Dissolve 31 ml of TIOA in 500 ml of re~gent-grade

q

Tri(iso-octyl)amine-carbontetrachloride (TIOA-CClb), 5%. Dissolve 31 ml of TIOA ir 500 ml of CC14.

Equipment
q q

Extractors Laboratory volumetric

(see

figure

in Reference (beakers, pipet.s,

302). syringes, and

glassware flasks).

Spectrophotometer,
uatched

Beckman model DU or equivalent, cells having l-cm light paths.

with

fused-silica

Pretreatment The sample material chlorofom. is of metal or alloy oil is inspected, and extraneous

remved. For each

Cutting Pu uetal

is remwed by washing with methyl take two accurately

containing on each Np, less sample, reagent

sample,
200

weighed
than on a

portions, each not greater than

60 ~g of solution blank Np. Make duplicate a known

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

and 2.5 ml of water. by adding 1 ml of reduc-

solutions

ing solution 3. Prepare standard

and 4 ml of 4M HC1 to each of two extractors. by adding contains expected an aliquot

an amunt of

known Np solutions Np solution equal that to that

of
Np

approximately

in the

sample

and Dilute

1 ml of reducing the 4. solutions

solution

to each of two extractors. 4M WI. solutions 2 rein, prepared and then

to 5 ml with

Add 5 ml of

TIOA-CCl~ to each of the steps, mix the to separate layer

phases

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

extractor, to separate taining 8.

Wash the acid-al

phases

for
Remove

3 min and allo~

the aqueous

phases
con-

for Pu.

1 min.

phase

the

inside HC1,

of

the

extractor

wit~h 53 ascorbic

mix

the

phases

for

2 min. and allow

Rcmnm

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

and allow phase.

to separlatc

1 min.

Remove the
10.
Add

4 ml of O.lM HC1 to each extractor. Mix the phases 3 tin,

and allow to separate

for

for

1 min.

- 195 -

11.

Remove

the

aqueous

phase

into

a 25-ml volumetric

flask

containing ~ 1~, 13.

0.6 ml of H3POb, 1 ml of 5% ascorbic acid-

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

Add ~.5 ml of 0.23 flask, the and dilute

to 25 ul with fdsk. of the

contents the

of the absorbance
paths (As-Ah) at

14.

Measure

solution
of 66S

in cells nm.

having

l-cm light 15, p

a wavelength (Wk, LIE ofN@

pm = (Ak-Ab) Ab = absorbance Ak = absorbance As = ahsorbancc

(sqle

wt in grama

of blank of known Np solution of unknan saqIlc

Wk = ug of Np in known NF solution Uclative measuring

tested only

standard

deviations

range

between

7.2

and 1.1S in
Of 45 elements but

8.S to 330 ppm of Np in 200 mg samples.

Pd, Th, U, and Zr cause serious

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

some U, and Th Also, analysis. lilPOh HF

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.

Microvolumetrfc with EDTA A. P,

N. P. Smirnov-Averin, Ermoloev,

Complexonetrlc Method for Np

G. and N. N, S. Kovalenko,

Krot:26

Outline
Np(IV]

of Method
is

titrated with a solution of EDTA at pH 1.3 to 2.0

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

0.:1%xylenol orange Centrifuge tubes Micro or semimicroburet

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

per ml, water

6.

bath. solution, dilute towldO ml with water, and add

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

NI[2011IIC1. Ascorbic decomposition products

with the titration. (Mn2+, Ni2, titration, are

2.

Doubly charged readily hydrolyzable ions U3Z2+), which used as carriers. with amounts an error of alkali, do not interfere with the

3.

Np can bc determined presence rare

of

of tO.03 alkaline
Cd2+,

mg in the earth, and Cr3+ (up

are

large

earths

elements, by strong

Mn2*, Zn2+, base precipitation Cr2072-, interfere they

Pb2+, which include

to 20 mg), Ni2+, separated (3{@0-, to Pu(III) SOk2-,

C02+ and lM322+. C@42-,

Anions

NO]-, Pu is 2rh+, with reduced fib+, Np(lV).

and EMA-. up to 2 mg. arc cotitrated

and does not

and Fe3+ interfere

because

- 198 -

Procedure 22.

Photanetrlc Determination of Canplex

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,

Np(V) forms (pH >8) . molar

in alkaline is

solutions 1:1; the 5010 t210 for Np.

The ratio

to Hz02 in the complex at

complex

absorptivities

430 and 370 nm are is highly selective

and 7950 t350,

respectively.

The method

t?eagenta and Eq? - :ent .

q

NaOtl,

Cl)

grade

11202, CP grade Spectrophotometer

and cells.

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

to Np(V) by adding ~atcr bath

ml of 30% 11Z02, and keep

in a boiling 3. 4. Cool the Neutralize of 4N NaOH. 5. 6. Dilute Measure realtive 7, Detenninc

10 min. ml of 0..5}1 IIzOZ.

nd

solution,

and add 0.1

to pl{ 1 to 3 with

NaOi,

add an extra

1 ml

to exactly the

4 ml with

water,

and mix thoroughly.

iit

absorbance

in a 1 cm cell

430 or 370 nm

to a blank. the Np content using a calibration curve,

- 199 -

Note8

1.

Np(V),

but not Np(IV)

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

In O.lM NaOl{ solution, two hours. not

Increasing change the the time

HZOZ concentratio~ At higher absorbance

to >? x 10-3M does H202 concentrations,

increases.

?l~sorbance. constant

4.

When the solution contains U, 7 to 10 mg of

(lUi~)zHPOk of the phosphate

is added before reduce s. Fluoride complex. absorbance reduces Tartrate,

the

NaOH.

Greatm

amounts

of the the

Np(V)

complex.

absorbance carbonate,

of the

Np(V) peroxide ions to O.lM amounts Fe(OH).q precipitates of Pu do not

and sulfate

have no effect. and is removed of Fe do not interfere.

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

Np mmpounds solution dilute

and

is heated

is dissolved

HN09, and Np oxidation acid.

is made with

sulfamic

The hexanitrato base resin. anion resin;

cornplcx of Np(IV) impurities and the are

is

sorbed not

on strong by the

c~tionic rspeated,

sorbed

The cycle at 4110C. impurities

effluents in

are evaporated
6M

and baked cationic

The residue are determned

is dissolved by emission

HC1, and the

spectroscopy. Reagente
q q q q q q q

and Equipment HNOg

Double-distilled Hydrazine Sulfamic Cobalt Small (N2H~] acid solution glass

Dowex 1-4 100 mesh

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

ml of llM aqueous 30 min for

- 201

3.

Add one-half

ml of

3M sulfamic solution. solution

acid

,and 2.5 ml of 16M

HN03, and mix the 4. Pass the adjusted resin

thrwgh

a 3 ml bed of ILd-mesh and collect the

Dowex l-X4 effluent. 5. Hash the effluent 6.

Elute

at <3 ml/(min-cm2j,

resin with

with that the

w1O ml of from Step

N llN03, and combine 2. 0.35M N3,

the

Np from

resin

with

and condition

the 7.

coluam with

8M HNOs for

re~se. effluents to dryness, Np was

Evaporate and repeat rermved

the sorption Steps with the two cycles sorption

and wasl 6. of anim and wasl

2 through

(99.96% of the
exchange].

8.

Evaporate to dryness

effluents

from Step

and bake at 400C t~ expel hydrazine. the residue

in 1 ml of

9.

Dissolve to dryness.

aqua regia,

and evaporate

10.

Dissolved

the

last

residue serves

in as

1 ml of 6M HCI cont~ining m internal solution standard. to dryness on

100 ug of Co, which 11. Evaporate two hundred

Bg of ths

top of a l/4-inch-diameter 12. Excite large the sample region. filter is for

flat-top

electrode. using a

30 sec b? a 10-amp dc arc in width is

Littrow

spectrograph The slit

the 2500 to 3S00 A 10 Urn, and a twoin the slit.

wavelength
step neutral

100%/3S% i; used. large

inserted

SA-2 emulsion Because a reagent distilled of the

relatively be carried

volume of reagents the procedure.

used, Doubly

blank

should

throu,~h

tlNOJ was used.

202

Recovery 65%.

was 88 to 106% for

all

elements

except Ni which was

The coefficient the several 17%. elements

of variation varies

for a single

determination an average of

of

from 9 to 24% with by large iupuritics

of

The precision remval

is affected of cationic

volumes

of reagents resin

and

inco~lete

from the
Fe, Cr,

column.

The method was applied Al, andMg.

to determination

Ni, Mn, Cu,

- 203 -

Procedure 24.

Photometric Determination of Np as the Xylenol Orange Complex

N.
and

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

complex with coefficient than

an absorbance of 5.5 x 10b. thorin

but only

maximum at 550

nm and molar extinction

is three times

Xylenol
one-half

orange
as

more sensitive

sensitive as Arsenazo advantage of xylenol

111 as a reagent orange coupared

for Np[lV). to thorin of U.

The greatest 111

and Arsena:o

is the relatively

minor

interference

Ff&aLJect8 Umi Qaipme):t

tlc 1
30. ~al

Test

solution,

10 q

M112 and 50 mg of XIIZOIIIIC1pcr ml

100 ug Sll@HllCl per ul in 7S1IK1 31 xm~ai

0.0S3

xylcnol

orange

pll 3wtcr Spcctrophoto=tcr Centrifuge

tdms

1.

M tube, @

solution

containing to

S to

20 us of then

Sp to a centrifuge

and dilute

S to 8 ql;

mdd S0% S3Wuncil

>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

the precipitate. ml. boiling

Discard

the

liquid;

then dissolve ing 4.

the precipitate

in 2 ml cf 7M HC1 contain-

100 mg NHzOtltlCl per solution to almst

Np[IV).

Heat the
25

on a water

bath

for

min to obtain

5.

Dilute

to %15 ml with water, add exactl,y

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

and measure Instrument

FEK-M

fitted

with

green

filter

and using

cells

sith

a path

of 5 cm at 550 nm.

The reference

solution is the sam Sp solution. ;1012?8 1. the SF concentration

cali~ration

plland reagtnt coqositictn as the

is detcrminrd

from a standard

cume.

* -.

The

determination

wq~ircs -3

hours,

and the error

usually

{s <slug. 3.

~p

c=

be detcmined

by the abovr

method

in IKI,

IMI,

llCZlllOIo and NzSOb solutions

containing other anions that

an9J also

I,a solutions
by the strong

arm remowd and phosphate

base

precipitation:

flmride

interfere.

-ms-

Procedure

25.

Analysis

for

Np by Controlled Potential Coulanetry

R. W. Stro.matt

Intrv&ctwn
Controlled little as 2 ug potential coulmetry is useful for detecting as

of Np, and general Ce(IV),

reduced

7 vg can

be dettnnined

with

6% standard

deviation.

The

procedure then
to

is to first

oxidize

all

the are the

Np

to Np[VI) with electrolytically

is coulo-trically

the Np(VI)
Np(V)

and excess

Ce(IV) Finally the

and Ce(l II). to determine

Np(V)

oxidized

to Np(VI)

concentration

of Np. RmgeRta
q q q q

and ~uipment

lM H2S04 Mercury Mercuric

Pure

metal sulfate gas solution coulo~ter electrode Pt wirt Pt gauze, and saturated isolated calomel (working electrode reference) potential cell

heli=

Q
q q

Sodium silicate Controlled Titration

Plvra2df4n2

1.

Add the and adjust to %lN. between Np(V/VI)

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

(The hydrogen 0.4

to 2N but

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

Ce(IV)]. 4. Apply the potential to reduce Ce[IV) constant.

5. to

the until

\p(v1)

and

cxccss

Np(V) and Cc(Ill)

chc current

bccomcs

Apply the potential The oxidation obtained. current,

zero

to oxidize until readings the

the Np(V) to Np(VI). a constant of the current curve is intcgrat~d :urrent

to

is continued Make several

and extrapolate

integrated

time. a blank and after solution titrations containing at the the same amount of perform reduction as used

6.

Prepare Ce(IV), for

S min of de-aeration

and oxidation

same potentials

the Np titration.
the

After constant current is rcachcd integrate current several times

for oxidation, read and extrapolate

7.

to zero

time.

Subtract the zero-time integrated current of the hliinti

from of Np that for the Np titration,

ar.d calculztc calibration.

de-mration and

tlm mount
(lor
from

based

on the the

instrument
in into the

Illg!lcst migration

accuracy, in the cell

Np lost
taken

are

account.)

Noh?a 1. The ,Np(V]/[YI] reversibly

reproducible potentials of

couple

can be titr;lted arc obtmincd with

quantitatit-cly
more

and

in 10101, IIC106, and 112!;Ob; hcnicrcrp

results the

112SO~.

Also, the COIIIIICS arc

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,

and Pu(IV) is not oxidized

significantly in H2SOk. 3. Coulornetric titrations in solutions containing organic

contaminants are often slow and yield low values. 4. The concentration states of Np in the the different oxidation
cell. The

can be made using

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

interference reduction is to Np(V).

by coulometric coulcmetrically, two titrations

and the the Np(V) is detercalculated of Np(V) is

difference between present. as previously Np(VI) and the

The total discussed, between total

Np concentration and Np(lV) the concentrations

from the difference plus

Np. method for Np

s.

Propst 31 has utilizing

reported

a coulometric

a conducting

glass ele:trode in a thin-layer

electrochemical CC1l. Organic conta.mirlants interfered and were remved

by a bisulfate

fusion

procedure.

- 208

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- 217 -

1!s0.
1!51
q

E.

Shepard

and U.

U. Meinke,

l#AEC

@qIIort

AECU-W9

(MSS&

S. 60 Wrray,

USAEC Report
tbrset

*-S~6
c, Id.

( i968).
~. Ckw. &w@. i?wip

lsz.

E. U. bkes qnd g. S. f-wwbp. 3, 333 (1964).

154. 0.,C. f%rricos

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R. W. Perkins,

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A.

T?waassea,
W-SOSl I

KR-$S
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(196SjI.

(1964].

USAEC Report

1S6.
1s7.

U. Lindner,
II. P. NoIco*,

lEiAEC Report

W&L- lJ~SB
0$ -$86

USAEC Report

[I$MJ).

lS8a. J59.

J.
8.

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#.

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lk?k~.

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Acids, Pqter

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K.

u. Isroun, - Maeck. Cbl.

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-- ....-.>
M. E.

-.

..-.

Y (lYbUJ

.. ...
E.

W. J.

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R.

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ENI)

DATE FI LIMIED 2 / .~m~, .-... ~pv~s -9,d -